CN103694191A - Polyfunctional group nitrile resin monomer and polymer and preparation method thereof - Google Patents

Polyfunctional group nitrile resin monomer and polymer and preparation method thereof Download PDF

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CN103694191A
CN103694191A CN201310667183.8A CN201310667183A CN103694191A CN 103694191 A CN103694191 A CN 103694191A CN 201310667183 A CN201310667183 A CN 201310667183A CN 103694191 A CN103694191 A CN 103694191A
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resin monomer
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刘孝波
徐明珍
邹兴强
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University of Electronic Science and Technology of China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G73/0644—Poly(1,3,5)triazines

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Abstract

The invention discloses a polyfunctional group nitrile resin monomer and polymer and a preparation method thereof, and belongs to the technical field of an organic high polymer material. The polyfunctional group nitrile resin monomer is a bisphthalonitrile resin monomer containing allyl and a benzoxazine ring, and the nitrile resin polymer is a heated and polymerized product of the nitrile resin monomer; the nitrile resin monomer has low viscosity and good mobility at low temperature, and the processing performances of low-temperature curing and the like; the nitrile resin polymer has good curing performances such as flame retardancy, adhesion, heat stability and the like. The resin monomer has good processing performance of the benzoxazine resin; the resin polymer also has high-temperature resistance of the nitrile resin, so that the curing temperature is reduced, the resin polymer can be used in a high-temperature environment, has the advantages of being 'low-temperature in processing, medium-temperature in molding, and high-temperature in use', and can be applied to the fields of paints, adhesives, electronic encapsulation materials, aviation, spaceflight, ships, resin composite materials, and the like. The preparation method is simple and easy to control, low in reaction temperature, energy-saving, and applicable to industrial production.

Description

A kind of polyfunctional group itrile group resin monomer and polymkeric substance and preparation method thereof
Technical field
The invention belongs to organic polymer material technical field, relate to bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, polymkeric substance and preparation method thereof.
Background technology
O-phthalonitrile resin as resistant to elevated temperatures type material the eighties in 20th century by the Keller of US Naval Research Laboratory and team develops thereof out.Because completely crued O-phthalic nitrile polymer has good thermostability and mechanical property, and good thermo-oxidative stability, flame retardant resistance and higher moisture resistivity, thereby this resinoid has been widely used at field tools such as aerospace, naval vessel, microelectronics and machinofacture.Yet; the melt temperature of bi-phthalonitrile resin (monomer) is up to 235 ℃; only low 20 ℃ than its curing reaction temperature; this makes its processing temperature window too narrow; and its thermofixation reaction is very slow; if just thermofixation, need to just can observe obvious gel in nearly hundred hours 280 ℃ of processing.Therefore, the high processing temperature of o-phthalonitrile resin, low solidification rate, high after fixing temperature has seriously limited processibility and the overall application of this kind of resin.
Benzoxazine colophony is as a kind of novel phenolic resins, not only there is good thermotolerance and flame retardant resistance, and overcome traditional resol and in shaping solidification process, discharged micromolecular shortcoming, the more important thing is that benzoxazine monomer has lower viscosity and good processibility, can be at lower temperature curing molding.Nineteen forty-four, Holly and Cope are at the favorite outer discovery benzoxazine compound of synthetic Mannich reaction product.Since 1949, the people Dui benzoxazines such as Burke synthetic carried out comparatively deep research, synthesized a series of compounds containing benzoxazine.1973, Schreiner reported first through benzoxazine ring-opening polymerization, prepare the research work of phenoplast, in succession applied for several patents.But the whole eighties in 20th century, the fundamental research of benzoxazine is in stagnating situation.Since the nineties, the people such as Hatsuo Ishida of U.S. Case Western Reserve university start polymerization reaction mechanism, structure and performance, the kinetics of polymerization reaction of Dui benzoxazine, the Thermal Decomposition Mechanism of polymkeric substance has been carried out systematic research, have greatly promoted the development of benzoxazine.Chinese invention patent CN99114603.4, CN03126518.9, CN02108772.5, CN03146797.0, CN02806290.6 etc. have invented preparation method and the application in veneer sheet and coating of multiple benzoxazine intermediate and resin, research and the application further enriching and expanded benzoxazine colophony.Yet, owing to existing the cross-linking density of chelating hydrogen bond Dao Zhi oxazine ring in a large amount of molecules lower than traditional thermosetting resins such as epoxy resin in benzoxazine ring-opening polymerization process, therefore thermotolerance and the flame retardant resistance of benzoxazine colophony are difficult to meet space flight, boats and ships, the requirement of the extreme field such as aviation to material thermal resistance and flame retardant resistance.
In addition, allyl group has been widely used in molecular designing and preparation in recent years, because allylic introducing provides extra cross-linking set, has improved the cross-linking density of system when reducing system curing initiation temperature.
Summary of the invention
The present invention is in conjunction with the reactive behavior of the low viscosity of benzoxazine resinoid, good mobility, low-temperature curing performance and allyl group, and the good thermostability of o-phthalonitrile resin, mechanical property, flame retardant resistance and higher anti-moisture performance, a kind of polyfunctional group itrile group resin monomer and polymkeric substance are provided.Described itrile group resin monomer is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, there is lower softening temperature and viscosity and mobility, make the more excellent processing characteristics of the more existing O-phthalic nitrile resin of this resin monomer, possess the more excellent heat-resistant fireproof performance of more existing benzoxazine resinoid simultaneously.Described itrile group resinous polymer is polymerized by described itrile group resin monomer, has the feature of machining at low temperature, middle temperature moulding, applied at elevated temperature, can be used for the fields such as coating, caking agent, electronic package material, Aeronautics and Astronautics, boats and ships and polymer matrix composites.The present invention provides the preparation method of described itrile group resin monomer and polymkeric substance simultaneously, and it is simply controlled that described preparation method has method, is suitable for the feature of suitability for industrialized production.
Technical solution of the present invention is:
(1) polyfunctional group itrile group resin monomer.
A polyfunctional group itrile group resin monomer, is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, and as shown in Figure 1, its structural formula is:
Figure BDA0000433958590000021
Wherein Ar as shown in Figure 2, represents:
Figure BDA0000433958590000022
Figure BDA0000433958590000023
in a kind of.
(2) preparation method of polyfunctional group itrile group resin monomer.
A preparation method for polyfunctional group itrile group resin monomer, as shown in Figure 3, comprises the following steps:
Step 1: an amido phenoxy group phthalonitrile, the organic monomer, formaldehyde and the solvent 1 that contain one or two phenyl ring and contain two allyl groups and two hydroxyl structures are added in the reaction vessel with division box, are heated at 60～90 ℃ back flow reaction 3～5 hours; Then emit water byproduct and toluene that in water trap, reaction generates, continue after intensification distills out toluene residual in reaction system to be cooled to room temperature.
Step 2: by precipitation, filtration in the reaction mixture impouring clear water of step 1, filter gained cured article with fully dry after a large amount of distilled water washs, obtain final product polyfunctional group itrile group resin monomer.
The molecular volume proportioning of the organic monomer that wherein, contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures, m-aminophenyl oxygen base phthalonitrile, formaldehyde is as follows:
The described organic monomer that contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures is diallyl bisphenol, diallyl '-biphenyl diphenol, two (3-allyl group-4-hydroxy phenyl) ketone, diallyl bisphenol S, 2, a kind of in 3-diallyl Resorcinol or 2,4-diallyl Resorcinol; Described solvent 1 is the arbitrary combination of toluene, dimethylbenzene or dioxane.
(3) polyfunctional group itrile group resinous polymer.
A kind of polyfunctional group itrile group resinous polymer, it is a kind of polymkeric substance of polyfunctional group itrile group resin monomer, its structure contains 2-methyl-2, the reticulated structure (as shown in Figure 4) of the Polybenzoxazine of 3-Dihydrobenzofuranes, nitrogenous Mannich bridge construction, π-pi-conjugated phthalocyanine ring and triazine ring for comprising.
The described structural formula containing Ju Yi Xi oxazine ring as described in Fig. 4 (a), for:
Figure BDA0000433958590000032
The Polybenzoxazine structural formula of described nitrogenous Mannich bridge construction as shown in Figure 4 (b), for:
Figure BDA0000433958590000033
The structural formula of described triazine ring as shown in Figure 4 (c), for:
Figure BDA0000433958590000041
The structural formula of described phthalocyanine ring as shown in Fig. 4 (d), for:
Figure BDA0000433958590000042
Wherein, described polyfunctional group itrile group resin monomer, is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, and as shown in Figure 1, its structural formula is:
Figure BDA0000433958590000043
Wherein Ar as shown in Figure 2, represents:
Figure BDA0000433958590000044
in a kind of.
(4) preparation method of polyfunctional group itrile group resinous polymer.
A preparation method for polyfunctional group itrile group resinous polymer, as described below: polyfunctional group itrile group resin monomer heating is reacted 1～5 hour at 120～200 ℃, then thermal treatment 3～5 hours at 250 ℃, polyfunctional group itrile group resinous polymer obtained.Wherein, described polyfunctional group itrile group resin monomer is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, and as shown in Figure 1, its structural formula is:
Figure BDA0000433958590000052
Wherein Ar as shown in Figure 2, represents:
Figure BDA0000433958590000054
in a kind of.Gained polyfunctional group itrile group resinous polymer is the polymkeric substance of described polyfunctional group itrile group resin monomer, and its structure is the reticulated structure (as shown in Figure 4) comprising containing Polybenzoxazine, π-pi-conjugated phthalocyanine ring and the triazine ring of Ju Yi Xi oxazine ring, nitrogenous Mannich bridge construction.
The described structure containing Ju Yi Xi oxazine ring as shown in Figure 4 (a), for:
The Polybenzoxazine structural formula of described nitrogenous Mannich bridge construction as shown in Figure 4 (b), for:
The structural formula of described triazine ring as shown in Figure 4 (c), for:
Figure BDA0000433958590000063
The structural formula of described phthalocyanine ring as shown in Fig. 4 (d), for:
Figure BDA0000433958590000064
Reaction mechanism of the present invention can be described below:
Polyfunctional group itrile group resin monomer provided by the present invention is by m-aminophenyl oxygen base phthalonitrile, the organic monomer that contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures, in the selected anhydrous solvent of the present invention, under the condition simultaneously existing at formaldehyde, through Mannich condensation reaction, obtain.
Itrile group resin monomer provided by the present invention is the ring-opening reaction of Fa Sheng oxazine ring first under heating or katalysis, the polymerization simultaneously of open loop oxazine structure forms the Polybenzoxazine of nitrogenous Mannich bridge construction, meanwhile, ring-opening polymerization produces a large amount of activity hydroxies.Between the active phenolic hydroxyl group producing and allyl group, can, by carbonium ion mechanism generation addition reaction, form the ring texture of dihydro substituted furan.In addition, the people such as Keller finds: in o-phthalonitrile resin cyano group can under certain heating condition, there is polyaddition reaction, in the process of catalysis bi-phthalonitrile polymerization, the effectively polymerization of catalysis itrile group of a large amount of activity hydroxies that the ring-opening polymerization of benzoxazine ring produces.In addition, the people such as Burchill think that cyano group crosslinking reaction, its product are to take triazine ring and phthalocyanine cyclic cpds as main.What form take the network structure that the fragrant heterocycles such as phthalocyanine ring and triazine ring are cross-linking set, has given the resistance toheat of this kind of resin excellence.
The structure of itrile group resin monomer provided by the invention and polymkeric substance is used Fourier infrared (FTIR) spectrograph to carry out characterization test.The thermal analysis experiment of itrile group resinous polymer provided by the invention adopts differential scanning calorimeter MQ100 (DSC) and the thermal gravimetric analyzer Q50 of U.S. TA company of U.S. TA company to carry out.Wherein, the fusing point of itrile group resin monomer and curing summit temperature adopt DSC10 ℃/min to test; The carbon yield when temperature while decomposing 5% and 800 ℃ adopts TGA20 ℃/min to test.
Itrile group resin monomer provided by the invention and polymkeric substance, used Fourier infrared (FTIR) spectrograph to carry out characterization test to its structure.Wherein, the charateristic avsorption band of itrile group resin monomer exists: 1171 and 832cm -1(C-N-C); 2967cm -1(CH 3); 2230cm -1(CN); 1246,1208cm -1(Ar-O-Ar); 832,782,729cm -1(charateristic avsorption band of phenyl ring), 1638,997,912cm -1(CH 2=CH), this test result shows that itrile group resin monomer provided by the invention is a kind of bi-phthalonitrile resin monomer (because having occurred above charateristic avsorption band on resin infared spectrum) containing allyl group and benzoxazine ring.The charateristic avsorption band of itrile group resinous polymer exists: 1010cm -1(phthalocyanine ring); 1360cm -1and 1520cm -1(triazine ring); 1246,1208cm -1(ehter bond); 832,782,729cm -1(charateristic avsorption band of phenyl ring), this test result shows that described itrile group resinous polymer is for the bi-phthalonitrile resin polymkeric substance (having occurred above charateristic avsorption band on the infared spectrum because of resin cured matter) containing allyl group and benzoxazine ring.
The performance perameter of the bi-phthalonitrile resin containing allyl group and benzoxazine ring provided by the invention is:
Softening temperature: 70～110 ℃; DSC solidifies peak temperature: 220～260 ℃; The temperature of decomposition 5%: 440～490 ℃; The carbon yield of 800 ℃: 75-85%.
Itrile group resin monomer provided by the invention, thering is excellent shaping performance and thering is the macromolecule resin matrix of extensive use of a kind of introducing benzoxazine structure of new acquisition and allylic structure, there is good Molecular Structure Design, the type of the organic monomer that is contained one or two phenyl ring and contained two hydroxyl structures by change, can regulate and control structure and the performance of resin monomer and polymkeric substance thing thereof well.Itrile group resin monomer provided by the invention has lower softening temperature and melting viscosity, has good mobility under lesser temps, has improved greatly the processibility of resin.Itrile group resinous polymer provided by the invention has good activity of curing reaction, and water-intake rate is extremely low, has curing processing temperature that benzoxazine colophony is low and the resistance to elevated temperatures of bi-phthalonitrile.In addition, itrile group resinous polymer provided by the invention contains polarity-CN group, can greatly increase cementability and affinity with material, for preparing high performance composite; There is reactable with metal ion, be applied to the better effects if of metal high temperature resistant adhesive; There is insulativity, can be used for high-temperature insulation material field.Preparation method of the present invention is simply effective, and reaction process is simply controlled, and product has good market outlook.
In sum, beneficial effect of the present invention is embodied in:
1, by regulating raw materials used (organic monomer that contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures) and formula, can obtain and possess benzoxazine resinoid low viscosity, the serial polyfunctional group itrile group resin monomer of the processing advantages such as excellent fluidity and low-temperature curing performance.
2, by serial itrile group resin monomer heated polymerizable gained series itrile group resinous polymer, contain Polybenzoxazine structure and π-pi-conjugated phthalocyanine ring structure and the triazine ring structure that replaces benzo furan structure, nitrogenous Mannich bridge containing dihydro, thereby give the thermal stability that material is very high.
3, the raw material (organic monomer that contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures) that uses different structure is structure and the performance of regulation and control itrile group resin monomer and polymkeric substance in very large range.
4, described itrile group resin monomer and polymkeric substance meet the requirement of " machining at low temperature, middle temperature moulding, applied at elevated temperature ", can be widely used in the fields such as coating, caking agent, electronic package material, Aeronautics and Astronautics, boats and ships and polymer matrix composites.And preparation method is simple and easy to control, temperature of reaction is lower, energy-conservation, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the structural formula of polyfunctional group itrile group resin monomer provided by the invention.
Fig. 2 is the six kinds of structures of Ar in polyfunctional group itrile group resin monomer provided by the invention.
Fig. 3 is a kind of preparation method's schematic flow sheet of polyfunctional group itrile group resin monomer provided by the invention.
Fig. 4 is four kinds of structures that comprise in polyfunctional group itrile group resinous polymer provided by the invention, wherein (a) is the structure containing Ju Yi Xi oxazine ring, (b) being the Polybenzoxazine structural formula of nitrogenous Mannich bridge construction, (c) being the structural formula of triazine ring, is (d) structural formula of phthalocyanine ring.
Embodiment
Below the present invention will be further described for the description by embodiment, but this is not limitation of the present invention, those skilled in the art, according to basic thought of the present invention, can make various modification or modification, only otherwise depart from basic thought of the present invention, all within the scope of the present invention.
Embodiment mono-
(1) preparation of bisphenol A-type polyfunctional group itrile group resin monomer:
Step 1: amido phenoxy group phthalonitrile, diallyl bisphenol, formaldehyde, dioxane/toluene are added in the reaction vessel with division box, are heated at 90 ℃ back flow reaction 5 hours; Then emit water byproduct and toluene that in water trap, reaction generates, continue after intensification distills out toluene residual in reaction system to be cooled to room temperature.
Step 2: by precipitation, filtration in the reaction mixture impouring clear water of step 1, filter gained cured article with fully dry after a large amount of distilled water washs, obtain final product bisphenol A-type polyfunctional group itrile group resin monomer.
Wherein, diallyl bisphenol, m-aminophenyl oxygen base phthalonitrile, formaldehyde, dioxane/toluene molecular volume proportioning as follows:
Diallyl bisphenol (mole) 1
M-aminophenyl oxygen base phthalonitrile (mole) 2
Formaldehyde (mole) 4
Dioxane/toluene (milliliter) 10～50
The bisphenol A-type polyfunctional group itrile group resin monomer softening temperature making is thus 70 ℃, and curing summit temperature is 220 ℃.The infared spectrum of this resin monomer is 1171 and 832cm -1(C-N-C); 2967cm -1(CH 3); 2231cm -1(CN); 1246,1208cm -1(Ar-O-Ar); 832,782,729cm -1(phenyl ring), 1638,997,912cm -1(CH 2=CH) locate to have occurred charateristic avsorption band, shown to obtain the bi-phthalonitrile resin containing allyl group and benzoxazine ring.
(2) preparation of bisphenol A-type polyfunctional group itrile group resinous polymer:
The bisphenol A-type polyfunctional group itrile group resin monomer of preparing is above heated to react 1-5 hour at 120～200 ℃, then thermal treatment 3～5 hours at 250 ℃, bisphenol A-type polyfunctional group itrile group resinous polymer obtained.
This bisphenol A-type polyfunctional group itrile group resinous polymer 1010cm -1(phthalocyanine ring); 1360cm -1and 1520cm -1(triazine ring); 1246,1208cm -1(Ar-O-Ar); 832,782,729cm -1(phenyl ring) locates all to have occurred charateristic avsorption band, shown to obtain the bi-phthalonitrile resin polymkeric substance containing allyl group and benzoxazine ring.250 ℃ of processing of bisphenol A-type polyfunctional group itrile group resinous polymer of preparing according to the method are after 3 hours, and the temperature while decomposing 5% is 429 ℃; Carbon yield under the nitrogen atmosphere of 800 ℃ is 75%.
Embodiment bis-
(2) preparation of '-biphenyl diphenol type polyfunctional group itrile group resin monomer:
Step 1: amido phenoxy group phthalonitrile, '-biphenyl diphenol, formaldehyde, dioxane/toluene are added in the reaction vessel with division box, are heated at 90 ℃ back flow reaction 5 hours; Then emit water byproduct and toluene that in water trap, reaction generates, continue after intensification distills out toluene residual in reaction system to be cooled to room temperature.
Step 3: by precipitation, filtration in the reaction mixture impouring clear water of step 1, filter gained cured article with fully dry after a large amount of distilled water washs, obtain final product '-biphenyl diphenol type polyfunctional group itrile group resin monomer.
Wherein, '-biphenyl diphenol, m-aminophenyl oxygen base phthalonitrile, formaldehyde, dioxane/toluene, molecular volume proportioning are as follows:
'-biphenyl diphenol (mole) 1
M-aminophenyl oxygen base phthalonitrile (mole) 2
Formaldehyde (mole) 4
Dioxane/toluene (milliliter) 10～50
The '-biphenyl diphenol type itrile group resin monomer softening temperature making is thus 85 ℃, and curing summit temperature is 230 ℃.The infared spectrum of this resin monomer is 1171 and 832cm -1(C-N-C); 2967cm -1(CH 3); 2231cm -1(CN); 1246,1208cm -1(Ar-O-Ar); 832,782,729cm -1(phenyl ring), 1638,997,912cm -1(CH 2=CH) locate to have occurred charateristic avsorption band, shown to obtain the bi-phthalonitrile resin containing allyl group and benzoxazine ring.
(2) preparation of '-biphenyl diphenol type polyfunctional group itrile group resinous polymer:
'-biphenyl diphenol type polyfunctional group itrile group resin monomer noted earlier is heated to react 1-5 hour at 120～200 ℃, then thermal treatment 3～5 hours at 250 ℃, '-biphenyl diphenol type polyfunctional group itrile group resinous polymer obtained.
This '-biphenyl diphenol type polyfunctional group itrile group resinous polymer is at 1010cm -1(phthalocyanine ring); 1360cm -1and 1520cm -1(triazine ring); 1246,1208cm -1(Ar-O-Ar); 832,782,729cm -1(phenyl ring) locates all to have occurred charateristic avsorption band, shown to obtain the bi-phthalonitrile resin polymkeric substance containing allyl group and benzoxazine ring.The resin cured matter of preparing according to this step is processed after 3 hours at 250 ℃, and the temperature while decomposing 5% is 450 ℃; Carbon yield under the nitrogen atmosphere of 800 ℃ is 80%.
By above-mentioned embodiment, can be found out: polyfunctional group itrile group resin monomer provided by the invention and polymkeric substance have low softening point, wide processing temperature window, on DSC spectrogram, curing exothermic peak appears at 220～260 ℃.Under the nitrogen atmosphere of 800 ℃, decompose 440～490 ℃ of 5% temperature; Thermolysis carbon yield surpasses 70%.Thereby polyfunctional group itrile group resin monomer provided by the invention and polymkeric substance have significantly been widened the process window of bi-phthalonitrile, have improved its processibility.The itrile group resinous polymer obtaining by this method had both improved traditional narrow shortcoming of bi-phthalonitrile process window, thermotolerance is also kept simultaneously, can prepare matrix material for fields such as Aeronautics and Astronautics, naval vessels, can prepare insulating material, caking agent, electronic package material for electronic applications again; Can also prepare for mechanical manufacturing field matrix material, caking agent of high strength and modulus etc.

Claims (4)

1. a polyfunctional group itrile group resin monomer, is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, and as shown in Figure 1, its structural formula is:
Wherein Ar as shown in Figure 2, represents:
Figure FDA0000433958580000012
Figure FDA0000433958580000013
in a kind of.
2. a preparation method for polyfunctional group itrile group resin monomer, as shown in Figure 3, comprises the following steps:
Step 1: an amido phenoxy group phthalonitrile, the organic monomer, formaldehyde and the solvent 1 that contain one or two phenyl ring and contain two allyl groups and two hydroxyl structures are added in the reaction vessel with division box, are heated at 60～90 ℃ back flow reaction 3～5 hours; Then emit water byproduct and toluene that in water trap, reaction generates, continue after intensification distills out toluene residual in reaction system to be cooled to room temperature.
Step 2: by precipitation, filtration in the reaction mixture impouring clear water of step 1, filter gained cured article with fully dry after a large amount of distilled water washs, obtain final product polyfunctional group itrile group resin monomer.
The molecular volume proportioning of the organic monomer that wherein, contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures, m-aminophenyl oxygen base phthalonitrile, formaldehyde is as follows:
The described organic monomer that contains one or two phenyl ring and contain two allyl groups and two hydroxyl structures is diallyl bisphenol, diallyl '-biphenyl diphenol, two (3-allyl group-4-hydroxy phenyl) ketone, diallyl bisphenol S, 2, a kind of in 3-diallyl Resorcinol or 2,4-diallyl Resorcinol; Described solvent 1 is the arbitrary combination of toluene, dimethylbenzene or dioxane.
3. a polyfunctional group itrile group resinous polymer, it is a kind of polymkeric substance of polyfunctional group itrile group resin monomer, its structure contains 2-methyl-2, the reticulated structure (as shown in Figure 4) of the Polybenzoxazine of 3-Dihydrobenzofuranes, nitrogenous Mannich bridge construction, π-pi-conjugated phthalocyanine ring and triazine ring for comprising.
Described containing 2-methyl-2, the structural formula of 3-Dihydrobenzofuranes as described in Fig. 4 (a), for:
Figure FDA0000433958580000022
The Polybenzoxazine structural formula of described nitrogenous Mannich bridge construction as shown in Figure 4 (b), for:
Figure FDA0000433958580000023
The structural formula of described triazine ring as shown in Figure 4 (c), for:
Figure FDA0000433958580000031
The structural formula of described phthalocyanine ring as shown in Fig. 4 (d), for:
Figure FDA0000433958580000032
Wherein, described polyfunctional group itrile group resin monomer, is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, and as shown in Figure 1, its structural formula is:
Figure FDA0000433958580000033
Wherein Ar as shown in Figure 2, represents:
Figure FDA0000433958580000034
Figure FDA0000433958580000041
in a kind of.
4. a preparation method for polyfunctional group itrile group resinous polymer, as described below: the heating of polyfunctional group itrile group resin monomer is reacted 1～5 hour at 120～200 ℃, then thermal treatment 3～5 hours at 250 ℃, polyfunctional group itrile group resinous polymer obtained.Wherein, described polyfunctional group itrile group resin monomer is a kind of bi-phthalonitrile resin monomer containing allyl group and benzoxazine ring, and as shown in Figure 1, its structural formula is:
Figure FDA0000433958580000042
Wherein Ar as shown in Figure 2, represents:
Figure FDA0000433958580000044
in a kind of.Gained polyfunctional group itrile group resinous polymer is the polymkeric substance of described polyfunctional group itrile group resin monomer, its structure contains 2-methyl-2, the reticulated structure (as shown in Figure 4) of the Polybenzoxazine of 3-Dihydrobenzofuranes, nitrogenous Mannich bridge construction, π-pi-conjugated phthalocyanine ring and triazine ring for comprising.
Described containing 2-methyl-2, the structure of 3-Dihydrobenzofuranes as shown in Figure 4 (a), for:
Figure 20131066718381000011
the Polybenzoxazine structural formula of described nitrogenous Mannich bridge construction as shown in Figure 4 (b), for:
The structural formula of described triazine ring as shown in Figure 4 (c), for:
Figure FDA0000433958580000053
The structural formula of described phthalocyanine ring as shown in Fig. 4 (d), for:
Figure FDA0000433958580000054
。
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CN109593070A (en) * 2018-11-14 2019-04-09 广东汕头超声电子股份有限公司覆铜板厂 Nitrile-based resin for high-frequency and high-speed copper-clad plate and preparation method thereof
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