CN101899014A - 2,4-di (4-carboxyphenyl)-6-phenyl-1,3,5-triazine, derivative and preparation method thereof - Google Patents

2,4-di (4-carboxyphenyl)-6-phenyl-1,3,5-triazine, derivative and preparation method thereof Download PDF

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CN101899014A
CN101899014A CN201010253521XA CN201010253521A CN101899014A CN 101899014 A CN101899014 A CN 101899014A CN 201010253521X A CN201010253521X A CN 201010253521XA CN 201010253521 A CN201010253521 A CN 201010253521A CN 101899014 A CN101899014 A CN 101899014A
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CN101899014B (en
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喻桂朋
潘春跃
李彬
赵菲
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Central South University
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Abstract

The invention relates to a 2,4-di (4-carboxyphenyl)-6-phenyl-1,3,5-triazine, a derivative and a preparation method thereof. The preparation method comprises the following steps of: reacting 2,4,6-trichloro-1,3,5-triazine under the actions of 4-alkyl phenyl magnesium halide as a Grignard reagent, phenyl magnesium halide or a derivative thereof; and oxidizing with a catalyst to prepare a compound disclosed by a formula I. The compound of the formula I can be used as a useful organic or medicine intermediate and is an important monomer for preparing 1, 3, 5-triazine high-performance polymer, wherein R stands for hydrogen, phenyl, naphthyl or a linear chain with 1-10 carbon atoms or alkoxyl with a branched chain.

Description

2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative and preparation method
Technical field
The invention belongs to the organic synthesis field, be specifically related to 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof and their preparation method.
Background technology
Aryl-1,3,5-triazines and derivative thereof are important organic and medicine intermediates.Wherein, contain the aryl-1,3,5-triazines of bifunctional, also can be used as antitumor drug or UV stabilizer.In addition, the develop rapidly in fields such as aerospace, military affairs, machinery, electronic apparatus, urgent day by day to the demand of high-performance polymer material.And contain 1,3,5-triazine structure polymkeric substance is owing to have high temperature resistant, high strength, good flame-retardance and excellent over-all propertieies such as unique optics and chemical property, therefore can be used as high performance engineering plastics, electron transport material and separation function material and has broad application prospects in above-mentioned field.Wherein, a kind of important source material that is used to prepare this base polymer is exactly the aryl-1,3,5-triazines monomer that contains bifunctional.
Contain the synthetic of bifunctional aryl-1,3,5-triazines, replace by functional group often that fragrant nitrile and corresponding acyl chlorides prepare under the Friedel-Crafts condition.As 2,4-two (4-chloro-phenyl-)-6-phenyl-1,3,5-triazines and 2,4-two (4-nitrophenyl)-6-phenyl-1,3,5-triazines synthetic is exactly respectively to be raw material to 6-chlorophenyl nitrile and p-nitrophenyl nitrile, with the Benzoyl chloride single step reaction.But the characteristics of this class reaction are exactly: the requirement of louis catalyst usage quantity is excessive, productive rate is lower and by product such as simple function group product and trifunctional product content height, for example see (Cook A.Journal of the American Society 1941,72,278-282; Spencer R.Analytical chemistry 1963,35,1633-1636).In this method, the discharging of excessive louis catalyst and processing also may bring the problem of aspects such as production safety and environmental pollution.Another synthetic method is: functional group replaces fragrant nitrile and corresponding aromatic aldehyde, in the presence of aniline, ethanol and benzene etc., makes through four step rule and to contain bifunctional aryl-1,3,5-triazines.By as 2, the preparation of 4-two (4-fluorophenyl)-6-phenyl-1,3,5-triazines is being raw material to fluorobenzonitrile, phenyl aldehyde, aniline, ethanol and benzene.At first, phenyl aldehyde and aniline react in chloroform and generate Schiff's base.Fluorobenzonitrile and ethanol are fed dry hydrogen chloride gas react and generate 4-fluorobenzene carbonamidine ethyl ether hydrochloride in benzene, under the ammoniacal liquor effect, obtain 4-fluorobenzene amitraz hydrochloride.4-fluorobenzene amitraz hydrochloride obtains final product (Fink R.Macromolecules 1997,30,8177-81 with the schiff base reaction that makes again then; WO.P.NO 9,811,150to RolfW).Though effectively avoided the generation of simple function group product and trifunctional product, the defective of this method is that productive rate extremely low (theoretical yield about 10%), reactions steps are many.And the product of each step enters next step reaction after all need making with extra care, thereby the production cycle is longer, and this makes it be difficult to be applied in plant-scale production.The method of the third synthetic bifunctional aryl-1,3,5-triazines is, 2,4,6-three chloro-1,3, the 5-triazine in the presence of suitable Grignard reagent, staged reaction, for example see 2, synthetic (the Tigelaar D.Macromolecules 2009 of 4-two (4-hydroxy phenyl)-6-phenyl--1,3,5-triazines, 42,1888-1896).The characteristics of this class reaction are: the reactive behavior height, the cycle is short, productive rate is higher, and can effectively avoid the generation of by products such as simple function group aryl-1,3,5-triazines and trifunctional aryl-1,3,5-triazines.
Up to now, preparation 2, the method for 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof is not seen any public publication report as yet.
Summary of the invention
The present invention prepares 2, and 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines or derivatives thereof is by having formula 4-alkyl phenyl halogenide and phenyl halogenide or their derivatives accordingly, making corresponding Grignard reagent with the capacity MAGNESIUM METAL respectively.In same reaction system, 2,4,6-three chloro-1,3,5-triazines make corresponding Grignard reagent with 4-alkyl phenyl magnesium halide and phenyl-magnesium-halide or their derivatives respectively successively, react, intermediate product formula V; At last, intermediate product formula V makes final product through the catalyst action oxydrolysis.In this method, by products such as simple function group aryl-1,3,5-triazines and trifunctional aryl-1,3,5-triazines do not appear.In addition, this method cycle is short, productive rate is high and simple, easy to operate, easily is applied in plant-scale production.
Therefore, the invention provides a kind of two substituted aryls-1 that prepare brand new, 3, the 5-triazine, promptly 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3, the preparation method that 5-triazine and derivative thereof are feasible, and avoid technical problem (productive rate is low, step is many, the cycle is long etc.) in the traditional method, and safety problem and environmental problem (excessive catalyzer).
One of purpose of the present invention is to be to provide 2 of a class brand new, 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof.
Two of purpose of the present invention provide a kind of easy, be easy to control, under the high yield preparation above-mentioned 2, the method for 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof.
Technical scheme of the present invention is as follows:
Synthetic 2 of the present invention, 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof, its chemical structure is shown in general formula I:
Figure BDA0000024445470000031
Formula I
Wherein: R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom.
Of the present invention 2, the synthetic method of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof, its reaction formula is suc as formula shown in the II:
Figure BDA0000024445470000032
Reaction formula II
Wherein: X is chlorine, bromine or iodine; THF is a tetrahydrofuran (THF); R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom; R ' is the straight chained alkyl that contains 1 to 7 carbon atom;
Of the present invention 2, the preparation method of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof may further comprise the steps:
The first step reaction: use 4-alkyl phenyl halogenide and the phenyl halogenide or derivatives thereof shown in general formula III and the IV:
Figure BDA0000024445470000033
Wherein: X is chlorine, bromine or iodine; R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom; R ' is the straight chained alkyl that contains 1 to 7 carbon atom;
Respectively with the capacity MAGNESIUM METAL 0-80 ℃ of reaction 4-20 hour, be solvent with ethers such as tetrahydrofuran (THF) etc. in the reaction, adopt protection of inert gas, make corresponding Grignard reagent;
The second step reaction: 2,4,6-three chloro-1,3,5-triazines with make 4-alkyl phenyl magnesium halide by general formula III, 1: 1.5 in molar ratio～2.5 (being preferably 1: 2) are reacted.Reaction is a solvent with ethers such as tetrahydrofuran (THF) etc., and controlled temperature lasts 0.5-48 hour at-20-40 ℃, and adopts protection of inert gas;
Three-step reaction: in above-mentioned reaction system, add capacity or excessively make the phenyl-magnesium-halide or derivatives thereof by general formula I V and MAGNESIUM METAL, in molar ratio 1: 1-1: 1.5 react.Reaction is a solvent with ethers such as tetrahydrofuran (THF) etc., and controlled temperature lasts 0.5-48 hour at 45-80 ℃, adopts protection of inert gas, must be suc as formula the intermediate product shown in the V.Intermediate product gets brown powder through sedimentation, filtration, washing, drying and recrystallization;
Figure BDA0000024445470000041
Formula V
Wherein: R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom; R ' is the straight chained alkyl that contains 1 to 7 carbon atom.
Four-step reaction: with above-mentioned suc as formula the intermediate product shown in the V, catalyzer and water or add simultaneously and the isopyknic alcoholic solvent of water, mix, reaction is a solvent with water, alcohol or alcohol-water mixture, and controlled temperature is at 50-100 ℃, last 2-48 hour, get head product.Head product obtains pale yellow powder through cooling, filtration, molten, the acid out of alkali.
Wherein, the catalyzer that uses in the four-step reaction is preferably manganese salt such as potassium permanganate as cobalt salt or manganese salt etc.The rare gas element that uses in first and second and the three-step reaction is nitrogen, neon or argon gas.
Description of drawings
Fig. 1 is 2, the infrared spectrogram of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines;
Fig. 2 is 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines 1H NMR spectrogram.
Embodiment
Provided by the invention shown in general formula I 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof, its synthetic method specifically comprised as the next stage:
(1) preparation of Grignard reagent: under protection of inert gas; 4-alkyl phenyl halogenide shown in general formula III and IV and phenyl halogenide or derivatives thereof; last 4-20 hour with the capacity MAGNESIUM METAL 0-80 ℃ of reaction respectively; the employing ethers is a solvent; get deep brown solution, make corresponding Grignard reagent 4-alkyl phenyl magnesium halide and phenyl-magnesium-halide.Wherein, the rare gas element that uses is nitrogen, argon gas etc.;
The preparation of (2) 2,4 two (4-alkyl phenyl)-6-chloro-1,3,5-triazines: 2,4, the ethereal solution of 6-three chloro-1,3,5-triazines is added drop-wise in the ethereal solution of above-mentioned 4-alkyl phenyl magnesium halide in batches, and the design reactant molar ratio is to react at 1: 2.Stir in the reaction process, and adopt protection of inert gas, controlled temperature lasts 0.5-48 hour at-20-40 ℃.Wherein, the rare gas element that uses is nitrogen, argon gas etc.;
(3) 2, the preparation of 4-two (4-alkyl phenyl)-6-phenyl-1,3,5-triazines or derivatives thereof: in above-mentioned reaction system, drip capacity in batches or excessively make the ethereal solution of phenyl-magnesium-halide or derivatives thereof by general formula I V and MAGNESIUM METAL, by reactant molar ratio 1: 1-1: 1.2 react.Reaction control temperature is lasted 0.5-48 hour at 45-80 ℃, adopts protection of inert gas, gets intermediate product.Intermediate product gets brown powder through sedimentation, filtration, washing, drying and recrystallization.Wherein, the rare gas element that uses is nitrogen, argon gas etc.;
The preparation of (4) 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof:, mix with above-mentioned intermediate product, catalyzer and solvent.Reaction is a solvent with water, alcohol or alcohol-water mixture, and controlled temperature lasts 2-48 hour at 50-100 ℃, gets head product.Head product obtains pale yellow powder through cooling, filtration, molten, the acid out of alkali.Wherein, the catalyzer that uses is preferably manganese salt such as potassium permanganate as cobalt salt, manganese salt etc.
In the case, product has very high purity and remarkable higher productive rate (purity＞99%, overall yield＞50%) after drying.
Synthetic of the present invention shown in general formula I 2, the structure of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof, by fusing point test, FT-IR, 1Analytical procedures such as H NMR, ultimate analysis and high resolution chromatogram/mass spectrometry are confirmed.
Compare with method well known in the prior art, preparation provided by the invention shown in general formula I 2, the method for 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof, reactions steps is simple, has only the separation and purification process of an intermediate product.Compared with prior art, present method is not used strong acid or severe corrosive raw material, and uses stoichiometric reagent in the reaction, nearly all reacts completely.After remaining reagent all easily recycles, and can use repeatedly.In addition, starting raw material magnesium, 2,4, all commercializations such as 6-three chloro-1,3,5-triazines and the 4-alkyl phenyl halogenide shown in general formula III and IV and phenyl halogenide or derivatives thereof, the catalyzer such as cobalt salt, the manganese salt etc. that adopt are the commercially available prod, thereby are applicable to industrial production.
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment according to the present invention.
In following embodiment, except that specifying, described umber is molfraction, and described feed composition is effective feed composition.In the specific embodiment of the invention 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof, and the reaction intermediate structured testing is being carried out on the following instrument: carry out the FT-IR test on Nicolet-20DXB type infrared spectrometer, with the sample preparation of KBr pressed disc method; (2 ℃/min of temperature rise rate, 50～300 ℃ of test specifications) carried out in the fusing point test on WRS-1A fusing point instrument; The matrix flight mass spectrum (MALDI-TOF/MS) that dissociates carries out on GC-TOF CA 156MALDI-TOF/MS; Ultimate analysis (Elemental analysis) is carried out on Vario EL III CHNOS Elementaranalysator; Nuclear magnetic resonance spectroscopy (NMR) carries out on Brucker spectrometer 400, and TMS is interior mark, 25 ℃ of probe temperatures.
Exemplary embodiments
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Example 1:2, the preparation of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines
In the 500mL there-necked flask that has induction stirring, thermometer, reflux condensing tube and drying tube, add the tetrahydrofuran (THF) (THF) of Cynuric Chloride 5.1g (27.1mmo1), 15mL successively.The ice bath protection drips in batches and makes also refrigerative Grignard reagent 4-aminomethyl phenyl magnesium bromide 10.6g (54.2mmo1) in advance down.Finish, behind the stirring reaction 20min, be warmed up to 25 ℃ of reactions and last 12h.Be warmed up to 50 ℃ of reactions again and last 12h.Cooling, and with the ice bath protection, drip again and make also refrigerative Grignard reagent phenyl-magnesium-bromide 4.9g (27.2mmo1) in advance.Stirring reaction 30min is warming up to system 85 ℃ of reactions then and lasts 12h, obtains the brown oily liquids.Reaction product through revolve steaming, extraction, filtration, again revolve steam and drying after, obtain white powder 2,4-two (4-aminomethyl phenyl)-6-phenyl-1,3,5-triazines (Yield=86.3%; M.p.150.5～150.9 ℃ ultimate analysis calculated value: (C 23H 19N 3), calculated value: C, 81.87; H, 5.68; N, 12.46; Experimental value: C, 82.06; H, 5.57; N, 12.33%.High resolution chromatogram/mass spectrometry result shows that its molecular ion peak is 337.4167, with its molecular weight calculated value 337.4172 (molecular formula C 23H 19N 3) conform to.
With make 2,4-two (4-aminomethyl phenyl)-6-phenyl-1,3,5-triazine 8.1g (23.4mmo1), potassium permanganate 3.644g (23.057mmo1), Tetrabutyl amonium bromide 0.002g, distilled water 50mL, join the 250mL round-bottomed flask, connect spherical condensation tube, vigorous stirring, be heated to boiling, reaction 7h under 90 ℃ keeps solution steadily to reflux, and obtains pale brown look liquid.Filtration obtains yellow clarified liq, and regulating pH to pH value with hydrochloric acid is 1, and crystal is separated out, after filtration, dry must pale yellow powder.Yield=80.2% (7.6g), fusing point m.p.＞300 ℃, purity 99.8%.High resolution chromatogram/mass spectrometry result shows that its molecular ion peak is 397.3817, with its molecular weight calculated value 397.3830 (molecular formula C 23H 15N 3O 4) conform to.Ultimate analysis calculated value: (C 23H 15N 3O 4), calculated value: C, 69.52; H, 3.78; N, 10.58%; Experimental value: C, 69.44; H, 3.59; N, 10.71%.
Product 2, the infrared spectrum of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines is seen Fig. 1, therefrom can observe the following characteristics absorption band:
3071cm -1C-H stretching vibration absorption band on the aromatic ring;
2240cm -1Cyano group C ≡ N feature stretching vibration absorption band
1597cm -1Aromatic ring C=C stretching vibration absorption band;
1485cm -1Aromatic ring C=C stretching vibration absorption band;
1310cm -1Aromatic ring SO 2Stretching vibration symmetry absorption band;
1230cm -1Aryl oxide C-O stretching vibration absorption band;
1180cm -1Aromatic ring SO 2Stretching vibration unsymmetrically absorption band
920cm -1Epoxide group stretching vibration absorption band
Product 2, the proton magnetic spectrum figure of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines sees Fig. 2, therefrom can observe the following characteristics proton signal:
Because the strong electrophilic effect of 1,3,5-triazines ring and hydroxy-acid group, the chemical shift of H2, H3 almost overlaps, and the H1 proton signal on the corresponding carboxyl appears at the 10.56ppm place.In addition, each proton signal absorption peak area ratio conforms to fully with target product hydrogen proton ratio, has further proved the target product structure.
The solubility property test result of product shows, be dissolvable in water NMP (N-Methyl pyrrolidone), DMAc (N under this compound room temperature, the N-N,N-DIMETHYLACETAMIDE), DMF (N, dinethylformamide), DMSO, etc. polar solvent commonly used, illustrate that it has good solubility, therefore can be easily as solution condensation polymeric reaction monomers.
The effect that contains the important monomer of 1,3,5-triazines high-performance polymer with reference to following experimental example explanation The compounds of this invention as preparation.
Experimental example 1: contain the preparation of 1,3,5-triazines polyaramide
In the there-necked flask of being furnished with mechanical stirrer, prolong and nitrogen conduit; add 20.0mmol (7.938g) 2 under the nitrogen protection successively; 4-two (4-carboxyphenyl phenyl)-6-phenyl-1; 3,5-triazine, 18.0mmol (3.604g) 4; the 4-diaminodiphenyl oxide; 86.0mmol (9.546g) Calcium Chloride Powder Anhydrous, 40.0mmol (12.411g) triphenyl phosphite, 20mL pyridine and 60mL N-Methyl pyrrolidone (NMP).Behind the about 6h of reaction under 110 ℃, be cooled to room temperature.With reaction solution pour into ethanol and water mixed liquid (1: 1, V/V) in sedimentation, agitating deionized water constantly in the process of pouring into obtains the white fiber shaped polymer at last.Product after filtration, washing, alcohol wash.Polymkeric substance is dissolution with solvents with NMP, vacuum filtration.With filtrate be deposited to the second alcohol and water (1: 1, V/V) in the mixed liquid, vacuum filtration, vacuum-drying is 24 hours in 100 ℃ of vacuum drying ovens, white filament shape product, yield is 95.4%.Adopt solution shop embrane method can prepare polymeric film.
The polymer thermostable performance characterizes through thermal weight loss test analysis (TGA).NETZSCH TGA209 type thermogravimetric analyzer is adopted in the TGA test, under the nitrogen atmosphere, and 20 ℃/min of heat-up rate, 100～800 ℃ of test specifications.Test result shows, this polymkeric substance has excellent thermal stability, under the nitrogen atmosphere 5% of polymkeric substance and the thermal weight loss temperature of 10% o'clock correspondence be respectively 484 ℃ and 521 ℃.

Claims (6)

1.2 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines or derivatives thereof is characterized in that containing the structure just like shown in the general formula I:
Figure FDA0000024445460000011
Formula I
Wherein: R is hydrogen, phenyl, naphthyl or straight chain or the branched alkoxyl group that contains 1 to 10 carbon atom.
2. one kind prepares claim 1 described 2,4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3, the method of 5-triazine or derivatives thereof, it is characterized in that: phenyl halogenide or their derivatives by structure shown in 4-alkyl phenyl halogenide with structure shown in the formula III and the formula IV make corresponding Grignard reagent with the capacity MAGNESIUM METAL respectively; In same reaction system, 2,4,6-three chloro-1,3,5-triazines respectively successively with the Grignard reagent that makes by 4-alkyl phenyl magnesium halide and phenyl-magnesium-halide or their derivatives, react, intermediate product formula V; At last, intermediate product formula V makes final product formula I through the catalyst action oxydrolysis;
Figure FDA0000024445460000012
Wherein: X is chlorine, bromine or iodine; R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom; R ' is the straight chained alkyl that contains 1 to 7 carbon atom.
3. described 2 according to claim 2, the preparation method of 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines or derivatives thereof is characterized in that: reaction is undertaken by following reaction formula II:
Figure FDA0000024445460000021
Reaction formula II
Wherein: X is chlorine, bromine or iodine; THF is a tetrahydrofuran (THF); R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom; R ' is the straight chained alkyl that contains 1 to 7 carbon atom;
Figure FDA0000024445460000022
Be that 4-alkyl phenyl halogenide by structure shown in the formula III makes;
Figure FDA0000024445460000023
Be that phenyl halogenide by structure shown in the formula IV makes.
4. described 2 according to claim 2, the method for 4-two (4-carboxyphenyl phenyl)-6-phenyl-1,3,5-triazines and derivative thereof is characterized in that may further comprise the steps:
The first step reaction: use 4-alkyl phenyl halogenide and phenyl halogenide or their derivative shown in general formula III and the IV:
Figure FDA0000024445460000024
Wherein: X is chlorine, bromine or iodine; R is a hydrogen, phenyl, naphthyl or contain the straight chain or the branched alkoxyl group of 1 to 10 carbon atom; R ' is the straight chained alkyl that contains 1 to 7 carbon atom;
Respectively with the capacity MAGNESIUM METAL 0-80 ℃ of reaction 4-20 hour, be solvent with the ethers in the reaction, adopt protection of inert gas, make corresponding Grignard reagent;
The reaction of second step: with 2,4,6-three chloro-1,3, the 5-triazine with make 4-alkyl phenyl magnesium halide or its derivative by general formula III, 1: 1.5 in molar ratio～2.5 react, reaction is a solvent with the ethers, controlled temperature lasts 0.5-48 hour at-20-40 ℃, and adopts protection of inert gas;
Three-step reaction: in above-mentioned reaction system, add capacity or excessively make phenyl-magnesium-halide or its derivative by general formula I V and MAGNESIUM METAL, in molar ratio 1: 1-1: 1.5 react, reaction is solvent with the ethers, and controlled temperature lasts 0.5-48 hour at 45-80 ℃, adopt protection of inert gas, get intermediate product, intermediate product gets brown powder through sedimentation, filtration, washing, drying and recrystallization;
Four-step reaction:, mix with above-mentioned intermediate product, catalyzer and solvent; Solvent is water, alcohol or alcohol-water mixture, and controlled temperature reacted 2-48 hour at 50-100 ℃, gets head product; Head product obtains pale yellow powder through cooling, filtration, molten, the acid out of alkali.
5. according to claim 3 or 4 described methods, it is characterized in that described catalyzer is cobalt salt or manganese salt.
6. method according to claim 4 is characterized in that, described rare gas element is nitrogen, neon or fluorine gas.
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CN102585186A (en) * 2012-02-06 2012-07-18 中南大学 Aryl-1,3,5-triazine polyarylester and preparation method thereof
CN102585186B (en) * 2012-02-06 2014-01-29 中南大学 Aryl-1,3,5-triazine polyarylester and preparation method thereof
CN103012297A (en) * 2012-12-13 2013-04-03 中南大学 Cyanate ester and polymer containing s-triazine structure and preparation methods of cyanate ester and polymer
CN103012297B (en) * 2012-12-13 2015-05-06 中南大学 Cyanate ester and polymer containing s-triazine structure and preparation methods of cyanate ester and polymer

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