CN102516766A - Hexagonal boron nitride/thermosetting resin composite material and preparation method thereof - Google Patents
Hexagonal boron nitride/thermosetting resin composite material and preparation method thereof Download PDFInfo
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- CN102516766A CN102516766A CN2011103872681A CN201110387268A CN102516766A CN 102516766 A CN102516766 A CN 102516766A CN 2011103872681 A CN2011103872681 A CN 2011103872681A CN 201110387268 A CN201110387268 A CN 201110387268A CN 102516766 A CN102516766 A CN 102516766A
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Abstract
The invention discloses a hexagonal boron nitride/thermosetting resin composite material and a preparation method thereof. The method comprises the following steps of: uniformly mixing 100 parts by weight of thermosetting resin and 5-50 parts by weight of surface modified hexagonal boron nitride at resin melting temperature; and defoaming and then curing according to a curing process of resin to obtain the hexagonal boron nitride/thermosetting resin composite material. The surface modified hexagonal boron nitride is formed by converting a secondary amino group and a hydroxyl group with weak activity on the original surface into a primary amine group with strong activity through a chemical method; and -NH2 contained in the surface of the modified hexagonal boron nitride reaches over 0.5 percent by weight. Compared with the conventional thermosetting resin, the composite material prepared by the invention has superior performance of high heat conductivity, low thermal expansion coefficient and low dielectric loss on the basis of keeping the heat resistance of the original thermosetting resin. The adopted preparation method has the characteristics of broad applicability and simple operation process.
Description
Technical field
The present invention relates to a kind of hexagonal boron nitride/thermoset ting resin composite and preparation method thereof, belong to technical field of polymer composite materials.
Background technology
Excellent comprehensive performances such as performance resins is big owing to its rigidity, hardness is high, heatproof is high, nonflammable are widely used in industrial circle, become the research emphasis of field of materials.But at some special industrial circles, like aerospace, electric etc., existing high-performance thermosetting resin exists defectives such as thermal conductivity is low, thermal expansivity is high, dielectric loss height, and increasingly high leading-edge field can't meet the demands.Therefore, how on the stable on heating basis that keeps existing thermosetting resin to be had, make it to have concurrently characteristics such as high heat conduction, low thermal coefficient of expansion, low-dielectric loss, have crucial meaning.
Adding mineral filler to improve the thermosetting resin performance, is the simplest, convenient, economy, effective means.Bibliographical information adopt hexagonal boron nitride or similar pottery to prepare the technology of highly heat-conductive material, for example, document (1. Tung-lin Li is arranged; Steve Lien-chung Hsu; Preparation and properties of thermally conductive photosensitive polyimide/boron nitride nanocomposites, Journal of Applied Polymer Science, 2011; 121,916 – 922; 2. Wen-ying Zhou, Shu-hua Qi, Hong-zhen Zhao and Nai-liang Liu; Thermally conductive silicone rubber reinforced with boron nitride particle; Polymer Composites, 2007,28; 23-28) reported hexagonal boron nitride has been filled in the polymkeric substance, improved the thermal conductivity of polymkeric substance significantly; These research work prove that adding hexagonal boron nitride is an effective way that improves thermal conductivity in polymkeric substance.But there is the group that can be used for chemical reaction hardly in the surface of hexagonal boron nitride, has only amino and the hydroxyl that there be minute quantity in the edge of its laminate structure (referring to document Mitchell T. Huang; Hatsuo Ishida; Investigation of the boron nitride/polybenzoxazine interphase, Journal of Polymer Science:Part B:Polymer Physics, 1999; 37,2360-2372).Therefore, usually, the dispersiveness of hexagonal boron nitride in polymkeric substance is difficult to guarantee that the interfacial property of prepared matrix material is not good, causes the performance advantage of hexagonal boron nitride in matrix material, not to be not fully exerted.Therefore the surface treatment of hexagonal boron nitride becomes the preparation and the key in application of high-performance hexagonal boron nitride/polymer composites.
At present; People often adopt silane coupling agent that hexagonal boron nitride is carried out surface treatment; But because this method is mainly used in the more inorganics of surperficial hydroxyl; For SP 1 is not very to be suitable for, and causes the interfacial adhesion between hexagonal boron nitride and the polymkeric substance not good, thereby makes the over-all properties of hexagonal boron nitride be difficult in matrix material, embody.Document (R. Kochetov, T. Andritsch, U. Lafont are arranged; P.H.F. Morshuis, S.J. Picken, J.J. Smit; Preparation and dielectric properties of epoxy-BN and epoxy-AlN nanocomposites, IEEE Electrical Insulation Conference, 2009; 397-400) spell out, as hexagonal boron nitride surface-treated domestic method, silane coupling agent is handled partly success of SP 1; This is because silane coupling agent can only react with one deck boron oxide on SP 1 surface, and the course of processing that how much depends on SP 1 of boron oxide.Yet; Except the silane coupling agent facture; At present do not see the method that better hexagonal boron nitride surface-treated is arranged, therefore, adopt new hexagonal boron nitride surface treatment method; And then keeping on the stable on heating basis of thermosetting resin, comprehensive exsertile high-performance hexagonal boron nitride/polymkeric substance that preparation has performance characteristics such as high heat conduction, low thermal coefficient of expansion, low-dielectric loss has important significance for theories and actual application value.
Summary of the invention
In order to overcome the deficiency that prior art exists; The object of the present invention is to provide a kind of the maintenance on the stable on heating basis of thermosetting resin, with hexagonal boron nitride/thermoset ting resin composite of performance characteristics such as high heat conduction, low thermal coefficient of expansion, low-dielectric loss and preparation method thereof.
For reaching the foregoing invention purpose; The technical scheme that the present invention adopts provides a kind of hexagonal boron nitride/thermoset ting resin composite; By weight; It comprises the hexagonal boron nitride of 100 parts of thermosetting resins and 5～50 parts of surface-treateds, the hexagonal boron nitride of said surface-treated be the surface contain 0.5 wt% above-NH
2Hexagonal boron nitride.
Thermosetting resin of the present invention is bimaleimide resin, cyanate ester resin, epoxy resin, or their arbitrary combination.
Technical scheme of the present invention also provides a kind of method for preparing above-mentioned hexagonal boron nitride/thermoset ting resin composite, comprises the steps:
1, press mass ratio 1:20～1:100, hexagonal boron nitride is mixed with anhydrous organic solvent, homodisperse under the ultrasonic agitation condition obtains mixture;
2, under the protection of inert gas, adding is the vulcabond of 1:0.5～1:2 with hexagonal boron nitride by mass ratio in mixture, under 50～110 ℃ temperature, reacts 20～50 minutes; After reaction finishes, immediately reaction product is filtered, washed, obtain intermediate product;
3, press mass ratio 1:20～1:100, the resulting intermediate product of step 2 is dispersed in the anhydrous organic solvent, obtain dispersion liquid; To be that the diaminodiphenylsulfone(DDS) of 1:1～1:2 slowly joins in the dispersion liquid by mass ratio with vulcabond in the step 2, be reaction 8～16 hours under 40～70 ℃ the agitation condition in temperature; After reactant filtration, washing, obtain the hexagonal boron nitride of surface-treated;
4, by weight, 100 parts of thermosetting resins and 5～50 parts of hexagonal boron nitrides through surface-treated are mixed, after deaeration, solidifying, obtain a kind of hexagonal boron nitride/thermoset ting resin composite.
Organic solvent of the present invention is acetone, toluene, N, a kind of in the dinethylformamide, or their arbitrary combination.
Compared with prior art, the beneficial effect that the present invention obtained is:
1, the surface-treated hexagonal boron nitride that the present invention adopted is converted into active strong primary amino with the form of chemical bond secondary amino group and the hydroxyl a little less than with surfactivity; Not only increased the number of functional groups of hexagonal boron nitride surface and thermosetting resin reaction; Also strengthened the activity of functional group, for hexagonal boron nitride obtains good dispersion and consistency provides very favorable condition in resin matrix.
2, the prepared matrix material of the present invention has excellent comprehensive performances such as high heat-resisting, high heat conduction, low thermal coefficient of expansion, low-dielectric loss, has a extensive future.
3, the starting material source that the present invention adopted is abundant, inexpensive, and preparation technology's suitability is wide, simple to operate.
Description of drawings
Fig. 1 is the reaction mechanism synoptic diagram of the hexagonal boron nitride surface-treated that provides of the embodiment of the invention 3;
Fig. 2～4th, the infared spectrum comparison diagram of the hexagonal boron nitride before and after the modification that the embodiment of the invention 3 provides;
Fig. 5 is the XPS collection of illustrative plates comparison diagram of the hexagonal boron nitride before and after the modification that provides of the embodiment of the invention 3;
Fig. 6 is the TG collection of illustrative plates comparison diagram of the hexagonal boron nitride before and after the modification that provides of the embodiment of the invention 3;
Wideband dielectric loss curve comparison diagram under hexagonal boron nitride/bismaleimide resin composite material room temperature that bimaleimide resin that Fig. 7 is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 3 provide;
The thermal conductivity curve comparison diagram of hexagonal boron nitride/bismaleimide resin composite material that bimaleimide resin that Fig. 8 is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 2 and 3 provide;
The thermal expansivity curve comparison diagram of hexagonal boron nitride/bismaleimide resin composite material that bimaleimide resin that Fig. 9 is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 2 and 3 provide;
The loss tangent curve comparison diagram of hexagonal boron nitride/bismaleimide resin composite material that bimaleimide resin that Figure 10 is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 3 provide.
Embodiment
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is done to describe further.
Embodiment 1
1, the preparation of surface-treated hexagonal boron nitride
(1) the 4A molecular sieve after the activation is put into N, 24 h in the dinethylformamide, underpressure distillation then, the cut of collection 76 ℃/4800 Pa (36 mmHg) obtains anhydrous N, dinethylformamide.
(2) in 250 ml there-necked flasks, add the N that 2 g hexagonal boron nitrides and 50 ml handle through step (1), the dinethylformamide solvent, ultrasonic agitation 20 min make hexagonal boron nitride be evenly dispersed in N, in the dinethylformamide solvent.
(3) under the nitrogen protection, in there-necked flask, add 2 g 4,4 '-methylene-bis (phenylcarbimide) is at 50 ℃ of back flow reaction 20 min.After reaction finishes, the reaction product fast vacuum is filtered, use N, dinethylformamide washs 4 times, and unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product, is designated as IhBN.
(4) 2 g IhBN are dispersed in N, in the dinethylformamide, obtain dispersion liquid, then in dispersion liquid, add 2 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 40 ℃ of lower magnetic force stirring reactions 8 hours; After reaction finished, with reactant vacuum filtration, washing 4 times, the product that obtains was designated as OhBN.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 25 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 2.36 g OhBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+160 ℃/2h+180 ℃/2h+200 ℃/2h and 220 ℃/4 h.
Embodiment 2
1, the preparation of surface-treated hexagonal boron nitride
(1) the 4A molecular sieve after the activation is put into N, 24 h in the dinethylformamide, underpressure distillation then, the cut of collection 76 ℃/4800 Pa (36 mmHg) obtains anhydrous N, dinethylformamide.
(2) in 250 ml there-necked flasks, add the N that 5 g hexagonal boron nitrides and 200 ml handle through step (1), the dinethylformamide solvent, ultrasonic agitation 60 min make hexagonal boron nitride be evenly dispersed in N, in the dinethylformamide solvent.
(3) under the nitrogen protection, in there-necked flask, add 5 g 4,4 '-methylene-bis (phenylcarbimide) is at 110 ℃ of back flow reaction 50 min.After reaction finishes, the reaction product fast vacuum is filtered, use N, dinethylformamide washs 6 times, and unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product, is designated as IhBN.
(4) 5 g IhBN are dispersed in N, in the dinethylformamide, obtain dispersion liquid, then in dispersion liquid, add 5 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 70 ℃ of lower magnetic force stirring reactions 16 hours; After reaction finished, with reactant vacuum filtration, washing 6 times, the product that obtains was designated as OhBN.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 35 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 28.6 g OhBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 160 ℃/2h of technology+180 ℃/2h+200 ℃/2h+230 ℃/2h and 250 ℃/4 h
Embodiment 3
1, the preparation of surface-treated hexagonal boron nitride
(1) the 4A molecular sieve after the activation is put into N, 24 h in the dinethylformamide, underpressure distillation then, the cut of collection 76 ℃/4800 Pa (36 mmHg) obtains anhydrous N, dinethylformamide.
(2) in 250 ml there-necked flasks, add the N that 3 g hexagonal boron nitrides and 100 ml handle through step (1), the dinethylformamide solvent, ultrasonic agitation 30 min make hexagonal boron nitride be evenly dispersed in N, in the dinethylformamide solvent.
(3) under the nitrogen protection, in there-necked flask, add 3 g 4,4 '-methylene-bis (phenylcarbimide) is at 70 ℃ of back flow reaction 30 min.After reaction finishes, the reaction product fast vacuum is filtered, use N, dinethylformamide washs 5 times, and unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product, is designated as IhBN.Take out part IhBN, behind the baking oven inner drying, carry out the test of ir spectra, its infrared spectrum is shown in Fig. 2～4.
(4) 3 g IhBN are dispersed in N, in the dinethylformamide, obtain dispersion liquid, then in dispersion liquid, add 3 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 50 ℃ of lower magnetic force stirring reactions 12 hours; After reaction finished, with reactant vacuum filtration, washing 5 times, the product that obtains was designated as OhBN.With carrying out the analyses of ir spectra (IR), x-ray photoelectron power spectrum (XPS) and thermogravimetric (TG) after the OhBN drying, with functional group that identifies the hexagonal boron nitride surface grafting and the organic content of measuring the hexagonal boron nitride surface grafting.The gained spectrogram is seen Fig. 2～4,5 and 6 respectively.
Referring to accompanying drawing 1, it is the reaction mechanism synoptic diagram of the hexagonal boron nitride surface-treated in the embodiment of the invention; Among the figure, hBN is a hexagonal boron nitride, and IhBN is an intermediate product, and OhBN is the hexagonal boron nitride of surface-treated.As shown in Figure 1, hexagonal boron nitride (hBN) and 4, after 4 '-methylene-bis (phenylcarbimide) reaction, the functional group that it is surperficial comprises that hydroxyl, primary amino, secondary amino group have all passed through in the chemical bond grafting NCO, has obtained intermediate product (IhBN); Warp reacts with diaminodiphenylsulfone(DDS) again, and NCO all transforms for primary amino, and soon active weak secondary amino group and hydroxyl are converted into active strong primary amino on the original surface, obtain the hexagonal boron nitride (OhBN) of surface-treated.
Accompanying drawing 2 is infared spectrum comparison diagrams of the hexagonal boron nitride before and after the modification that provides in the present embodiment, and accompanying drawing 3 is wave number (cm in Fig. 2 spectrogram
-1) at the partial enlarged drawing at 2000～2500 places, accompanying drawing 4 is wave number (cm in Fig. 2 spectrogram
-1) at the partial enlarged drawing at 1400～2000 places.Referring to accompanying drawing 3, compare with the spectrogram of hBN, from the spectrogram of IhBN, can clearly see at 2270 cm
-1There is a new absorption peak in the place; This is the vibration absorption peak of NCO functional group, shows 4, and 4 '-methylene-bis (phenylcarbimide) has arrived the hBN surface through the chemical bond grafting; And the NCO functional group in the grafting still has activity, can further react.Referring to accompanying drawing 4, can see from the spectrogram of OhBN, the absorption peak completely dissolve of NCO functional group, this shows NCO functional group fully and the diaminodiphenylsulfone(DDS) reaction, OhBN has been with amino in the surface; In addition, amino I and II absorption peak (1647 and 1551 cm among the OhBN
-1) intensity be higher than the respective peaks of IhBN, further show on the OhBN surface and contain amino.
Referring to accompanying drawing 5, it is the XPS collection of illustrative plates comparison diagram of the hexagonal boron nitride before and after the modification that provides in the present embodiment; As shown in Figure 5; In the scanning wide range of hBN, can observe absorption peak at bound energy 531,398,286,190,152 and 102 eV places; The corresponding O 1s of difference, N 1s, C 1s; B 1s, the absorption peak of Si 2s and Si 2p (appearance of Si 2s and Si 2p bound energy absorption peak is owing to when carrying out the XPS test, used silicon chip to work as carrier).A new small peak occurred and in the scanning wide range of OhBN, can observe at bound energy 165 eV places, this is the absorption peak of S 2p, and further strong proof title product OhBN successfully obtains.
Referring to accompanying drawing 6, it is the TG collection of illustrative plates comparison diagram of the hexagonal boron nitride before and after the modification that provides of present embodiment, and the percentage of grafting that therefrom can obtain OhBN is 17.6 wt% ,-NH
2Content be 0.562 wt%, be about hexagonal boron nitride before the modification-NH
2The amount 5 times.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 2.61 g OhBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 4
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds prepared surface-treated hexagonal boron nitride among the 7.83 g embodiment 3, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 5
1, the preparation of surface-treated hexagonal boron nitride
(1) in 250 ml toluene, add 4 g sodium, 2 h that reflux add 150 mg UVNUL MS-40 again, become blueness after, 110～111 ℃ of cuts are collected in distillation, obtain dry toluene.
(2) in 250 ml there-necked flasks, add the toluene solvant that 3 g hexagonal boron nitrides and 100 ml handle through step (1), ultrasonic agitation 30 min make hexagonal boron nitride be evenly dispersed in the toluene solvant.
(3) under the nitrogen protection, in there-necked flask, add 3 g 4,4 '-methylene-bis (phenylcarbimide) is at 70 ℃ of back flow reaction 30 min.After reaction finishes, the reaction product fast vacuum is filtered, with toluene wash 5 times, unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product, is designated as IhBN.
(4) 3 g IhBN are dispersed in the toluene, obtain dispersion liquid, then in dispersion liquid, add 3 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 50 ℃ of lower magnetic force stirring reactions 12 hours; After reaction finished, with reactant vacuum filtration, washing 5 times, the product that obtains was designated as OhBN.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 3 g OhBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 6
1, the preparation of surface-treated hexagonal boron nitride
(1) 100 mL acetone are packed in the separating funnel, add 4 ml, 10 % silver nitrate solutiones earlier, add 3.6 ml, 1 mol/L sodium hydroxide solution again, jolting 10 min tell the acetone layer, add anhydrous potassium sulfate or anhydrous calciumsulphate again and carry out drying.55～56.5 ℃ of cuts are collected in distillation at last, obtain anhydrous propanone.
(2) in 250 ml there-necked flasks, add the acetone solvent that 3 g hexagonal boron nitrides and 100 ml handle through step (1), ultrasonic agitation 30 min make hexagonal boron nitride be evenly dispersed in the acetone solvent.
(3) under the nitrogen protection, in there-necked flask, add 3 g 4,4 '-methylene-bis (phenylcarbimide) is at 70 ℃ of back flow reaction 30 min.After reaction finishes, the reaction product fast vacuum is filtered, with washing with acetone 5 times, unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product, is designated as IhBN.
(4) 3 g IhBN are dispersed in the acetone, obtain dispersion liquid, then in dispersion liquid, add 3 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 50 ℃ of lower magnetic force stirring reactions 12 hours; After reaction finished, with reactant vacuum filtration, washing 5 times, the product that obtains was designated as OhBN.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 4 g OhBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
3, the preparation of Comparative Examples
Comparative Examples 1, the preparation of bimaleimide resin: take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of bimaleimide resin according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Comparative Examples 2, the preparation of hexagonal boron nitride/bismaleimide resin composite material: take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 2.61 g hBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Comparative Examples 3; The preparation of another kind of hexagonal boron nitride/bismaleimide resin composite material: take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes transparent brown back and adds 7.83 g hBN, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Referring to accompanying drawing 7, the wideband dielectric loss curve comparison diagram under hexagonal boron nitride/bismaleimide resin composite material room temperature that bimaleimide resin that it is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 3 provide.Can find out by Fig. 7; Compare with the bimaleimide resin that Comparative Examples 1 provides; Three kinds of different hexagonal boron nitride/bismaleimide resin composite materials that provided not only have lower dielectric loss; Also have better frequency stability, this is because hexagonal boron nitride has excellent dielectric loss.Simultaneously; Can also see; Greater than unmodified hexagonal boron nitride, and along with the increase of modification hexagonal boron nitride content, the dielectric loss of matrix material is low more, low more to the dependency of frequency to the reduction of matrix material dielectric loss and stable effect for the hexagonal boron nitride of surface-treated.For example, the matrix material that embodiment 4 provides contains the hexagonal boron nitride after the 15 wt% modifications has only 56 % (106 Hz) and 68 % (109 Hz) of the matrix material that contains 15 wt% hexagonal boron nitrides that Comparative Examples 3 provides.Above result shows that the dielectric loss of the bismaleimide resin composite material of the hexagonal boron nitride of interpolation surface-treated has obtained very big improvement.
Referring to accompanying drawing 8, the thermal conductivity curve comparison diagram of hexagonal boron nitride/bismaleimide resin composite material that bimaleimide resin that it is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 2 and 3 provide.Compare with the bimaleimide resin that Comparative Examples 1 provides, the matrix material that embodiment 3 and 4, Comparative Examples 2 and 3 provide all has high thermal conductivity, and along with the increase of filler content, the thermal conductivity of matrix material increases.But; The thermal conductivity of the matrix material that contains OhBN that embodiment 3,4 provides is higher than the analog value of the matrix material that contains unmodified hexagonal boron nitride that Comparative Examples 2,3 provides respectively; This is because the thermal conductivity of OhBN and hBN itself is high more a lot of than matrix resin; The interfacial adhesion of OhBN and bimaleimide resin is more excellent simultaneously, so the high heat conductance of OhBN can better embody in matrix material.Above result shows that the thermal conductivity performance of the bismaleimide resin composite material that adds the surface-treated hexagonal boron nitride has obtained very big improvement.
Referring to accompanying drawing 9, the thermal expansivity curve comparison diagram of hexagonal boron nitride/bismaleimide resin composite material that bimaleimide resin that it is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 2 and 3 provide.As can be seen from Figure 9; Compare with the bimaleimide resin that Comparative Examples 1 provides; Surface-treated hexagonal boron nitride/bismaleimide resin composite material that embodiment 3 and 4 provides has lower thermal expansivity, and its increase along with surface-treated hexagonal boron nitride OhBN content constantly descends; Simultaneously, can find that under identical filler content, the thermal expansivity that contains surface-treated hexagonal boron nitride matrix material that embodiment 3 and 4 provides is lower than the analog value that contains unmodified hexagonal boron nitride hBN matrix material that Comparative Examples 2 and 3 provides respectively.This is because the thermal expansivity of OhBN and hBN is all much lower than matrix resin; Simultaneously OhBN have than hBN excellent with interfacial adhesion bimaleimide resin; This molecule segment motion that just means the resin in the OhBN/ matrix material is comparatively difficult, thereby causes lower thermal expansivity.Above result shows that the thermal expansivity performance of the bismaleimide resin composite material that adds the surface-treated hexagonal boron nitride has obtained very big improvement.
Referring to accompanying drawing 10; The loss tangent curve comparison diagram of hexagonal boron nitride/bismaleimide resin composite material that bimaleimide resin that it is hexagonal boron nitride/bismaleimide resin composite material of providing of the embodiment of the invention 3 and 4, Comparative Examples 1 provides and Comparative Examples 3 provide, the peak value of curve is represented second-order transition temperature.From Figure 10, can see; Compare with the bimaleimide resin that Comparative Examples 1 provides; Surface-treated hexagonal boron nitride/bismaleimide resin composite material that embodiment 3 and 4 provides has high glass transition, and its increase along with surface-treated hexagonal boron nitride OhBN content constantly raises; Simultaneously, can also see that under identical filler content, the second-order transition temperature that contains surface-treated hexagonal boron nitride matrix material that embodiment 4 provides is higher than the analog value that contains unmodified hexagonal boron nitride hBN matrix material that Comparative Examples 3 provides.This mainly is because the interfacial adhesion of OhBN and bimaleimide resin is better, has limited the motion of molecule segment, thereby has improved second-order transition temperature.Above result shows that the resistance toheat of adding the bismaleimide resin composite material of surface-treated hexagonal boron nitride has obtained very big improvement.
Embodiment 7
1, the preparation of surface-treated hexagonal boron nitride
(1) the 4A molecular sieve after the activation is put into N, 24 h in the dinethylformamide, underpressure distillation then, the cut of collection 76 ℃/4800 Pa (36 mmHg) obtains anhydrous N, dinethylformamide.
(2) in 250 ml there-necked flasks, add the N that 3 g nano-hexagonal boron nitrides and 100 ml handle through step (1); The dinethylformamide solvent; Ultrasonic agitation 30 min make nano-hexagonal boron nitride be evenly dispersed in N, in the dinethylformamide solvent.
(3) under the nitrogen protection, in there-necked flask, add 3 g 4,4 '-methylene-bis (phenylcarbimide) is at 70 ℃ of back flow reaction 30 min.After reaction finishes, the reaction product fast vacuum is filtered, use N, dinethylformamide washs 5 times, and unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product, is designated as IhBN.
(4) 3 g IhBN are dispersed in N, in the dinethylformamide, obtain dispersion liquid, then in dispersion liquid, add 3 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 50 ℃ of lower magnetic force stirring reactions 12 hours; After reaction finished, with reactant vacuum filtration, washing 5 times, the product that obtains was designated as OhBN.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes the nano-hexagonal boron nitride that transparent brown back adds 7.83 g surface-treateds, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 8
1, the preparation of surface-treated hexagonal boron nitride
(1) the 4A molecular sieve after the activation is put into N, 24 h in the dinethylformamide, underpressure distillation then, the cut of collection 76 ℃/4800 Pa (36 mmHg) obtains anhydrous N, dinethylformamide.
(2) in 250 ml there-necked flasks, add 3 g nanometers and micron hexagonal boron nitride mixture (nano-hexagonal boron nitride 1.5 g; Micron hexagonal boron nitride 1.5 g) and the N that handles through steps (1) of 100 ml; The dinethylformamide solvent; Ultrasonic agitation 30 min make nanometer and micron hexagonal boron nitride mixture be evenly dispersed in N, in the dinethylformamide solvent.
(3) under the nitrogen protection, in there-necked flask, add 3 g 4,4 '-methylene-bis (phenylcarbimide) is at 70 ℃ of back flow reaction 30 min.After reaction finishes, the reaction product fast vacuum is filtered, use N, dinethylformamide washs 5 times, and unreacted 4 to remove, 4 '-methylene-bis (phenylcarbimide) obtains intermediate product.
(4) 3 g intermediate products are dispersed in N, in the dinethylformamide, obtain dispersion liquid, then in dispersion liquid, add 3 g diaminodiphenylsulfone(DDS)s lentamente, obtain mixture B; Under agitation, mixture B was 50 ℃ of lower magnetic force stirring reactions 12 hours; After reaction finished, with reactant vacuum filtration, washing 5 times, the product that obtains was the nano-micrometre hexagonal boron nitride mixture after the surface-treated.
2, the preparation of hexagonal boron nitride/bismaleimide resin composite material
Take by weighing 22.2 g diallyl bisphenols in beaker, under 130～135 ℃, join 30 g bimaleimide resins in the diallyl bisphenol and carry out mechanical stirring; Thing to be mixed becomes nanometer and the micron hexagonal boron nitride (nano-hexagonal boron nitride is 1:1 with the mass ratio of micron hexagonal boron nitride) after transparent brown back adds 7.83 g surface-treateds, continues to stir 25 min down at 130～135 ℃; Then, liquid is poured in the mould of preheating, at 130 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimide resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 9
Take by weighing 50 g cyanate ester resins in beaker, under 150 ℃, carry out mechanical stirring; Treat that cyanate ester resin dissolves fully, obtain adding prepared surface-treated hexagonal boron nitride among the 7.83 g embodiment 3 behind the clarified liq, continue to stir 25 min down at 150 ℃; Then, liquid is poured in the mould of preheating, at 150 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/cyanate ester resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4 h.
Take by weighing 50 g bisphenol A type epoxy resin (trade mark E51; Oxirane value 0.51 mole/100 grams) in beaker; Be heated to 70 ℃ and make it to become low-viscosity (mobile) liquid, add surface-treated hexagonal boron nitride prepared among the 7.8 g embodiment 3,2 g solidifying agent (2; The 4-imidazoles), continue to stir 25 min down at 70 ℃; Then, liquid is poured in the mould of preheating, at 70 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/epoxy resin composite material according to 80 ℃/2h of technology+100 ℃/2h+120 ℃/2h and 150 ℃/4 h.
Embodiment 11
Take by weighing 52 g bimaleimide resins, 35 g cyanate ester resins carry out mechanical stirring under 150 ℃ in beaker; Treat that resin dissolves the back fully and adds prepared surface-treated hexagonal boron nitride among the 13.1 g embodiment 3, continue to stir 25 min down at 150 ℃; Then, liquid is poured in the mould of preheating, at 150 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/bismaleimides/cyanate ester resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 12
Take by weighing 10 g epoxy resin, 40 g cyanate ester resins carry out mechanical stirring under 150 ℃ in beaker; Treat that resin dissolves the back fully and adds prepared surface-treated hexagonal boron nitride among the 7.5 g embodiment 3, continue to stir 25 min down at 150 ℃; Then, liquid is poured in the mould of preheating, at 150 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven, be cured and aftertreatment, promptly obtain a kind of hexagonal boron nitride/epoxy resin/cyanate ester resin composite material according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4 h.
Embodiment 13
Take by weighing the 20g bimaleimide resin, 5 g epoxy resin, 15 g cyanate ester resins carry out mechanical stirring under 150 ℃ in beaker; Treat that resin dissolves the back fully and adds prepared surface-treated hexagonal boron nitride among the 6.0 g embodiment 3, continue to stir 25 min down at 150 ℃; Then, liquid is poured in the mould of preheating, at 150 ℃ of following vacuum outgas 30 min; At last mould is put into baking oven; Be cured and aftertreatment according to 150 ℃/2h of technology+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/8 h, promptly obtain a kind of hexagonal boron nitride/dimaleimide/epoxy resin/cyanate ester resin composite material.
Claims (4)
1. hexagonal boron nitride/thermoset ting resin composite, it is characterized in that: by weight, it comprises the hexagonal boron nitride of 100 parts of thermosetting resins and 5～50 parts of surface-treateds, the hexagonal boron nitride of said surface-treated be the surface contain 0.5 wt% above-NH
2Hexagonal boron nitride.
2. a kind of hexagonal boron nitride/thermoset ting resin composite according to claim 1 is characterized in that: described thermosetting resin is bimaleimide resin, cyanate ester resin, epoxy resin, or their arbitrary combination.
3. a method for preparing hexagonal boron nitride/thermoset ting resin composite as claimed in claim 1 is characterized in that comprising the steps:
(1) press mass ratio 1:20～1:100, hexagonal boron nitride is mixed with anhydrous organic solvent, homodisperse under the ultrasonic agitation condition obtains mixture;
(2) under the protection of inert gas, adding is the vulcabond of 1:0.5～1:2 with hexagonal boron nitride by mass ratio in mixture, under 50～110 ℃ temperature, reacts 20～50 minutes; After reaction finishes, immediately reaction product is filtered, washed, obtain intermediate product;
(3) press mass ratio 1:20～1:100, the resulting intermediate product of step (2) is dispersed in the anhydrous organic solvent, obtain dispersion liquid; To be that the diaminodiphenylsulfone(DDS) of 1:1～1:2 slowly joins in the dispersion liquid by mass ratio with vulcabond in the step (2), be reaction 8～16 hours under 40～70 ℃ the agitation condition in temperature; After reactant filtration, washing, obtain the hexagonal boron nitride of surface-treated;
(4) by weight, 100 parts of thermosetting resins and 5～50 parts of hexagonal boron nitrides through surface-treated are mixed, after deaeration, solidifying, obtain a kind of hexagonal boron nitride/thermoset ting resin composite.
4. the preparation method of a kind of hexagonal boron nitride/thermoset ting resin composite according to claim 3, it is characterized in that: described organic solvent is acetone, toluene, N, a kind of in the dinethylformamide, or their arbitrary combination.
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