CN1900068A - Benzoxazine resin intermediate, resin and solidified matter and their preparing method and use - Google Patents
Benzoxazine resin intermediate, resin and solidified matter and their preparing method and use Download PDFInfo
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- CN1900068A CN1900068A CN 200610021315 CN200610021315A CN1900068A CN 1900068 A CN1900068 A CN 1900068A CN 200610021315 CN200610021315 CN 200610021315 CN 200610021315 A CN200610021315 A CN 200610021315A CN 1900068 A CN1900068 A CN 1900068A
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Abstract
The present invention provides benzoxazine resin intermediate prepared with diamine with side cyano radical, benzoxazine resin and benzoxazine resin condensate. The preparation process is simple and high in yield, and the benzoxazine resin and the benzoxazine resin condensate have good self fire retarding property, adhering property, heat stability and flowability, and may be applied widely in paint, electronic packaging material and resin base composite material.
Description
Technical field
The present invention relates to a kind of benzoxazine intermediate, specifically, the resin that relates to the benzoxazine intermediate and be prepared from belongs to the synthetic field of macromolecular material.
Background technology
Benzoxazine colophony is a kind of intermediate (claiming the benzoxazine intermediate) that got by the compound that contains the benzoxazine ring structure, by the intermediate preparation macromolecule resin.The material that benzoxazine colophony can further react formation is called " benzoxazine so-and-so material ", and 945cm-1 has typical characteristic absorbance on FTIR.This resinoid is because of the intermediate structure difference, and resin of Xing Chenging and after product structure difference cause its physicochemical characteristics, performance function difference at last; Preparation technology adds the raw material mode difference, or adopts the reaction method difference, as solution reaction, dispersion reaction, suspended dispersed reaction etc.
" thermosetting resin ", 18 (2), 3 (2003); 19 (2), 3 (2004) employing allyl amines are to introduce allyl group on the ， Zai oxazine ring of amine source, prepare the novel benzoxazine that contains reactive allyl group and have studied curing reaction." Jilin Institute of Chemical Technology journal " 20 (3), 9 (2003), research has been reported with formaldehyde, aniline, phenol and has been the benzoxazine of raw material and has studied curing reaction; " polymer material science and engineering ", 18 (2), 3 (2002) have reported the polyreaction of benzoxazine-epoxy compounds-amines catalyst system.; " polymer material science and engineering ", 18 (3), 3 (2004) have reported the blending and modifying progress of benzoxazine colophony." Jingmen Vocationl Technical College journal " 6 (2) 11 (2001) reported the benzoxazine of the benzoxazine of solution method and scorification synthesis of bisphenol A, formaldehyde, methylamine methyl alcohol and dihydroxyphenyl propane, Paraformaldehyde 96, aniline and characterized; Polymer 37 (20), and 4487-4495 is based on the mechanical property of the multipolymer of epoxy and benzoxazine.Polymer, the influence that 40 (1999) 4365-4367 phenol structure Dui benzoxazine polymkeric substance thermolysiss and thermooxidizing are decomposed.Aniline, various phenol generate Polybenzoxazine to the stable on heating .polymer that influences, the thermosetting resin structure .Polymer of 43 (2002) 5,069 5076 fire-retardant linear phenolic aldehyde-para-Phthalonitrile structures, 46 (2005), 5588-5595, synthetic and the sign of the benzoxazine of a synthetic maleimide norbornylene functional group, studying different initiators to the influence of the synthetic influence of maleimide benzoxazine monomer and extent of polymerization and kind to the final product structure. this paper also studies the benzoxazine monomer .Thermochnical Acta of the low high Tg of viscosity, 357-358 (2000), 195-203 have reported the benzoxazine polymkeric substance thermal characteristics that contains (neighbour) benzene dicarbonitrile functional group." Wuhan Institute of Chemical Technology's journal ", 23 (1), 3 (2001), adopt solvent method prepared Resorcinol, aniline, formaldehyde benzoxazine synthetic with characterize.Chinese invention patent CN99114603.4, CN03126518.9, CN02108772.5, CN03146797.0, CN02806290.6 etc. have invented the preparation method and the application in veneer sheet and coating of benzoxazine intermediate and resin, basically all be based on phenol, aldehyde and amine component compound, Shang Weiyou is the feedstock production benzoxazine colophony with the cyano group binary amine, and the benzoxazine monomer of cyano-containing is only relevant for the report of p-aminophenyl nitrile.
Summary of the invention
Technical problem to be solved by this invention provides a kind of benzoxazine intermediate, and another technical problem that the present invention solves has provided a kind of benzoxazine colophony, benzoxazine cured article and preparation method thereof.
The invention provides a kind of benzoxazine colophony intermediate, its structural formula is as follows:
With determination of elemental analysis molecular weight and infrared measurement typical absorption peak: benzoxazine intermediate, molecular weight 553, FTIR have-CN ,-characteristic absorbance of O-, benzoxazine ring: at 943.13cm
-1The characteristic peak that oxazine ring occurs; The characteristic peak that has occurred itrile group at the 2227.63cm-1 place; At the stronger absorption peak in 1222.79cm-1 place, it is an Ar-O ehter bond stretching vibration peak, and this explanation phenolic hydroxyl group has been participated in reaction, generates the ehter bond in the oxazine ring structure.1245.93cm
-1Occurred-stretching vibration of C-O-C-absorbs; 835.12cm
-1Phenyl ring skeleton peak has appearred; 1458cm
-1Be indicated as 1,2,4-phenyl ring three replaces; 754.12cm
-1Occurred 1,2-phenyl ring two replaces characteristic peak.
The invention provides a kind of benzoxazine colophony, it is by the benzoxazine colophony intermediate, adds the copolymerization ring opening agent, is polymerized, and its structural formula is as follows:
Wherein, described copolymerization ring opening agent is a kind of in resol, general benzoxazine colophony or the Resins, epoxy, and wherein, the copolymerization ring opening agent accounts for the 30-70% of the gross weight of copolymerization ring opening agent and benzoxazine colophony intermediate.
The invention provides the method for preparing the benzoxazine colophony intermediate, comprise the steps:
A, preparation cyano group side group diamine;
B, take off the component of stating mole proportioning:
Cyano group side group diamine 1mol, phenol 2mol, formaldehyde (or Paraformaldehyde 96 or 30%w/w formalin) 4mol, one or both 10-50mol among toluene, the dimethylbenzene, Evil;
C, get cyano group side group diamine, phenol and be dissolved in toluene (or dimethylbenzene or or dioxane or toluene, dimethylbenzene arbitrary proportion mixture), slowly drip formaldehyde, heating, temperature is controlled at 40～60 ℃, formaldehyde dropwises reaction 3～5 hours, and stopped reaction is with 40-70 ℃ hot wash 3-5 time, vacuumized 1～4 hour at 80～90 ℃, promptly get the benzoxazine colophony intermediate.
Wherein, the described method for preparing cyano group side group diamine of step a can adopt existing open source literature reported method, also can select following method preparation:
A, take off the component of stating mole proportioning:
P-aminophenol 2mol, 2,6-dichlorobenzonitrile 1mol, catalyzer 1.1-1.5mol;
B, make p-aminophenol, 2, the 6-dichlorobenzonitrile, catalyzer, solvent, one or both in toluene, the dimethylbenzene are at 140-180 ℃ of reaction 4-8 hour, stopped reaction;
C, get in the step b gained reaction mixture impouring water and precipitate, add the dilute hydrochloric acid acidifying, filter, wash with water, in the 80-130 ℃ of vacuum drying oven dry 10-24 hour, promptly get cyano group side group diamine;
With determination of elemental analysis molecular weight and infrared measurement typical absorption peak: cyano group side group diamine, molecular weight 317, FTIR have the characteristic absorbance of cyano group: at 2231.49cm
-1The characteristic peak of itrile group has appearred in the place, NH occurred at 3413.77 places
2Characteristic peak is at 780cm
-1Phenyl ring 1,2 has appearred, the t subsn characteristic peak of 3-; 830cm
-1 Phenyl ring 1 has appearred, the characteristic peak that the 4-binary replaces.1247cm
-1Occurred-stretching vibration of C-O-C-absorbs, and illustrates that phenolic hydroxyl group and chlorine nucleophilic substitution reaction have taken place generated the aryl oxide key.
Wherein, the described catalyzer of step a is one or both in Anhydrous potassium carbonate, the anhydrous sodium carbonate;
The described solvent of step b is one or more in anhydrous dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, the N-Methyl pyrrolidone, and consumption is 100-500mol;
The described toluene consumption of step b is 10-50mol.
The invention provides a kind of method for preparing benzoxazine colophony, it comprises the steps:
A, get the benzoxazine colophony intermediate, add the copolymerization ring opening agent, wherein, the copolymerization ring opening agent accounts for the 30-70% of the gross weight of copolymerization ring opening agent and benzoxazine colophony intermediate;
B, 60-80 ℃ of reaction 2-3 hour, obtain benzoxazine colophony.
The invention provides a kind of benzoxazine colophony cured article, it is that being heating and curing forms by after described benzoxazine intermediate, benzoxazine colophony or its mixing.
Both mix and form (intermediate also can only be arranged or the open loop body is only arranged) by intermediate, intermediate open loop after product for it, and resin of the present invention forms the cured article system through further reaction, is feature by benzoxazine mainly all.
The invention provides a kind of method for preparing this benzoxazine colophony cured article, it is characterized in that: it is by benzoxazine intermediate or resin or co-blended heating, under 160～220 ℃ of temperature curing reaction 1-5 hour, obtained the benzoxazine colophony cured article again at 250 ℃ of postheat treatment 3-8 hours.
The present invention also provides this application of benzoxazine colophony cured article in coating, electronic package material, polymer matrix composites.
The present invention also provides this benzoxazine colophony and the application of cured article in coating, electronic package material, polymer matrix composites thereof.Benzoxazine colophony of the present invention and cured article thereof belong to thermosetting resin, have adhesiveproperties and flowability preferably, and cured article has higher mechanical strength and thermostability, can realize such use.Owing to the introducing of cyano group, the flame retardant resistance of resin and cured article thereof be can increase simultaneously, the application resin of the present invention and the coating of cured article thereof, the cementability of matrix material improved.
Preparation process reaction process of the present invention as shown in Figure 1, preparation technology is simple to operate effectively, the productive rate height, can adjust the structure and the performance of product to a great extent, reaction provides new architecture basics by the synthetic cyano group of introducing of monomer for the functionalization of intermediate of the present invention or resin and potential are crosslinked, improved resin from flame retardant resistance.The present invention adopts the benzoxazine colophony intermediate, the benzoxazine colophony thermostability of preparation (second-order transition temperature with 160-200 ℃) and preferably from flame retardant properties.Resin of the present invention and resin cured matter thereof are except that the typical absorption of 945cm-1 Ju You oxazine, and mainly the aryl oxide key at the CN of 2227CM-1 group and 1247CM-1 has characteristic absorbance.At 160-220 ℃ gelation time is 4-30 minute, and it is 220-250 ℃ that DSC solidifies summit temperature; Cured article second-order transition temperature (Tg) is higher than 50% at 180-200 ℃ at 800 ℃ thermolysis carbon yields, and it is fire-retardant that cured article reaches the V0 level.
Benzoxazine colophony intermediate of the present invention has the crosslinkable of activity of curing reaction and cyano group preferably and has given higher thermal stability of resin and mechanical strength preferably; Can in very large range control the structure and the performance of resin simultaneously by crosslinking structure control.
Obviously, according to foregoing of the present invention,,, can also make modification, replacement or the change of other various ways not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite according to the ordinary skill knowledge and the customary means of this area.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Description of drawings
Fig. 1 cyano group side group of the present invention diamine, benzoxazine colophony intermediate, benzoxazine colophony, benzoxazine colophony cured article preparation flow figure
Embodiment
The preparation and the physico-chemical property of embodiment 1 benzoxazine intermediate of the present invention
(1) proportioning raw materials of preparation cyano group side group diamine:
P-aminophenol 218 grams, 2,6-dichlorobenzonitrile 172 grams, catalyzer carbonic acid potassium 151 grams.
(2) preparation of cyano group side group diamine: with p-aminophenol, 2,6-dichlorobenzonitrile, catalyzer, anhydrous dimethyl formamide, toluene are added in the four-necked bottle of band water trap, the feeding nitrogen replacement goes out air wherein, and elevated temperature is at 4 hours stopped reaction of 140 ℃ of reactions, to precipitate in the reaction mixture impouring water, add the dilute hydrochloric acid acidifying, filter, wash with water three times, drying is 24 hours in 80 ℃ of vacuum drying ovens, obtain cyano group side group diamine, productive rate 96%.
(3) proportioning raw materials of preparation benzoxazine intermediate:
Get phenol 188 gram, 30%w/w formalin 400 grams, (2) and be prepared into cyano group side group diamine 317 grams.
(the preparation of 4) benzoxazine colophony intermediates: exsiccant cyano group side group diamine, phenol are dissolved in and are added in the four-necked bottle in the toluene, the feeding nitrogen replacement goes out air wherein, slowly drip formaldehyde solution, temperature is controlled at 40-60 ℃, dropwise 4 hours stopped reaction of reaction,, vacuumized 2 hours at 80-90 ℃ with hot wash 3-5 time, obtain the benzoxazine colophony intermediate, productive rate 85%.
The infared spectrum of benzoxazine intermediate is at 943.13cm
-1The characteristic peak that oxazine ring occurs; At 2227.63cm
-1The characteristic peak of itrile group has appearred in the place; At 1222.79cm
-1Locate stronger absorption peak, it is an Ar-O ehter bond stretching vibration peak, and this explanation phenolic hydroxyl group has been participated in reaction, generates the ehter bond in the oxazine ring structure.1245.93cm
-1Occurred-stretching vibration of C-O-C-absorbs; 835.12cm
-1Phenyl ring skeleton peak has appearred; 1458cm
-1Be indicated as 1,2,4-phenyl ring three replaces; 754.12cm
-1Occurred 1,2-phenyl ring two replaces characteristic peak.
The preparation and the physico-chemical property of embodiment 2 benzoxazine intermediates of the present invention
(1) proportioning raw materials of preparation cyano group side group diamine:
P-aminophenol 218 grams, 2,6-dichlorobenzonitrile 172 grams, catalyzer carbonic acid sodium 115 grams.
(2) preparation of cyano group side group diamine: with p-aminophenol, 2,6-dichlorobenzonitrile, catalyzer, N,N-DIMETHYLACETAMIDE, dimethylbenzene are added in the four-necked bottle of band water trap, the feeding nitrogen replacement goes out air wherein, and elevated temperature is at 4 hours stopped reaction of 160 ℃ of reactions, to precipitate in the reaction mixture impouring water, add the dilute hydrochloric acid acidifying, filter, wash with water three times, drying is 24 hours in 80 ℃ of vacuum drying ovens, obtain cyano group side group diamine, productive rate 97%.
(3) proportioning raw materials of preparation benzoxazine intermediate:
Cyano group side group diamine 317 grams, phenol 188 grams, Paraformaldehyde 96 120 grams.
(the preparation of 4) benzoxazine colophony intermediates: exsiccant cyano group side group diamine, phenol are dissolved in and are added in the four-necked bottle in the dimethylbenzene, the feeding nitrogen replacement goes out air wherein, slowly drip formaldehyde solution, temperature is controlled at 40-60 ℃, dropwise 4 hours stopped reaction of reaction,, vacuumized 2 hours at 80-90 ℃ with hot wash 3-5 time, obtain the benzoxazine colophony intermediate, productive rate 85%.
The infared spectrum of benzoxazine intermediate is at 943.13cm
-1The characteristic peak that oxazine ring occurs; At 2227.63cm
-1The characteristic peak of itrile group has appearred in the place; At 1222.79cm
-1Locate stronger absorption peak, it is an Ar-O ehter bond stretching vibration peak, and this explanation phenolic hydroxyl group has been participated in reaction, generates the ehter bond in the oxazine ring structure.1245.93cm
-1Occurred-stretching vibration of C-O-C-absorbs; 835.12cm
-1Phenyl ring skeleton peak has appearred; 1458cm
-1Be indicated as 1,2,4-phenyl ring three replaces; 754.12cm
-1Occurred 1,2-phenyl ring two replaces characteristic peak.
The preparation and the physico-chemical property of embodiment 3 benzoxazine intermediates of the present invention
(1) proportioning raw materials of preparation cyano group side group diamine:
P-aminophenol 218 grams, 2,6-dichlorobenzonitrile 172 grams, catalyzer carbonic acid potassium 151 grams.
(2) preparation of cyano group side group diamine: with p-aminophenol, 2,6-dichlorobenzonitrile, catalyzer, N,N-DIMETHYLACETAMIDE, dimethylbenzene are added in the four-necked bottle of band water trap, the feeding nitrogen replacement goes out air wherein, and elevated temperature is at 4 hours stopped reaction of 140 ℃ of reactions, to precipitate in the reaction mixture impouring water, add the dilute hydrochloric acid acidifying, filter, wash with water three times, drying is 24 hours in 80 ℃ of vacuum drying ovens, obtain cyano group side group diamine, productive rate 96.5%.
(3) proportioning raw materials of preparation benzoxazine intermediate:
Cyano group side group diamine 317 grams, phenol 188 grams, 30%w/w formalin 400 grams.
(the preparation of 3) benzoxazine colophony intermediates: exsiccant cyano group side group diamine, phenol are dissolved in and are added in the four-necked bottle in the dioxane, the feeding nitrogen replacement goes out air wherein, slowly drip formaldehyde solution, temperature is controlled at 40-60 ℃, dropwise 2 hours stopped reaction of reaction,, vacuumized 2 hours at 80-90 ℃ with hot wash 5 times, obtain the benzoxazine colophony intermediate, productive rate 60%.
The infared spectrum of benzoxazine monomer is at 943.13cm
-1The characteristic peak that oxazine ring occurs; At 2227.63cm
-1The characteristic peak of itrile group has appearred in the place; At 1222.79cm
-1Locate stronger absorption peak, it is an Ar-O ehter bond stretching vibration peak, and this explanation phenolic hydroxyl group has been participated in reaction, generates the ehter bond in the oxazine ring structure.1245.93cm
-1Occurred-stretching vibration of C-O-C-absorbs; 835.12cm
-1Phenyl ring skeleton peak has appearred; 1458cm
-1Be indicated as 1,2,4-phenyl ring three replaces; 754.12cm
-1Occurred 1,2-phenyl ring two replaces characteristic peak.
The preparation and the physico-chemical property of embodiment 4 benzoxazine cured articles of the present invention
Benzoxazine intermediate (embodiment 1 preparation) 50g is warming up to 200 ℃ of reactions 30 minutes again 160 ℃ of frit reactions 30 minutes, and 220 ℃ were reacted 30 minutes, were warming up to 250 ℃ of postheat treatment and got the benzoxazine colophony cured article in 3 hours.
The FTIR of benzoxazine colophony cured article of the present invention has at the 2227cm-1 place-the CN absorption; Second-order transition temperature is at 160 ℃; (5%) 393 ℃ of decomposition temperature; Carbon yield 57% in the time of 600 ℃; Flame retardant resistance V0 level.
The preparation and the physico-chemical property of embodiment 5 benzoxazine Resins, epoxy of the present invention and cured article
(proportioning raw materials of 1) benzoxazine Resins, epoxy:
Benzoxazine intermediate (embodiment 1 preparation) 50g, E-44 Resins, epoxy 50g.
(2) Qing base benzoxazine intermediate, E-44 Resins, epoxy, small amount of acetone are added in the four-necked bottle as solvent, feed nitrogen replacement and go out wherein air, elevated temperature, 60-80 ℃ of hybrid reaction 2 hours, resin; In the room temperature vacuum drying oven dry 24 hours, 160-220 ℃ of curing reaction 1 hour, be warming up to 250 ℃ of postheat treatment 3 hours the benzoxazine colophony cured article.
The FTIR of benzoxazine colophony cured article of the present invention has at the 2227cm-1 place-the CN absorption; Second-order transition temperature is at 176.41 ℃; (5%) 363 ℃ of decomposition temperature; Carbon yield 46.7% in the time of 600 ℃; Flame retardant resistance V0 level.
The preparation and the physico-chemical property of embodiment 6 benzoxazine Resins, epoxy of the present invention and cured article
(proportioning raw materials of 1) benzoxazine Resins, epoxy:
Qing base benzoxazine intermediate (embodiment 1 preparation) 40g, E-44 Resins, epoxy 60g.
(2) Qing base benzoxazine intermediate, E-44 Resins, epoxy, small amount of acetone are added in the four-necked bottle as solvent, and the feeding nitrogen replacement goes out air wherein, and elevated temperature mixed 3 hours at 60-80 ℃, got resin; In the room temperature vacuum drying oven dry 24 hours, 160-220 ℃ of curing reaction 5 hours, be warming up to 250 ℃ of postheat treatment 8 hours the benzoxazine colophony cured article.
The FTIR of benzoxazine colophony cured article of the present invention has at the 2227cm-1 place-the CN absorption; Second-order transition temperature is at 169.5 ℃; (5%) 365 ℃ of decomposition temperature; Carbon yield 34% in the time of 600 ℃; Flame retardant resistance V0 level.
The preparation and the physico-chemical property of embodiment 7 benzoxazine Resins, epoxy of the present invention
(proportioning raw materials of 1) benzoxazine Resins, epoxy:
Qing base benzoxazine intermediate (embodiment 1 preparation) 60g, E-44 Resins, epoxy 40g.
(2) Qing base benzoxazine intermediate, E-44 Resins, epoxy, small amount of acetone are added in the four-necked bottle as solvent, and the feeding nitrogen replacement goes out air wherein, and elevated temperature mixed 2.5 hours at 60-80 ℃, got resin; In the room temperature vacuum drying oven dry 24 hours, 160-220 ℃ of curing reaction 3 hours, be warming up to 250 ℃ of postheat treatment 5 hours the benzoxazine colophony cured article.
The FTIR of benzoxazine colophony cured article of the present invention has at the 2227cm-1 place-the CN absorption; Second-order transition temperature is at 197 ℃; (5%) 370 ℃ of decomposition temperature; Carbon yield 46.7% in the time of 600 ℃; Flame retardant resistance V0 level.
The curing of the phenol/aniline type benzoxazine of embodiment 8 Qing base benzoxazines of the present invention
(1) gets raw material: Qing base benzoxazine intermediate 50g (by embodiment 2 preparations), phenol/aniline type benzoxazine 50g.
(2) Qing base benzoxazine intermediate, phenol/aniline type benzoxazine, small amount of acetone are added in the four-necked bottle as solvent, and the feeding nitrogen replacement goes out air wherein, and elevated temperature mixed 2.5 hours at 60-80 ℃, got resin; In the room temperature vacuum drying oven dry 24 hours, 160-220 ℃ of curing reaction 4 hours, be warming up to 250 ℃ of postheat treatment 7 hours the benzoxazine colophony cured article.
The FTIR of benzoxazine colophony cured article of the present invention has CN to absorb at the 2227cm-1 place; Second-order transition temperature is at 175 ℃; (5%) 348 ℃ of decomposition temperature; Carbon yield 52% in the time of 600 ℃; Flame retardant resistance V0 level.
The curing of the resol of embodiment 9 Qing base benzoxazines of the present invention
(1) gets raw material: Qing base benzoxazine intermediate 50g (by embodiment 2 preparations), resol 50g.
(2) Qing base benzoxazine intermediate, resol, small amount of acetone are added in the four-necked bottle as solvent, and the feeding nitrogen replacement goes out air wherein, and elevated temperature mixed 2 hours at 60-80 ℃, got resin; In the room temperature vacuum drying oven dry 24 hours, 160-220 ℃ of curing reaction 8 hours, be warming up to 250 ℃ of postheat treatment 5 hours the benzoxazine colophony cured article.
The FTIR of benzoxazine colophony cured article of the present invention has CN to absorb at the 2227cm-1 place; Second-order transition temperature is at 198 ℃; (5%) 389 ℃ of decomposition temperature; Carbon yield 55% in the time of 600 ℃; Flame retardant resistance V0 level.
Show according to embodiment 4～9, adopt prepared resin of benzoxazine intermediate of the present invention and cured article thereof to have superior heat resistance and flame retardant resistance.Resin and cured article content thereof can both realized from fire-retardant more than 30%.
Claims (9)
1, a kind of benzoxazine colophony intermediate, its structural formula is as follows:
2, a kind of method for preparing the described benzoxazine colophony intermediate of claim 1 comprises the steps:
A, preparation cyano group side group diamine;
B, get the cyano group side group diamine 1mol of a step, phenol 2mol, formaldehyde or Paraformaldehyde 96 or 30%w/w formalin 4mol, one or both 10-50mol in toluene, dimethylbenzene, the dioxane;
C, get cyano group side group diamine, phenol is dissolved in toluene, slowly drips formaldehyde, the heating, temperature is controlled at 40～60 ℃, and formaldehyde dropwises reaction 3～5 hours, stopped reaction, with 40-70 ℃ hot wash 3-5 time, vacuumized 1～4 hour at 80～90 ℃, promptly get the benzoxazine intermediate.
3, according to the method for the described benzoxazine colophony intermediate of claim 2, it is characterized in that: the described method for preparing cyano group side group diamine of step a is:
A, take off the component of stating mole proportioning:
P-aminophenol 2mol, 2,6-dichlorobenzonitrile 1mol, catalyzer 1.1-1.5mol;
B, make p-aminophenol, 2, the 6-dichlorobenzonitrile, catalyzer, solvent, one or both in toluene, the dimethylbenzene are at 140-180 ℃ of reaction 4-8 hour, stopped reaction;
C, get in the step b gained reaction mixture impouring water and precipitate, add the dilute hydrochloric acid acidifying, filter, wash with water, in the 80-130 ℃ of vacuum drying oven dry 10-24 hour, promptly get cyano group side group diamine;
Wherein, the described catalyzer of step a is one or both in Anhydrous potassium carbonate, the anhydrous sodium carbonate;
The described solvent of step b is one or more in anhydrous dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, the N-Methyl pyrrolidone, and consumption is 100-500mol;
The described toluene consumption of step b is 10-50mol.
4, a kind of benzoxazine colophony, it is by the described benzoxazine colophony intermediate of claim 1, adds the copolymerization ring opening agent, is polymerized, its structural formula is as follows:
5, benzoxazine colophony according to claim 4, it is characterized in that: described copolymerization ring opening agent is a kind of in resol, general benzoxazine colophony or the Resins, epoxy, wherein, the copolymerization ring opening agent accounts for the 30-70% of the gross weight of copolymerization ring opening agent and benzoxazine colophony intermediate.
6, a kind of method for preparing claim 4 or 5 described benzoxazine colophonies, it comprises the steps:
A, get the benzoxazine colophony intermediate, add the copolymerization ring opening agent, wherein, the copolymerization ring opening agent accounts for the 30-70% of the gross weight of copolymerization ring opening agent and benzoxazine colophony intermediate;
B, 60-80 ℃ of reaction 2-3 hour, obtain benzoxazine colophony.
7, a kind of benzoxazine colophony cured article, it is that being heating and curing forms by after described benzoxazine intermediate, benzoxazine colophony or its mixing.
8, a kind of method for preparing the described benzoxazine colophony cured article of claim 7, it is characterized in that: it is by benzoxazine intermediate or resin or Hybrid Heating, under 160～220 ℃ of temperature curing reaction 1-5 hour, obtained the benzoxazine colophony cured article again at 250 ℃ of postheat treatment 3-8 hours.
9, the application of the described benzoxazine colophony cured article of claim 7 in coating, electronic package material, polymer matrix composites.
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| CN101265322B (en) * | 2008-05-08 | 2010-04-21 | 山东大学 | Preparation method of cyano-containing benzoxazine resin |
| WO2013056428A1 (en) * | 2011-10-18 | 2013-04-25 | 广东生益科技股份有限公司 | Benzoxazine intermediate and preparation method thereof |
| CN103963414A (en) * | 2014-05-27 | 2014-08-06 | 铜陵浩荣华科复合基板有限公司 | Method for preparing halogen-free and lead-free high-flame-retardant Tg copper-clad laminate |
| CN104356083A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
| CN104877133A (en) * | 2015-01-19 | 2015-09-02 | 广东顺德高耐特新材料有限公司 | Benzoxazine ring-containing aryl nitrile special resin and benzoxazine resin copolymer resin and industrial preparation method thereof |
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2006
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