CN101747288B - Monocyclic benzoxazine intermediate with low viscosity and a plurality of functional groups and synthesis method thereof - Google Patents
Monocyclic benzoxazine intermediate with low viscosity and a plurality of functional groups and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a monocyclic benzoxazine intermediate with low viscosity and a plurality of functional groups, a preparation method thereof and application thereof in the preparation of high-temperature resistant resin. The process method is simple, practicable, and suitable for industrial production in most of factories; a cross-linked polymer prepared by the benzoxazine intermediate has very high vitrification conversion temperature (Tg is larger than 250 DEG C), is available to high-temperature resistant materials used in the temperature more than 250 DEG C, and has higher carbon residue rate (800 DEG C, N2, PNB-ala: 57%; 800 DEG C, N2, FB-ala: 61%) and a certain application prospect in terms of the preparation of carbon materials and ablation resistant materials.
Description
Technical field
The present invention relates to benzoxazine midbody and compound method thereof; But relate in particular to a kind of novel benzoxazine midbody---low viscous, contain a plurality of reactive groups, monocycle benzoxazine midbody and the ring-opening polymerization of compound method and said midbody and the preparation of polymkeric substance thereof.Belong to novel monocycle benzoxazine intermediate preparation and fire resistant resin preparing technical field.
Background technology
The monocycle benzoxazine midbody of no sense substituent can not carry out crosslinking curing, and polymerization can only obtain oligopolymer, and its mechanical property, thermal property are not high, thereby does not receive enough attention, just often as the reactive thinner in the Polybenzoxazine system.The dicyclo benzoxazine midbody that the nineties occurs has changed this situation, because can crosslinkedly obtain superpolymer, thereby causes scientist's broad research interest.Yet; Monocycle benzoxazine midbody have dicyclo benzoxazine midbodys such as melt temperature is low, melt viscosity is low incomparable advantage; Just in time can satisfy liquid resin processing (transfer mould for example; RTM) to the low viscous requirement of matrix resin (being lower than 200mPas), therefore developing monocycle benzoxazine midbody still has crucial meaning.
Noticeable in recent years development is on monocycle benzoxazine midbody, to introduce the polymerizable functionalities group.The Ishida seminar of U.S. CaseWestern Reserve University is at " Molecular characterization of thepolymerization of acetylene-functional benzoxazine resins " [Polymer; 40,1815-1822] the monocycle benzoxazine midbody and the polymkeric substance thereof of having reported for work and having contained ethynyl in the article; At " Thermal study on thecopolymers of phthalonitrile and phenylnitrile-functional benzoxazines " [J.Appl.Polym.Sci.; 73,2937-2949] the monocycle benzoxazine midbody of the cyano-containing of having reported for work in the article; At " Synthesisand characterization of maleimide and norbornene functionalized benzoxazines " [Polymer; 46,5588-5595] the monocycle benzoxazine midbody of having reported for work and having contained maleimide in the literary composition; In patent PCT2000:742157 " Development of low viscosity benzoxazine resins ", reported contain simple function group, LV monocycle benzoxazine midbody; It is low that this midbody has viscosity, is beneficial to the advantage of forming process.The polymkeric substance that obtains behind these midbody crosslinking curings of Ishida seminar report all shows higher thermal property.Berger has reported cyano-containing functional group's monocycle benzoxazine midbody in patent US2005:497486 " Preparation of benzoxazine derivatives and pharmaceutical use ".The Takeichi seminar of Japan Toyohashi University of Technology is at " Novel benzoxazine monomers containing p-phenyl propargyl ether:polymerization of monomers and properties of polybenzoxazines " [Macromolecules; 34,7257-7263] the monocycle benzoxazine midbody of having reported for work and having contained propargyl in the article; Subsequently, in patent JP2002:654422 " Propargyl ether group-containing 1,3-benzoxazine monomer and itspolymers ", reported the monocycle benzoxazine midbody crosslinking curing polymkeric substance extremely that contains propargyl; At " Synthesis and characterization of novel benzoxazine monomers containing allyl groups andtheir high performance thermosets " [Macromolecules; 36,6010-6017] having reported for work in the article contains allylic monocycle benzoxazine midbody; At " Preparation polymerization ofmaleimidobenzoxazine monomers as a novel class of thermosetting resins " [J.Polym.Sci.Part A:Polym.Chem.2006 ] in also reported the monocycle benzoxazine midbody that contains maleimide, the Polybenzoxazine that is obtained by these midbody crosslinking curings of Takeichi seminar synthetic also all shows higher thermal property.Dingsheng Yu has reported in patent CN2004:1009833 " Preparation of N-allyl-containingbenzoxazine intermediate " and has contained allylic monocycle benzoxazine midbody; Zaijun Lu has reported the monocycle benzoxazine midbody polymkeric substance extremely that contains the alkynes propoxy-at patent CN2008:965144 " Method for preparing benzoxazine intermediate containing propargylether and benzoxazine esin ".
In addition; Aspect multiple functional radical benzoxazine intermediate and polymer thereof; The LuminitaCianga seminar of Turkey IstanbulTechnicalUniversity is in " SynthesisandCharacterizationofMaleimide(Co) polymerswithPendantBenzoxazineGroupsbyPhotoinducedRadica lPolymerizationandTheirThermalCuring " [J.Polym.Sci.PartA:PolymerChemistryDOI:10.1002/pola.22034] article; Reported that its glass transition temperature of polymer has reached 200 ℃ to be that raw material has made monocycle benzoxazine intermediate and the polymer thereof that contains a plurality of functional groups to maleimide phenol with to cyano-aniline.The GangYang seminar of China SichuanUniversity is at " Synthesisofabenzoxazinemonomercontainingmaleimideandally loxygroups " [ChineseChemicalLetters2007; 18; 973-976] reported for work in the literary composition at benzoxazine 6 contain the maleimide substituting group; Simultaneously contain the substituent monocycle benzoxazine of allyloxy intermediate, reported again that in patent CN2008:964979 " Processforpreparationofbenzoxazinecompoundcontainingmale imideandallyloxygroups " this contains the substituent monocycle benzoxazine of polyfunctional group intermediate at 3.This shows, contain multi-functional monocycle benzoxazine midbody and polymkeric substance thereof and will receive increasing concern.
People such as were at " Studies on the thermal polymerization of substitutedbenzoxazine monomers:electronic effects " [J.Polym.Sci.Part A:Polym.Chem.2008) in 2008] in the literary composition through the influence of different substituents divided ring polymerization temperature in the research benzoxazine intermediate structure, find in the amido contraposition of phenolic hydroxyl group contraposition or aniline, to introduce and inhale the ring-opening polymerization temperature that electrical group can significantly reduce the benzoxazine midbody.
Based on researching and analysing of above content; For as far as possible when keeping monocycle benzoxazine midbody LV advantages characteristic; Enable crosslinking curing; Obtain the high-molecular weight cross-linked polymer; Most effectual way is exactly to utilize the flexible molecular designing property of benzoxazine; Introduce functional groups such as polymerizable, electrophilic property therebetween in the body structure, thereby realization reduces the temperature of ring-opening polymerization when obtaining cross-linked polymer, obtain excellent mechanical property, resistance toheat; And can implement the monocycle benzoxazine is adopted liquid resin molding complete processing (for example RTM), reduce manufacturing cost greatly.
Summary of the invention
Requirement based on prior art; But the purpose of this invention is to provide a kind of novel benzoxazine midbody---low viscous, contain a plurality of reactive groups, monocycle benzoxazine midbody and the ring-opening polymerization of compound method and said midbody and the preparation of polymkeric substance thereof.
The present invention is a reaction raw materials with phenolic cpd, formaldehyde and aminated compounds, and controlling its reaction ratio is 1: 2: 1, and is synthetic and disclose six kinds of Lies, contain the novel monocycle benzoxazine midbody of a plurality of functional groups, is respectively:
Cyano-containing and allylic polyfunctional group benzoxazine monomer is characterized in that structural formula is:
Contain aldehyde radical and allylic polyfunctional group benzoxazine monomer, it is characterized in that structural formula is:
The polyfunctional group benzoxazine monomer of cyano-containing and propargyl is characterized in that, structural formula is:
Contain the polyfunctional group benzoxazine monomer of aldehyde radical and propargyl, it is characterized in that, structural formula is:
The polyfunctional group benzoxazine monomer of cyano-containing and ethynyl is characterized in that, structural formula is:
Contain the polyfunctional group benzoxazine monomer of aldehyde radical and ethynyl, it is characterized in that, structural formula is:
The above-mentioned method that contains multiple functional radical benzoxazine intermediate preparation is:
(1) under the ice bath, in the solvent of 0-80 weight part, add the aldehyde of 0-30 weight part and the amine of 0-50 weight part, and the pH of accent reaction system solution is 5-11; The phenol that adds the 0-40 weight part then; Mixing solutions reacts 4-6h down in reflux temperature, obtains yellow benzoxazine midbody solution;
(2) gained benzoxazine midbody solution is used alkali liquid washing, and use SX, combining extraction liquid, the pressure reducing and steaming solvent, recrystallization must contain multiple functional radical monocycle benzoxazine monomer after the vacuum-drying;
Wherein: above-mentioned solvent is dioxane, THF, ethanol, methyl alcohol, chloroform, toluene or YLENE; Above-mentioned aldehyde is that volume ratio is 37% formalin, trioxymethylene or Paraformaldehyde 96; Above-mentioned amine is allyl amine, to amine phenyl propargyl ether or to ethynyl aniline; Above-mentioned phenol is 4-hydroxybenzonitrile, p-methyl phenol, PARA HYDROXY BENZALDEHYDE or PHB; The employed alkali of above-mentioned reaction system pH regulator is triethylamine, N; N-dimethyl benzylamine, N; Accelerine, N, N-dimethylethanolamine, ammoniacal liquor, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, sodium bicarbonate aqueous solution or potassium bicarbonate aqueous solution; Above-mentioned benzoxazine midbody solution washing soda liquid is aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution or triethylamine; Above-mentioned extraction liquid is methylene dichloride or chloroform; The used solvent of above-mentioned recrystallization is anhydrous diethyl ether, ethanol, methyl alcohol or toluene.
In the above-mentioned method that contains multiple functional radical benzoxazine intermediate preparation, phenolic cpd, formaldehyde and aminated compounds reaction ratio are 1: 2: 1, and its building-up reactions equation is following:
Utilize the viscosity evaluation of the benzoxazine midbody of the inventive method acquisition
Viscosity is the important factor that influences benzoxazine midbody processing characteristics, and the viscosity test result of wherein typical example NB-ala and FB-ala sees table 1, table 2, table 3 and table 4.
The viscosity of table 1 benzoxazine midbody NB-ala under differing temps:
90 ℃ of benzoxazine midbodys of table 2 constant temperature NB-ala is in the viscosity of different time
The viscosity of table 3 benzoxazine midbody FB-ala under differing temps
50 ℃ of benzoxazine midbodys of table 4 constant temperature FB-ala is in the viscosity of different time
Can know by table 1 data, benzoxazine midbody NB-ala viscosity in 90 ℃ of-180 ℃ of TRs lower (＜200mPas), be fit to the requirement of RTM moulding process, so its processing characteristics is good.
Can know benzoxazine midbody NB-ala under 90 ℃ of steady temperatures by table 2 data, its viscosity is less over time, and its viscosity is merely 185mPas behind the 300min; Still less than 200mPas, can satisfy liquid resin processing to the low viscous requirement of matrix resin.
Can know by table 3 data, benzoxazine midbody FB-ala in 50 ℃ of-140 ℃ of TRs, that the increase of its viscosity with temperature changes is little (＜200mPas), be fit to the requirement of RTM moulding process, therefore have better machining property.
Can know benzoxazine midbody FB-ala under 50 ℃ of steady temperatures by table 4 data, its viscosity is less over time, and its viscosity is merely 174mPas behind the 300min; Still less than 200mPas, also can satisfy liquid resin processing to the low viscous requirement of matrix resin.
Utilize the solidification process of the benzoxazine midbody of the inventive method acquisition
For the solidify reaction process of benzoxazine midbody, the contriver uses intensification DSC (DSC) to research and analyse.The initial polymerization temperature of benzoxazine midbody NB-ala is 140 ℃; Maximum ring-opening polymerization exothermic peak temperature is 178 ℃; So its solidification value all decreases than the homologue that does not contain the functional group and only contain a functional group, the reduction value is 0-50 ℃, has reduced the requirement to contour machining procedure.The starting polymerization temperature of benzoxazine midbody FB-ala is 149 ℃, and maximum ring-opening polymerization exothermic peak temperature is 174 ℃, and its solidification value has reduced by 30 ℃ than the homologue that only contains a functional group, helps the forming process of polymkeric substance, has reduced processing requirement.
Application (the synthetic) of Polybenzoxazine of multiple functional radical benzoxazine midbody in the preparation fire resistant resin that contain according to the invention; It is characterized in that: will contain multiple functional radical benzoxazine midbody and pour in the setting mould; Temperature-gradient method in Constant Temp. Oven, curing obtains benzoxazine crosslinking curing resin; Wherein solidifying temperature-rise period is: in 100-260 ℃ of scope, and time variable control gradient increased temperature, the every rising 0-30 of temperature ℃, isothermal curing 2-3h.
Above-mentioned containing in the application of multiple functional radical benzoxazine midbody in the preparation fire resistant resin: preparation resin 3-allyl group-6-cyanic acid-3,4-dihydro-2H-1, the curing temperature-rise period of 3-benzoxazine polymkeric substance is preferably :140 ℃/2h; 160 ℃/2h; 180 ℃/2h; 200 ℃/2h; 230 ℃/2h; 260 ℃/6h..
Above-mentioned containing in the application of multiple functional radical benzoxazine midbody in the preparation fire resistant resin: preparation resin 3-allyl group-6-aldehyde radical-3,4-dihydro-2H-1, the curing temperature-rise period of 3-benzoxazine polymkeric substance is preferably :150 ℃/2h; 170 ℃/2h; 190 ℃/2h; 220 ℃/2h.
Utilize the thermal property of the benzoxazine midbody synthetic Polybenzoxazine of the inventive method acquisition
The thermal property of Polybenzoxazine is mainly analyzed through differential scanning calorimetric analysis (DSC), dynamic mechanical analysis (DMA) and thermogravimetic analysis (TGA) (TGA), and test gained result sees table 5.
The thermal property of table 5 Polybenzoxazine
a：Measurd?by?DSC。
b：Measurd?by?DMA。
Can find out by data in the table; Polybenzoxazine PNB-ala and PFB-ala have high glass transition; Tg is respectively 297 ℃ and 266 ℃; Homologue than not containing functional group is significantly improved; Cyanic acid and allyl group or aldehyde radical and allyl group are introduced in explanation in the benzoxazine intermediate structure; Can effectively improve the cross-linking density of gained Polybenzoxazine, thereby improve its second-order transition temperature.
5% and the 10% thermal weight loss temperature of Polybenzoxazine PNB-ala is respectively up to 340 ℃ with 370 ℃; This mainly is because allylic crosslinking reaction has avoided the mannich bridge to decompose at the amido that reaction starting stage premature failure causes, so its 5% and 10% thermal weight loss temperature improves greatly.Being heated to 800 ℃ of its carbon residue rates is 57%, improves greatly than its homologue, and this is likely because the annulation of cyanic acid improves the cross-linking density of polymkeric substance, and nitrogen element content increases in the polymkeric substance simultaneously, and then the carbon residue rate is increased.
5% and the 10% thermal weight loss temperature of Polybenzoxazine PFB-ala is respectively up to 345 ℃ with 393 ℃; Same this mainly is because allylic crosslinking reaction has avoided the mannich bridge to decompose at the amido that reaction starting stage premature failure causes; Next be because; Aldehyde radical in the high-polymer molecular system can be that the amino derivative that discharges in the short chain process reacts rapidly with the early molecule splitting of chain; Thereby being healed again, chemical bond is new organism; And then stoped micromolecular emitting; Cause its 5% and 10% thermal weight loss temperature, and the carbon residue rate when being heated to 800 ℃ improves.
The present invention has the following advantages:
1. contain multi-functional novel benzoxazine midbody and can carry out ring-opening polymerization and crosslinking reaction acquisition cross-linked polymer.But six kinds of novel benzoxazine midbodys of the present invention's preparation have been introduced reactive functionality respectively: allyl group, propargyl, alkynyl, cyanic acid, aldehyde radical can obtain having cancellated Polybenzoxazine after ring-opening polymerization and the crosslinking reaction.
2, the viscosity of novel benzoxazine midbody is low.The viscosity of monocycle benzoxazine midbody NB-ala and FB-ala is very low and very little with the temperature and time variation, and wherein the initial viscosity of midbody NB-ala in the time of 90 ℃ is 124mPas, and through behind the 300min, viscosity is merely 185mPas; The initial viscosity of FB-ala in the time of 50 ℃ is 142mPas, and through behind the 300min, viscosity is merely 174mPas.So these two kinds of midbodys all can be used as the RTM vacuum moulding and use resin matrix.
3. the solidification value of novel benzoxazine midbody is low.Two kinds of novel benzoxazine midbodys of the present invention's preparation have been introduced electrophilic aldehyde radical and cyanic acid respectively; The ring-opening polymerization temperature of midbody is further reduced than the homologue that does not contain aldehyde radical or cyanic acid; The starting polymerization temperature of midbody NB-ala and FB-ala is respectively 140 ℃ and 149 ℃, more helps the machine-shaping of Polybenzoxazine resin.
4, gained Polybenzoxazine PNB-ala and PFB-ala have excellent heat resisting.The T of PNB-ala wherein < > g <> Be 297 ℃, 5%, 10% thermal weight loss temperature respectively up to 340 ℃, 370 ℃; The Tg of PFB-ala is 266 ℃, 5%, 10% thermal weight loss temperature respectively up to 345 ℃, 393 ℃.So two kinds of polymkeric substance all can be used for making the high temperature material that uses more than 200 ℃.
5. gained Polybenzoxazine PNB-ala and PFB-ala have higher carbon yield.At N < > 2 <> Be heated to 800 ℃ in the atmosphere, carbon yield is respectively 57% and 61%.Has certain application prospect aspect the preparation ablation resistant material.
6, raw material used in the present invention: allyl amine, to the amido propargyl ether, to ethynyl aniline, formalin, to cyanic acid phenol and PARA HYDROXY BENZALDEHYDE etc., the overwhelming majority is a commerical prod, cost is lower.
7. the curing process of the compound method of the benzoxazine midbody of the present invention's enforcement and Polybenzoxazine is simple and easy to do, is fit to most of factories and carries out industrial production.
Description of drawings
Fig. 1 is the 1H NMR spectrogram of NB-ala and FB-ala;
Fig. 2 is the FTIR spectrogram of NB-ala and FB-ala;
Fig. 3 is the DSC spectrogram of midbody NB-ala;
Fig. 4 is the DSC spectrogram of midbody FB-ala;
When Fig. 5 is 90 ℃, viscosity-time plot of midbody NB-ala;
When Fig. 6 is 50 ℃, viscosity-time plot of midbody FB-ala;
Fig. 7 is midbody NB-ala temperature-viscosity curve figure;
Fig. 8 is midbody FB-ala temperature-viscosity curve figure;
Fig. 9 is the TGA spectrogram of Polybenzoxazine PNB-ala;
Figure 10 is the TGA spectrogram of Polybenzoxazine PFB-ala;
Figure 11 is the DMA spectrogram of Polybenzoxazine PNB-ala and PFB-ala.
Embodiment
Through specific examples the present invention is specifically described below, it is important to point out: this instance is only applicable to further specify of the present invention, but does not limit to its scope.This area professional is conspicuous in the various improvement of having done without prejudice to essence of the present invention after reading this patent, all belongs to requirement protection domain of the present invention.
In the 100mL there-necked flask, add 10.0g 4-hydroxybenzonitrile, 6.5mL allyl amine, 1ml triethylamine, the anhydrous dioxane of 40mL successively, stir misciblely, and lower the temperature with ice-water bath.Slowly add the 5g Paraformaldehyde 96, be warming up to 90 ℃ gradually, and under this temperature, react 4h, obtain yellow benzoxazine midbody solution.With the reaction mixture rotary evaporation, the gained crude product after with the anhydrous diethyl ether recrystallization light yellow crystal, productive rate 67%.
Ultimate analysis :C < > 12 <> H < > 12 <> N < > 2 <> O, theoretical value %:C, 72.00%; H, 6.00%; N, 14.00%. analytical value :0,71.43%; H, 5.92%; N, 13.77%. < > 1 <> H NMR(CDCl < > 3 <> , 300MHz, δ):3.34ppm(d, N-CH < > 2 <>-C), 3.99ppm(s, Ar-CH < > 2 <>-N), 4.94ppm(s, O-CH < > 2 <>-N), 5.19ppm(m ,=CH < > 2 <> ), 5.86ppm(m ,-CH=), 6.81-7.42ppm(Ar-H).FTIR(KBr)v:1028cm < >-1 <> The (C-O-C symmetry is flexible), 1237cm < >-1 <> The (C-O-C asymmetric stretch), 1496cm-1(trisubstituted benzene ring), 30cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 2217cm < >-1 <> (C ≡ N is flexible), 1642cm < >-1 <> (C=C is flexible), 3078cm < >-1 <> (=C-H is flexible).
In the 100mL there-necked flask, add 10.2g PARA HYDROXY BENZALDEHYDE, 6.5mL allyl amine, 1ml triethylamine, the anhydrous dioxane of 40mL successively, stir misciblely, and lower the temperature with ice-water bath.Slowly add the 50g Paraformaldehyde 96, be warming up to 90 ℃ gradually, and under this temperature, react 4h, obtain yellow benzoxazine midbody solution.With the reaction mixture rotary evaporation, the gained crude product is dissolved in the 30mL methylene dichloride, uses the 1N NaOH aqueous solution and deionized water wash for several times respectively, standing demix, and after getting methylene dichloride and concentrating mutually, column chromatography gets light yellow transparent liquid, productive rate 72%.
Ultimate analysis :C < > 12 <> H < > 13 <> NO < > 2 <> , theoretical value %:C, 70.94%; H, 6.40%; N, 6.90%. analytical value :C, 70.31%; H, 6.92%; N, 6.73%.
1H?NMR(CDCl
3，300MHz，δ)：3.36ppm(d，N-CH
2-C)，4.02ppm(s，Ar-CH
2-N)，4.93ppm(s，O-CH2-N)，5.18ppm(m，＝CH
2)，5.84ppm(m，-CH＝)，6.81-7.69ppm(Ar-H)，9.79ppm(-CHO)。FTIR(KBr)v:1025cm < >-1 <> The (C-O-C symmetry is flexible), 1237cm < >-1 <> The (C-O-C asymmetric stretch), 1495cm < >-1 <> (trisubstituted benzene ring), 22cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 1690cm < >-1 <> The (C=O stretching vibration), 2829cm < >-1 <> The (O=C-H)1644cm that stretches < >-1 <> (C=C is flexible), 3078cm < >-1 <> (=C-H is flexible).
Ultimate analysis :C < > 12 <> H < > 12 <> N < > 2 <> O, theoretical value %:C, 72.00%; H, 6.00%; N, 14.00%. analytical value :C, 71.43%; H, 5.92%; N, 13.77%. < > 1 <> H NMR(CDCl < > 3 <> , 300MHz, δ):3.34ppm(d, N-CH < > 2 <>-C), 3.99ppm(s, Ar-CH < > 2 <>-N), 4.94ppm(s, O-CH2-N), 5.19ppm(m ,=CH < > 2 <> ), 5.86ppm(m ,-CH=), 6.81-7.42ppm(Ar-H).FTIR(KBr)v:1028cm < >-1 <> The (C-O-C symmetry is flexible), 1237cm < >-1 <> The (C-O-C asymmetric stretch), 1496cm < >-1 <> (trisubstituted benzene ring), 30cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 2217cm < >-1 <> (C ≡ N is flexible), 1642cm < >-1 <> (C=C is flexible), 3078cm < >-1 <> (=C-H is flexible).
Embodiment 4., 3-allyl group-6-aldehyde radical-3,4-dihydro-2H-1,3-benzoxazine (FB-ala) synthetic
In the 500mL there-necked flask, add 61g PARA HYDROXY BENZALDEHYDE, 37.5mL allyl amine, 5ml triethylamine, 200mL absolute ethyl alcohol successively, stir misciblely, and lower the temperature with ice-water bath.Slowly add the 30g Paraformaldehyde 96, be warming up to backflow gradually, and react 4h down, obtain yellow benzoxazine midbody solution in reflux temperature.With the reaction mixture rotary evaporation, the gained crude product is dissolved in the 200mL methylene dichloride, uses the 1N NaOH aqueous solution and deionized water wash for several times respectively, and standing demix is got and got light yellow transparent liquid, productive rate 76% after methylene dichloride concentrates mutually.
Ultimate analysis :C < > 12 <> H < > 13 <> NO < > 2 <> , theoretical value %:C, 70.94%; H, 6.40%; N, 6.90%. analytical value :C, 70.31%; H, 6.92%; N, 6.73%.
1H?NMR(CDCl
3，300MHz，δ)：3.36ppm(d，N-CH
2-C)，4.02ppm(s，Ar-CH
2-N)，4.93ppm(s，O-CH2-N)，5.18ppm(m，＝CH
2)，5.84ppm(m，-CH＝)，6.81-7.69ppm(Ar-H)，9.79ppm(-CHO)。FTIR(KBr)v:1025cm < >-1 <> The (C-O-C symmetry is flexible), 1237cm < >-1 <> The (C-O-C asymmetric stretch), 1495cm < >-1 <> (trisubstituted benzene ring), 22cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 1690cm < >-1 <> The (C=O stretching vibration), 2829cm < >-1 <> The (O=C-H)1644cm that stretches < >-1 <> (C=C is flexible), 3078cm < >-1 <> (=C-H is flexible).
In the 50ml round-bottomed flask, add 2.9g 4-aminophenyl propargyl ether successively, 3.2ml Paraformaldehyde 96,2.4g 4-hydroxybenzonitrile, 110 ℃ of reaction 5h.With the dissolving of 30ml methylene dichloride, with the pure water washing, organic phase merges steaming and desolventizes, and column chromatography gets pale yellow crystals, productive rate 76%.
Ultimate analysis :C < > 18 <> H < > 14 <> N < > 2 <> O < > 2 <> , theoretical value %:C, 74.47%; H, 4.86%; N, 9.65%. analytical value :C, 73.31%; H, 4.92%; N, 9.73%.
1H?NMR(CDCl
3，300MHz，δ)：2.62，2.68ppm(≡C-H)，4.61ppm(s，Ar-CH
2-N)，5.33ppm(s，O-CH
2-N)，4.68ppm(O-CH
2-C)，6.61-7.89ppm(Ar-H)。FTIR(KBr)v:1025cm < >-1 <> The (C-O-C symmetry is flexible), 1237cm < >-1 <> The (C-O-C asymmetric stretch), 22cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 2230cm < >-1 <> (C ≡ N), 2114cm < >-1 <> (C ≡ C is flexible), 3178cm < >-1 <> (=C-H is flexible).
In the 50ml round-bottomed flask, add 2.9g 4-aminophenyl propargyl ether successively, 3.2ml Paraformaldehyde 96,2.5g are to aldehyde radical phenol, and 110 ℃ are reacted 3h.With the dissolving of 30ml methylene dichloride, with the pure water washing, organic phase merges steaming and desolventizes, and column chromatography gets pale yellow crystals, productive rate 72%.
Ultimate analysis :C < > 18 <> H < > 15 <> NO < > 3 <> , theoretical value %:C, 73.71%; H, 5.15%; N, 4.78%. analytical value :C, 74.25%; H, 5.26%; N, 4.73%.
1H?NMR(CDC
13，300MHz，δ)：2.52，2.61ppm(≡C-H)，4.60ppm(s，Ar-CH
2-N)，5.43ppm(s，O-CH
2-N)，4.65ppm(O-CH
2-C)，6.61-7.89ppm(Ar-H)，9.89ppm(-CHO)。FTIR(KBr)v:1023cm < >-1 <> The (C-O-C symmetry is flexible), 1238cm < >-1 <> The (C-O-C asymmetric stretch), 923cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 2230cm < >-1 <> (C ≡ N), 2114cm < >-1 <> (C ≡ C is flexible), 3178cm < >-1 <> (=C-H is flexible), 1691cm < >-1 <> The (C=O stretching vibration), 2831cm < >-1 <> The flexible vibrations of (O=C-H).
In the 50ml round-bottomed flask, add 14.7g 4-aminophenyl propargyl ether successively, 16ml Paraformaldehyde 96,11.9g 4-hydroxybenzonitrile, 110 ℃ of reaction 3h.With the dissolving of 50ml methylene dichloride, with the pure water washing, organic phase merges steaming and desolventizes ethyl alcohol recrystallization pale yellow crystals, productive rate 76%.
Ultimate analysis :C < > 18 <> H < > 14 <> N < > 2 <> O < > 2 <> , theoretical value %:C, 74.47%; H, 4.86%; N, 9.65%. analytical value :C, 73.31%; H, 4.92%; N, 9.73%.
1H?NMR(CDCl3，300MHz，δ)：2.62，2.68ppm(≡C-H)，4.61ppm(s，Ar-CH
2-N)，5.33ppm(s，O-CH
2-N)，4.68ppm(O-CH
2-C)，6.61-7.89ppm(Ar-H)。FTIR(KBr)v:1025cm < >-1 <> The (C-O-C symmetry is flexible), 1237cm < >-1 <> The (C-O-C asymmetric stretch), 22cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 2230cm < >-1 <> (C ≡ N), 2114cm < >-1 <> (C ≡ C is flexible), 3178cm < >-1 <> (=C-H is flexible).
In the 50ml round-bottomed flask, add 14.7g 4-aminophenyl propargyl ether successively, 16ml Paraformaldehyde 96,2.2g are to aldehyde radical phenol, and 110 ℃ are reacted 3h.With the dissolving of 50ml methylene dichloride, with the pure water washing, organic phase merges steaming and desolventizes ethyl alcohol recrystallization pale yellow crystals, productive rate 77%.
Ultimate analysis :C < > 18 <> H < > 15 <> NO < > 3 <> , theoretical value %:C, 73.71%; H, 5.15%; N, 4.78%. analytical value :C, 74.25%; H, 5.26%; N, 4.73%.
1H?NMR(CDC
13，300MHz，δ)：2.52，2.61ppm(≡C-H)，4.60ppm(s，Ar-CH
2-N)，5.43ppm(s，O-CH
2-N)，4.65ppm(O-CH
2-C)，6.61-7.89ppm(Ar-H)，9.89ppm(-CHO)。FTIR(KBr)v:1023cm < >-1 <> The (C-O-C symmetry is flexible), 1238cm < >-1 <> The (C-O-C asymmetric stretch), 923cm < >-1 <> The phenyl ring that (links to each other Yu the oxazine ring), 2230cm < >-1 <> (C ≡ N), 2114cm < >-1 <> (C ≡ C is flexible), 3178cm < >-1 <> (=C-H is flexible), 1691cm < >-1 <> The (C=O stretching vibration), 2831cm < >-1 <> The flexible vibrations of (O=C-H).
Embodiment 9: gather 3-allyl group-6-cyanic acid-3,4-dihydro-2H-1,3-benzoxazine (PNB-ala) synthetic
Get benzoxazine midbody sample NB-ala 2.5g and put into vacuum drying oven, behind 50 ℃ of vacuum-drying 3h of constant temperature, it is put in the aluminium matter rectangular parallelepiped mould of homemade 1.5cm * 1.0cm * 1.0cm, segmentation is solidified in Constant Temp. Oven.Concrete intensification solidification process is :140 ℃/2h; 160 ℃/2h; 180 ℃/2h; 200 ℃/2h; 230 ℃/2h; 260 ℃/6h.Obtain xanchromatic lump shape Polybenzoxazine PNB-ala at last.
Embodiment 10: gather 3-allyl group-6-aldehyde radical-3,4-dihydro-2H-1,3-benzoxazine (PFB-ala) synthetic
Get benzoxazine midbody sample FB-ala 2.8g and put into vacuum drying oven, behind 60 ℃ of freeze-day with constant temperature 3h, it is put in the aluminium matter rectangular parallelepiped mould of homemade 1.5cm * 1.0cm * 1.0cm, segmentation is solidified in Constant Temp. Oven.Concrete intensification solidification process is :110 ℃/3h; 150 ℃/2h; 170 ℃/2h; 190 ℃/2h; 220 ℃/2h.Obtain xanchromatic lump shape Polybenzoxazine PFB-ala at last.
Claims (1)
1. the polyfunctional group benzoxazine monomer of cyano-containing and propargyl is characterized in that structural formula is:
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| CN106928163A (en) * | 2017-02-22 | 2017-07-07 | 华南理工大学 | A kind of method with phenyl boric acid, amine and paraformaldehyde synthesizing mannich alkali and benzo-oxazine derivative |
| CN107674171A (en) * | 2017-11-17 | 2018-02-09 | 常州市宏发纵横新材料科技股份有限公司 | A kind of benzoxazine colophony for introducing propargyl and preparation method thereof |
| CN108840837B (en) * | 2018-07-27 | 2020-08-28 | 贵州理工学院 | Bio-based oxazine ring monomer, preparation method thereof and resin material containing bio-based oxazine ring |
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