CN101935453A - Thermoset polybenzoxazine-polyimide resin composite/mesoporous molecular sieve hybrid material and preparation method thereof - Google Patents

Thermoset polybenzoxazine-polyimide resin composite/mesoporous molecular sieve hybrid material and preparation method thereof Download PDF

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CN101935453A
CN101935453A CN2009100325318A CN200910032531A CN101935453A CN 101935453 A CN101935453 A CN 101935453A CN 2009100325318 A CN2009100325318 A CN 2009100325318A CN 200910032531 A CN200910032531 A CN 200910032531A CN 101935453 A CN101935453 A CN 101935453A
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molecular sieve
polybenzoxazine
polyimide resin
resin composition
mesopore molecular
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陈桥
吴祯祺
吴刚
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Toray Fibers and Textiles Research Laboratories China Co Ltd
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Toray Fibers and Textiles Research Laboratories China Co Ltd
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Abstract

The invention belongs to the field of organic/inorganic hybrid materials, and discloses a thermoset polybenzoxazine-polyimide resin composite/mesoporous molecular sieve hybrid material, which consists of a thermoset polybenzoxazine-polyimide resin composite and a mesoporous molecular sieve, wherein the mesoporous molecular sieve mass content of the hybrid material is 0.5 to 15 percent. Through a preparation method of the invention, the polybenzoxazine-polyimide resin composite/mesoporous molecular sieve hybrid material with a good interface structure and high comprehensive performance can be obtained. Compared with resin composites, the hybrid material not only maintains the heat resistance of substrate resin materials, but also has higher room-temperature storage modulus and lower dielectric constant so as to broaden the application prospect of the polybenzoxazine-polyimide resin composite in the fields of electrical engineering, electronics, information, military, aviation, aerospace and the like.

Description

A kind of heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material and preparation method thereof
Technical field
The invention belongs to the organic/inorganic hybridization material field, be specifically related to a kind of novel thermosetting type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material and preparation method thereof.
Background technology
Polybenzoxazine is a class novel thermosetting type resin that grows up on the basis of traditional resol, it is to be intermediate with the benzoxazine, under the effect of heating or catalyzer, ring-opening polymerization takes place, generate the cancellated polymkeric substance of nitrogenous and similar resol.Polybenzoxazine has not only kept advantages such as high temperature resistant, the good electrical properties of traditional resol and mechanical property and the prices of raw and semifnished materials be cheap, and improved the weak point of resol, as small molecules release, strong acid catalyzed corrosion equipment etc. are arranged when solidifying, it also has characteristic such as volumetric shrinkage approximate zero in low water absorbable, lower specific inductivity and the solidification process in addition.But there are defectives such as fragility is big, heat curing temperature is higher in pure Polybenzoxazine.
Polyimide, because of its performance and synthetic aspect outstanding feature, no matter be as structured material or as functional material, its great application prospect is familiar with fully.It has high thermostability, high strength and high-modulus, low thermal coefficient of expansion and specific inductivity, good insulating property and solvent resistance etc.Thereby industrial circles such as aerospace, military affairs, electric and electronic have been applied to.But with melamine resin, Resins, epoxy, unsaturated polyester resin etc. are compared, and it is on the high side.
Polybenzoxazine combined with polyimide, and [Polymer 2005,46,4909], can obtain to have the resin combination of cross-linked network structure, its thermal characteristics can be suitable with pure polyimide, but, has advantage on the cost so compare this resin combination material with pure polyimide because the cost of Polybenzoxazine will be lower than polyimide.In addition, because carboxylic acid Dui benzoxazine compound has the effect of catalysis open loop in the polyimide precursor polyamic acid, the solidification value of resin combination material can be starkly lower than purified petroleum benzin Bing oxazine, and the introducing of polyimide structures makes the fragility of benzoxazine colophony improve.But, since the resin combination material damage compound with regular structure of each simple resin, so its specific inductivity is higher than the one-component resin, and then limited its application at microelectronic.And, have the excellent thermal characteristics and the material of low-k and will have more application prospect along with more and more higher to the requirement of electronic unit densification (miniaturization) and signal transmission high speed.So far, still there is not bibliographical information at the research that improves Polybenzoxazine-polyimide resin composition dielectric properties.
By the mode of hybrid inorganic-organic, the research that improves the polymer materials dielectric properties has become one of focus of association area.And as the mesopore molecular sieve of new inorganic material, because of its have unique long-range order pore structure, [Nature 1992 for narrow pore size distribution, high-specific surface area, high porosity and higher thermostability, 359,710] etc. excellent specific property has caused extensive concern rapidly.Mesopore molecular sieve is introduced in the polymeric matrix, and the research of preparation low-k hybrid inorganic-organic materials aspect progressively becomes a new research direction.Part Study is presented at and introduces specific inductivity [Polymer48 (2007) 318-329 that a spot of mesopore molecular sieve can effectively reduce body material in polyimide or the Resins, epoxy; Composites Science and Technology (2008), 1570-1578; CN 100419011C], but more or less can cause simultaneously the loss of the original performance of matrix resin material.
Based on above-mentioned, the present invention introduces mesopore molecular sieve in Polybenzoxazine-polyimide resin composition by the method for hybrid inorganic-organic, to improve the dielectric properties of body material, widens its range of application.The present invention at first adopts solution blended method to prepare benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid, and obtains Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material after segmentation is solidified.
Summary of the invention
The purpose of this invention is to provide a kind of heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, solve Polybenzoxazine-higher deficiency of polyimide resin composition specific inductivity, thereby widen its Application Areas.
Another object of the present invention provides the preparation method of above-mentioned heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material.
Purpose of the present invention can reach by following measure:
A kind of heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, this hybrid material is made up of heat curing-type Polybenzoxazine-polyimide resin composition and mesopore molecular sieve, wherein said heat curing-type Polybenzoxazine-polyimide resin composition is made up of Polybenzoxazine and polyimide, and the mass content of described mesopore molecular sieve in hybrid material is 0.5～15%.More even for mesopore molecular sieve is disperseed in polymeric matrix, not reunite, the quality percentage composition of mesopore molecular sieve in hybrid material is preferably 1～7%.
Mesopore molecular sieve particulate of the present invention can adopt existing commercially available mesopore molecular sieve, also can pass through reported method (Microporous ﹠amp; Mesoporous Mater., 1999,27:131; Langmuir, 2000,16:4648) preparation voluntarily.
The mass ratio of Polybenzoxazine and polyimide is 1/99～99/1 (promptly 1: 99～99: 1) in heat curing-type Polybenzoxazine-polyimide resin composition of the present invention.In order to make in Polybenzoxazine-polyimide resin composition two components synergy more obvious, the hybrid material performance that is obtained is more excellent, and the mass ratio of Polybenzoxazine and polyimide is preferably 10/90～90/10 (promptly 10: 90～90: 10) in the composition
In heat curing-type Polybenzoxazine-polyimide resin composition of the present invention, Polybenzoxazine is formed (being that monomer is a benzo oxazinyl compound) by benzo oxazinyl compound.
Benzo oxazinyl compound of the present invention is selected from one or more in diamines type bi-benzoxazine compounds or the bisphenol type benzo oxazinyl compound, and structure is as follows:
Diamines type bi-benzoxazine compounds (formula I):
Figure B2009100325318D0000031
R 3For hydrogen, methyl or allyl group (promptly-CH 2-CH=CH 2),
Y is-(CH 2) 6-,-(CH 2) 8-,-(CH 2) 10-,-(CH 2) 12-,
Figure B2009100325318D0000033
Bisphenol type benzo oxazinyl compound (formula II):
Figure B2009100325318D0000034
R 1Be hydrogen, methyl or ethynyl (promptly-C ≡ CH), cyano group (promptly-C ≡ N) or the alkynes third alkoxyl group (O-CH 2-C ≡ CH),
R 2For hydrogen or allyl group (promptly-CH 2-CH=CH 2),
X is-CH 2-,-O-,-C (CH 3) 2-(promptly
Figure B2009100325318D0000041
) or-SO 2-(promptly
Figure B2009100325318D0000042
).
Benzo oxazinyl compound can adopt existing commercially available compound, also can be synthetic according to the technological line that Chinese patent ZL94111852.5 provides, formaldehyde, phenolic compound and aminated compounds, in toluene, dioxane, chloroform equal solvent, reaction is 4-5 hour under the solvent refluxing temperature, and product process vacuum extraction removes the solvent in the system.Because raw material is easy to get, nontoxic or low toxicity and low price, the benzo oxazinyl compound that preferably has following structure:
In heat curing-type Polybenzoxazine-polyimide resin composition of the present invention, polyimide is made up of dicarboxylic anhydride monomer and diamine monomer, and the monomeric mol ratio of diamine monomer and dicarboxylic anhydride is 1: 1.02～1.20, be preferably 1: 1.02～and 1.05.
Dicarboxylic anhydride monomer of the present invention can be pyromellitic acid anhydride (PMDA) or 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); Described diamine monomer is 4,4 '-diamines yl diphenyl ether (ODA) or p-phenylenediamine (p-PDA).
The dianhydride class monomer and the amine monomer of above-mentioned polyimide matrix have following structure:
Figure B2009100325318D0000044
Figure B2009100325318D0000045
Mesopore molecular sieve among the present invention is selected for use: MCM-41, MCM-48, SBA-15 or SBA-16 etc.; Can be through or without silane coupler modified; The median size of mesoporous molecule is 50～1000nm, and the aperture is 2～30nm, and specific surface area is 500～2000m 2/ g, pore volume is 0.7～1.2cm 3/ g.Adopt the mesopore molecular sieve of silane coupler modified mistake bring better effect can for hybrid material of the present invention, and the used silane coupling agent of modification is a Union carbide A-162, methyltrimethoxy silane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, or γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane etc., because the mesopore molecular sieve after having reactive group silane coupler modified has better consistency with Polybenzoxazine-polyimide resin composition, the interaction between easier formation interface, so the used silane coupling agent of modification is preferably: vinyltrimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-[(2,3)-and epoxy third oxygen] propyl trimethoxy silicane, more preferably γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane.Wherein, the method for modifying of mesopore molecular sieve is can articles of reference [J.Am.Chem.Soc.1981,103,5303-5307] described.Its main process is: the toluene solution of mesopore molecular sieve and an amount of silane coupling agent is placed there-necked flask, reflux more than 24 hours, filtration washing promptly obtains the mesopore molecular sieve of modification.
The silane coupling agent molecular formula that is used for the mesopore molecular sieve modification among the present invention is as follows:
CH 3-Si-(OCH 2CH 3) 3 CH 3-Si-(OCH 3) 3
The Union carbide A-162 methyltrimethoxy silane
CH 3CH 2-Si-(OCH 2CH 3) 3 CH 3CH 2-Si-(OCH 3) 3
The ethyl triethoxysilane ethyl trimethoxy silane
CH 2＝CH-Si-(OCH 2CH 3) 3 CH 2＝CH-Si-(OCH 3) 3
The vinyltriethoxysilane vinyltrimethoxy silane
H 2N-CH 2CH 2CH 2-Si-(OCH 2CH 3) 3 H 2N-CH 2CH 2CH 2-Si-(OCH 3) 3
The γ-An Bingjisanyiyangjiguiwan γ-An Bingjisanjiayangjiguiwan
Figure B2009100325318D0000051
The method for preparing above-mentioned heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, different according to Polybenzoxazine and polyimide mass ratio, concrete steps are different.
When Polybenzoxazine in the resin combination and polyimide mass ratio are 1/99～50/50 and do not comprise 50/50 when (promptly more than or equal to 1/99 less than 50/50 time), prepare the method for above-mentioned hybrid material, may further comprise the steps:
(1) mesopore molecular sieve is scattered in the organic solvent, it was uniformly dispersed in ultrasonic 1.5～20 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
(2) under the protection of rare gas element, diamine monomer is added in the above-mentioned mesopore molecular sieve dispersion liquid, stir, wait to dissolve the back to wherein slowly adding the dicarboxylic anhydride monomer, the whole reinforced time is 10～30 minutes; After reinforced the finishing, 10～35 ℃ were reacted 12～24 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
(3) benzoxazine compound is dissolved in organic solvent, obtain benzoxazine compound solution, this solution is added in polyamic acid/mesoporous molecular sieve hybrid solution that (2) obtain, continue down to stir 5～15 hours at 10～35 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
(4) with benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid after carrying out segmentation under 100～320 ℃ and solidifying, obtain heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material.
When Polybenzoxazine in the resin combination and polyimide mass ratio are 50/50～99/1 (promptly 50: 50～99: 1), prepare the method for above-mentioned hybrid material, may further comprise the steps:
(a) mesopore molecular sieve is scattered in the organic solvent, it was uniformly dispersed in ultrasonic 1.5～20 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
(b) in the mesopore molecular sieve dispersion liquid that benzoxazine compound adding (a) is obtained, continue down to stir 12～24 hours, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 10～35 ℃;
(c) under the protection of rare gas element, diamine monomer is added in the organic solvent, stir, wait to dissolve the back to wherein slowly adding the dicarboxylic anhydride monomer, the whole reinforced time is 10～30 minutes; After reinforced the finishing, 10～35 ℃ were reacted 12～24 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in benzoxazine compound/mesopore molecular sieve mixing liquid that (b) obtain, continue down to stir 5～15 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 10～35 ℃;
(d) with benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid after being cured under 100～250 ℃, obtain heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material.
Aforesaid method step (1), (3), (a) or (c) described in solvent be N independently respectively, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO), the middle organic solvent in wherein preferred (1) and (3) consistent, (a) with (c) in consistent.Employedly in the preparation method ultrasonicly be meant that adopting hyperacoustic method that ordinary method is difficult to the dispersive mesopore molecular sieve disperses, so the present invention there is no particular requirement to the ultrasonic wave of specifically selecting which kind of frequency and power for use, as long as mesopore molecular sieve fully can be disperseed.Consider the difference of different hyperacoustic dispersion effects, dispersion efficiency and energy consumption simultaneously, the present invention is limited to 1.5～20 hours with ultrasonic time.
Aforesaid method step (4) and (d) described in segmentation be cured as in certain temperature range stage by stage gradually that elevated temperature is cured reaction, according to the structure or the proportioning difference of two components in Polybenzoxazine-polyimide resin composition, it is two sections, three sections or four sections that solidification process can be divided into.
Heat curing-type Polybenzoxazine-polyimide resin composition/the mesoporous molecular sieve hybrid material of present method gained can be by being shaped benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid or be molded into mould solidifying formation then in stainless steel plate, sheet glass, metal aluminum foil, tetrafluoroethylene or other stromal surface.
Beneficial effect of the present invention: mesopore molecular sieve used in the present invention has the modifiability in regular pore structure and duct.According to preparation method of the present invention, can access heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material with good interface structure and excellent combination property.Compare with Polybenzoxazine-polyimide resin composition, hybrid material has not only kept the thermotolerance of matrix resin material, second-order transition temperature is constant or raising arranged slightly, and its room temperature storage modulus has improved 10-70%, specific inductivity has reduced 0.1-0.6, and then has widened the application prospect of heat curing-type Polybenzoxazine-polyimide resin composition in each side such as electrician, electronics, information, military affairs, aerospaces.
Embodiment
The present invention can obtain further elaboration by the embodiment of following preferred embodiment, but these embodiment only are to illustrate, and scope of the present invention is not made and being defined.
The starting material that use among the embodiment:
A) mesopore molecular sieve, the concrete preparation method of various different mesopore molecular sieves is as follows:
1. MCM-41: the 120g cetyl trimethylammonium bromide is dissolved in the 2L deionized water, and stirring at room 30min fully dissolves it; The ammoniacal liquor (25%) that adds 2.5L dehydrated alcohol and 680g stirs 25min; Add the 180ml tetraethoxy again, stirring at room 6h; Then room temperature is static aging 1 hour.Suction filtration, washing are to neutral, and drying obtains former powder; Former powder is placed muffle furnace, and 1 ℃/min is raised to 580 ℃ of roastings 6 hours under air atmosphere, obtains MCM-41.The proportioning that changes each reactant can make the particle diameter of MCM-41 particle change between 50～1000nm.Use particle diameter among this patent embodiment and be 150 and two kinds of MCM-41 particles of 500nm.
2. MCM-48: the 6g cetyl trimethylammonium bromide is dissolved in the 216ml deionized water stirring at room dissolving; The ammoniacal liquor (25%) that adds 125ml dehydrated alcohol and 34g stirs 10min; Add the 9ml tetraethoxy again, the room temperature ultrasonic concussion mixes 0.5h, and hydrolysis, condensation form gel; Room temperature ultrasonic concussion then continues to stir 2.5h, crystallization; Static aging 1 hour at 40 ℃.Suction filtration, washing are to neutral, and drying obtains former powder; Former powder is placed muffle furnace, and 1 ℃/min is raised to 580 ℃ of roastings 6 hours under air atmosphere, obtains MCM-48.
3. SBA-15: with 20gP123 (Aldrich, EO 20PO 70EO 20Molecular-weight average is 5800) and the 2g cetyl trimethylammonium bromide be dissolved in the 150g water, add 450g hydrochloric acid soln (2mol/Kg), make the solution of a clear 35 ℃ of stirrings, add tetraethoxy 58g again,, obtain a gelating soln in 40 ℃ of following stirring reactions 20 hours, be transferred in the polytetrafluoroethylcontainer container static 80 ℃ of following hydro-thermal reactions 24 hours.
B) benzoxazine compound, the concrete preparation method of various different benzoxazine compounds is as follows:
1. dihydroxyphenyl propane-aniline type benzoxazine compound (BZ): with 7.8g aniline, the 5g Paraformaldehyde 96 is dissolved in the 150ml dioxane, add the 9.5g dihydroxyphenyl propane subsequently, be warming up to backflow, mixing solutions reacted 4 hours down in reflux state, solvent is removed in underpressure distillation, and vacuum-drying obtains dihydroxyphenyl propane-aniline type benzoxazine compound (BZ), and its chemical structure is as follows:
Figure B2009100325318D0000081
2. dihydroxyphenyl propane-Ortho Toluidine type benzoxazine compound (O-BZ): with the 9.0g Ortho Toluidine, 5.0g Paraformaldehyde 96 be dissolved in the 150ml toluene, add the 9.5g dihydroxyphenyl propane subsequently, be warming up to backflow, mixing solutions reacted 5 hours down in reflux state, solvent is removed in underpressure distillation, and vacuum-drying obtains dihydroxyphenyl propane-Ortho Toluidine type benzoxazine compound (O-BZ), and its chemical structure is as follows:
Figure B2009100325318D0000091
3. dihydroxyphenyl propane-meta-aminotoluene type benzoxazine compound (M-BZ): with the 9.0g meta-aminotoluene, 5.0g Paraformaldehyde 96 be dissolved in the 150ml chloroform, add the 9.5g dihydroxyphenyl propane subsequently, be warming up to backflow, mixing solutions reacted 5 hours down in reflux state, solvent is removed in underpressure distillation, and vacuum-drying obtains dihydroxyphenyl propane-meta-aminotoluene type benzoxazine compound (M-BZ), and its chemical structure is as follows:
Figure B2009100325318D0000092
4. hexanediamine-phenol type benzoxazine compound (DHP-BZ): with 5.8g 1, the 6-hexanediamine, 6.0g Paraformaldehyde 96 be dissolved in the 300ml chloroform, add 9.4g phenol subsequently, be warming up to backflow, mixing solutions reacted 5 hours down in reflux state, and solvent is removed in underpressure distillation, vacuum-drying obtains hexanediamine-phenol type benzoxazine compound (DHP-BZ), and its chemical structure is as follows:
Figure B2009100325318D0000093
C) organic monomer: pyromellitic acid anhydride (PMDA): Chemical Reagent Co., Ltd., Sinopharm Group; 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA): Co., Ltd among the SIGMA-ALDRICH; 4,4 '-diamines yl diphenyl ether (ODA): Chemical Reagent Co., Ltd., Sinopharm Group; P-phenylenediamine (p-PDA): Chemical Reagent Co., Ltd., Sinopharm Group;
D) solvent: N,N-dimethylacetamide (DMAc): Chemical Reagent Co., Ltd., Sinopharm Group; N-Methyl pyrrolidone (NMP): Chemical Reagent Co., Ltd., Sinopharm Group; Dimethyl sulfoxide (DMSO) (DMSO): Chemical Reagent Co., Ltd., Sinopharm Group; N, dinethylformamide (DMF): Chemical Reagent Co., Ltd., Sinopharm Group;
E) silane coupling agent: γ-An Bingjisanyiyangjiguiwan: the magnificent chemical plant of shining, Shanghai; Union carbide A-162: Ninghua, road, Foshan City worker company limited; Vinyltrimethoxy silane: Ninghua, road, Foshan City worker company limited; γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane: the magnificent chemical plant of shining, Shanghai.
The measuring method of polybenzoxazine/mesoporous molecular sieve hybrid material structure and dielectric properties among the embodiment:
A) specific inductivity is measured: under 25 ℃, Novocontrol wideband dielectric and impedance spectrometer (BDS-40 Germany) adopt 2 centimetres of electrode diameters, test frequency scope: 0.01Hz～10MHz.Before the test, sample surfaces contact well between sample and test electrode guaranteeing through metalized (sputter or brush elargol).The gained material dielectric constant is three sample test results' a mean value.
B) room temperature storage modulus and second-order transition temperature test: dynamic viscoelasticity spectrum instrument (the TA Q800 U.S.), test frequency 1Hz, probe temperature: room temperature～400 ℃, 3 ℃/minute of heat-up rates.Test bars is of a size of: long 20mm, wide 5mm, thickness actual measurement.
Embodiment 1
With the 0.338g particle diameter is that the MCM-41 of 500nm is scattered in the 16ml N,N-dimethylacetamide (DMAc), it is uniformly dispersed in ultrasonic 15 hours under the room temperature, obtains the mesopore molecular sieve dispersion liquid;
2.470g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 20 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 27 ℃;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlDMAc, stirs, and waits to dissolve the back to wherein slowly adding 0.080g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is after reinforced the finishing, 25 ℃ were reacted 16 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 9 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 20 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 13%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 95/5.Directly surface sputtering thickness is about 0.1 micron gold layer thereon, carries out the dielectric properties test, and specific inductivity is 4.02 under the 100kHz.The room temperature storage modulus of hybrid material is 5.9GPa, and second-order transition temperature is 173 ℃.
Embodiment 2
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
MCM-41 after the 0.268g modification is scattered in the 16ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 16 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
2.546g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 24 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 18 ℃;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.084g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 13 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 26 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 10%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 95/5.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.76 under the 100kHz.The room temperature storage modulus of hybrid material is 6.9GPa, and second-order transition temperature is 176 ℃.
Embodiment 3
With particle diameter is that the MCM-41 of 150nm and the toluene solution of Union carbide A-162 place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain the modified MC M-41 that the surface has methyl.
MCM-41 after the 0.132g modification is scattered in 16ml N, it was uniformly dispersed in ultrasonic 18 hours under the middle room temperature of dinethylformamide (DMF), obtain the mesopore molecular sieve dispersion liquid;
2.508g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 22 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 20 ℃;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlDMF, stirs, and waits to dissolve the back to wherein slowly adding 0.082g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 27 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 12 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 24 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 5%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 95/5.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.86 under the 100kHz.The room temperature storage modulus of hybrid material is 7.8GPa, and second-order transition temperature is 177 ℃.
Comparative Examples 1
In 2.470g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) 16ml N-Methyl pyrrolidone (NMP), obtain the benzoxazine compound nmp solution;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.080g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 25 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in the above-mentioned benzoxazine compound nmp solution, continue down to stir 6 hours, obtain the nmp solution of benzoxazine compound-polyamic acid at 24 ℃;
The nmp solution of benzoxazine compound-polyamic acid of obtaining is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 95/5.Directly surface sputtering thickness is about 0.1 micron gold layer thereon, carries out the dielectric properties test, and specific inductivity is 4.22 under the 100kHz.The room temperature storage modulus of hybrid material is 5.1GPa, and second-order transition temperature is 178 ℃.
Comparative Examples 2
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
MCM-41 after the 0.4716g modification is scattered in the 16ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 20 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
2.489g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 24 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 26 ℃;
Under the protection of rare gas element, with 0.05g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.081g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 24 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 10 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 27 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 18%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 95/5.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 4.35 under the 100kHz.The room temperature storage modulus of hybrid material is 5.3GPa, and second-order transition temperature is 172 ℃.
Embodiment 4
With the 0.052g particle diameter is that the MCM-41 of 150nm is scattered in the 10ml N,N-dimethylacetamide (DMAc), it is uniformly dispersed in ultrasonic 12 hours under the room temperature, obtains the mesopore molecular sieve dispersion liquid;
1.170g dihydroxyphenyl propane-meta-aminotoluene type benzoxazine compound (M-BZ) is added in the aforesaid liquid, continue to stir 20 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 25 ℃;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlDMAc, stirs, and waits to dissolve the back to wherein slowly adding 0.080g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 15 ℃ were reacted 15 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 15 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 20 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the polyfluortetraethylene plate, through 160 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 4%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 90/10.Sample is taken off, and the thickness of lower surface sputter thereon is about 0.1 micron gold layer, carries out the dielectric properties test, and specific inductivity is 3.40 under the 100kHz.The room temperature storage modulus of hybrid material is 4.1GPa, and second-order transition temperature is 193 ℃.
Embodiment 5
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
MCM-41 after the 0.0665g modification is scattered in the 11ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 6 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
1.197g dihydroxyphenyl propane-meta-aminotoluene type benzoxazine compound (M-BZ) is added in the aforesaid liquid, continue to stir 14 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 25 ℃;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.083g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 14 ℃ were reacted 13 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 8 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 17 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 160 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 5%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 90/10.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.24 under the 100kHz.The room temperature storage modulus of hybrid material is 4.3GPa, and second-order transition temperature is 196 ℃.
Embodiment 6
The toluene solution of MCM-48 and vinyltrimethoxy silane is placed there-necked flask, reflux more than 24 hours, filtration washing can obtain the modified MC M-48 that the surface has vinyl.
MCM-41 after the 0.0133g modification is scattered in the 10ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 2 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
1.197g dihydroxyphenyl propane-meta-aminotoluene type benzoxazine compound (M-BZ) is added in the aforesaid liquid, continue to stir 14 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 25 ℃;
Under the protection of rare gas element, with 0.05g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.083g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 32 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 5 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 30 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 160 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-48 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 1%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 90/10.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.48 under the 100kHz.The room temperature storage modulus of hybrid material is 4.3GPa, and second-order transition temperature is 194 ℃.
Comparative Examples 3
1.170g dihydroxyphenyl propane-meta-aminotoluene type benzoxazine compound (M-BZ) is dissolved in 10ml N-Methyl pyrrolidone (NMP), obtains the nmp solution of benzoxazine compound;
Under the protection of rare gas element, with 0.050g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.080g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 30 ℃ were reacted 22 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in the nmp solution of above-mentioned benzoxazine compound, continue down to stir 5 hours, obtain the nmp solution of benzoxazine compound-polyamic acid at 28 ℃;
The nmp solution of benzoxazine compound-polyamic acid of obtaining is taken shape on the stainless steel plate, through 160 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 90/10.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.61 under the 100kHz.The room temperature storage modulus of hybrid material is 3.8GPa, and second-order transition temperature is 194 ℃.
Embodiment 7
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
MCM-41 after the 0.018g modification is scattered in the 16ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 3 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
1.519g hexanediamine-phenol type benzoxazine compound (DHP-BZ) is added in the aforesaid liquid, continue to stir 15 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 25 ℃;
Under the protection of rare gas element, with 0.100g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.168g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 23 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 5 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 26 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 120 ℃/1.5 hours, 150 ℃/1.5 hours, 180 ℃/2 hours, after four sections curing in 200 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 1%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 85/15.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.63 under the 100kHz.The room temperature storage modulus of hybrid material is 3.5GPa, and second-order transition temperature is 199 ℃.
Comparative Examples 4
1.519g hexanediamine-phenol type benzoxazine compound (DHP-BZ) is dissolved in the 16ml N-Methyl pyrrolidone (NMP), obtains the nmp solution of benzoxazine compound;
Under the protection of rare gas element, with 0.100g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 1.3mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.168g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 23 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in the nmp solution of above-mentioned benzoxazine compound, continue down to stir 5 hours, obtain the nmp solution of benzoxazine compound-polyamic acid at 26 ℃;
The nmp solution of benzoxazine compound-polyamic acid of obtaining is taken shape on the stainless steel plate, through 120 ℃/1.5 hours, 150 ℃/1.5 hours, 180 ℃/2 hours, after four sections curing in 200 ℃/1 hour, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 85/15.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.84 under the 100kHz.The room temperature storage modulus of hybrid material is 3.4GPa, and second-order transition temperature is 195 ℃.
Embodiment 8
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
MCM-41 after the 0.05g modification is scattered in the 12ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 18 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
1.26g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 15 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 22 ℃;
Under the protection of rare gas element, with 0.20g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 3.2mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.22g pyromellitic acid anhydride (PMDA); After reinforced the finishing, 24 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 10 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 28 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 3%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 75/25.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.44 under the 100kHz.The room temperature storage modulus of hybrid material is 4.3GPa, and second-order transition temperature is 192 ℃.
Embodiment 9
The toluene solution of SBA-15 and γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane is placed there-necked flask, reflux more than 24 hours, filtration washing can obtain modified SBA-15.
SBA-15 after the 0.0336g modification is scattered in the 12ml N-Methyl pyrrolidone (NMP) under the room temperature ultrasonic 18 hours it is uniformly dispersed, obtain the mesopore molecular sieve dispersion liquid;
1.26g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 15 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 22 ℃;
Under the protection of rare gas element, with 0.20g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 3.2mlNMP, stirs, and waits to dissolve the back to wherein slowly adding 0.22g pyromellitic acid anhydride (PMDA); After reinforced the finishing, 25 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 9 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 22 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 2%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 75/25.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.51 under the 100kHz.The room temperature storage modulus of hybrid material is 4.3GPa, and second-order transition temperature is 190 ℃.
Comparative Examples 5
1.26g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved in the 12ml N-Methyl pyrrolidone (NMP), obtains the nmp solution of benzoxazine compound;
Under the protection of rare gas element, with 0.2g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 3.2ml NMP, stirs, and waits to dissolve the back to wherein slowly adding 0.22g pyromellitic acid anhydride (PMDA); After reinforced the finishing, 23 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined the nmp solution of above-mentioned benzoxazine compound, continue down to stir 5 hours, obtain the nmp solution of benzoxazine compound-polyamic acid at 26 ℃;
The nmp solution of benzoxazine compound-polyamic acid of obtaining is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 75/25.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.76 under the 100kHz.The room temperature storage modulus of hybrid material is 3.4GPa, and second-order transition temperature is 179 ℃.
Embodiment 10
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
0.039g modified MC M-41 is scattered in the 8ml N-Methyl pyrrolidone, it was uniformly dispersed in ultrasonic 5 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
0.78g dihydroxyphenyl propane-Ortho Toluidine type benzoxazine compound (O-BZ) is added in the aforesaid liquid, continue to stir 15 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 20 ℃;
Under the protection of rare gas element, with 0.20g 4,4 '-diamines yl diphenyl ether (ODA) adds in the 5.2mlN-methyl-2-pyrrolidone, stirs, and waits to dissolve the back to wherein slowly adding 0.32g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 25 ℃ were reacted 16 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 8 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 28 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 3%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 60/40.Directly surface sputtering thickness is about 0.1 micron gold layer thereon, carries out the dielectric properties test, and specific inductivity is 3.87 under the 100kHz.The room temperature storage modulus of hybrid material is 4.1GPa, and second-order transition temperature is 243 ℃.
Comparative Examples 6
0.78g dihydroxyphenyl propane-Ortho Toluidine type benzoxazine compound (O-BZ) is dissolved in the 8ml N-Methyl pyrrolidone, obtains the nmp solution of benzoxazine compound;
Under the protection of rare gas element, with 0.20g 4,4 '-diamines yl diphenyl ether (ODA) adds in the 5.2mlN-methyl-2-pyrrolidone, stirs, and waits to dissolve the back to wherein slowly adding 0.32g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 25 ℃ were reacted 16 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in the nmp solution of above-mentioned benzoxazine compound, continue down to stir 5 hours, obtain the nmp solution of benzoxazine compound-polyamic acid at 28 ℃;
The nmp solution of benzoxazine compound-polyamic acid of obtaining is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 60/40.Directly surface sputtering thickness is about 0.1 micron gold layer thereon, carries out the dielectric properties test, and specific inductivity is 4.05 under the 100kHz.The room temperature storage modulus of hybrid material is 3.6GPa, and second-order transition temperature is 240 ℃.
Embodiment 11
0.156g MCM-48 is scattered in the 10ml N-Methyl pyrrolidone (NMP), it was uniformly dispersed in ultrasonic 17 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
1.3g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 20 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 28 ℃;
Under the protection of rare gas element, with 0.5g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 13ml NMP, stirs, and waits to dissolve the back to wherein slowly adding 0.8g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 29 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 10 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 26 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-48 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 6%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 50/50.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 4.02 under the 100kHz.The room temperature storage modulus of hybrid material is 4.2GPa, and second-order transition temperature is 252 ℃.
Embodiment 12
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
0.13g modified MC M-41 is scattered in the 10ml N-Methyl pyrrolidone (NMP), it was uniformly dispersed in ultrasonic 6 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
1.3g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is added in the aforesaid liquid, continue to stir 18 hours down, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 16 ℃;
Under the protection of rare gas element, with 0.5g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 13ml NMP, stirs, and waits to dissolve the back to wherein slowly adding 0.8g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in above-mentioned benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 7 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 18 ℃;
Benzoxazine compound-polyamic acid/mesopore molecular sieve the mixing liquid that obtains is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain the MCM-41 mass content and be heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material of 5%, wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 50/50.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.89 under the 100kHz.The room temperature storage modulus of hybrid material is 4.3GPa, and second-order transition temperature is 250 ℃.
Comparative Examples 7
1.3g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved in the 10ml N-Methyl pyrrolidone (NMP), obtains the nmp solution of benzoxazine compound;
Under the protection of rare gas element, with 0.5g 4,4 '-diamines yl diphenyl ether (ODA) adds among the 13ml NMP, stirs, and waits to dissolve the back to wherein slowly adding 0.8g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in the nmp solution of above-mentioned benzoxazine compound, continue down to stir 7 hours, obtain the nmp solution of benzoxazine compound-polyamic acid at 18 ℃;
The nmp solution of benzoxazine compound-polyamic acid of obtaining is taken shape on the stainless steel plate, through 150 ℃/1 hour, 200 ℃/1 hour, after three sections curing in 240 ℃/1 hour, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 50/50.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 4.60 under the 100kHz.The room temperature storage modulus of hybrid material is 4.0GPa, and second-order transition temperature is 246 ℃.
Embodiment 13
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
0.0519g modified MC M-41 is scattered in the 11ml N-Methyl pyrrolidone (NMP), it was uniformly dispersed in ultrasonic 6 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid.
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the above-mentioned mesopore molecular sieve dispersion liquid, stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 25 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
0.43g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 3.5ml NMP, this solution is added in above-mentioned polyamic acid/mesoporous molecular sieve hybrid solution, continue down to stir 7.5 hours at 27 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
Benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtaining the MCM-41 mass content is 3% heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, and wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 25/75.The thickness of lower surface sputter thereon is about 0.1 micron gold layer, carries out the dielectric properties test, and specific inductivity is 3.52 under the 100kHz.The room temperature storage modulus of hybrid material is 4.4GPa, and second-order transition temperature is 373 ℃.
Comparative Examples 8
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the 11ml N-Methyl pyrrolidone (NMP), stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 29 ℃ were reacted 20 hours down under the protection of rare gas element, obtained the nmp solution of polyamic acid;
0.43g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 3.5ml NMP, and this solution is added in the above-mentioned polyamic acid, continues down to stir 5 hours at 27 ℃, obtains the nmp solution of benzoxazine compound-polyamic acid;
The nmp solution of benzoxazine compound-polyamic acid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 25/75.The thickness of lower surface sputter thereon is about 0.1 micron gold layer, carries out the dielectric properties test, and specific inductivity is 4.10 under the 100kHz.The room temperature storage modulus of hybrid material is 4.0GPa, and second-order transition temperature is 331 ℃.
Embodiment 14
With the 0.153g particle diameter is that the MCM-41 of 150nm is scattered in the 11mlN-methyl-2-pyrrolidone (NMP), it is uniformly dispersed in ultrasonic 20 hours under the room temperature, obtains the mesopore molecular sieve dispersion liquid;
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the above-mentioned mesopore molecular sieve dispersion liquid, stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 24 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
0.23g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 2ml NMP, this solution is added in above-mentioned polyamic acid/mesoporous molecular sieve hybrid solution, continue down to stir 10 hours at 26 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
Benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid is taken shape on the sheet glass, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtaining the MCM-41 mass content is 10% heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, and wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 15/85.The thickness of lower surface sputter thereon is about 0.1 micron gold layer, carries out the dielectric properties test, and specific inductivity is 3.5 under the 100kHz.The room temperature storage modulus of hybrid material is 5.6GPa, and second-order transition temperature is 336 ℃.
Embodiment 15
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
0.0612g modified MC M-41 is scattered in the 11ml N-Methyl pyrrolidone (NMP), it was uniformly dispersed in ultrasonic 11 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid.
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the above-mentioned mesopore molecular sieve dispersion liquid, stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 25 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
0.23g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 2ml NMP, this solution is added in above-mentioned polyamic acid/mesoporous molecular sieve hybrid solution, continue down to stir 15 hours at 26 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
Benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtaining the MCM-41 mass content is 4% heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, and wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 15/85.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.36 under the 100kHz.The room temperature storage modulus of hybrid material is 4.5GPa, and second-order transition temperature is 333 ℃.
Comparative Examples 9
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the 11ml N-Methyl pyrrolidone (NMP), stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 30 ℃ were reacted 24 hours down under the protection of rare gas element, obtained the nmp solution of polyamic acid;
0.23g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 2ml NMP, and this solution is added in the above-mentioned polyamic acid, continues down to stir 5 hours at 28 ℃, obtains the nmp solution of benzoxazine compound-polyamic acid;
The nmp solution of benzoxazine compound-polymeric amide is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 15/85.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.95 under the 100kHz.The room temperature storage modulus of hybrid material is 4.2GPa, and second-order transition temperature is 337 ℃.
Embodiment 16
0.041g SBA-15 is scattered in the 11ml dimethyl sulfoxide (DMSO) (DMSO), it was uniformly dispersed in ultrasonic 8 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the mesopore molecular sieve dispersion liquid, stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 19 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
0.07g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 0.5ml DMSO, this solution is added in above-mentioned polyamic acid/mesoporous molecular sieve hybrid solution, continue down to stir 13 hours at 30 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
Benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtaining the SBA-15 mass content is 3% heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, and wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 5/95.Directly surface sputtering one layer thickness is about 0.1 micron gold layer thereon, carries out the dielectric properties test, and specific inductivity is 3.6 under the 100kHz.The room temperature storage modulus of hybrid material is 4.0GPa, and second-order transition temperature is 315 ℃.
Embodiment 17
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-An Bingjisanyiyangjiguiwan place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain the surface and have amino modified MC M-41.
0.137g modified MC M-41 is scattered in the 11ml N-Methyl pyrrolidone (NMP), it was uniformly dispersed in ultrasonic 11 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid.
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the above-mentioned mesopore molecular sieve dispersion liquid, stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 24 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
0.07g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 0.5ml NMP, this solution is added in above-mentioned polyamic acid/mesoporous molecular sieve hybrid solution, continue down to stir 12 hours at 25 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
Benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtaining the MCM-41 mass content is 10% heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, and wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 5/95.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.62 under the 100kHz.The room temperature storage modulus of hybrid material is 5.3GPa, and second-order transition temperature is 324 ℃.
Embodiment 18
With particle diameter is that the MCM-41 of 500nm and the toluene solution of γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane place there-necked flask, refluxes more than 24 hours, and filtration washing can obtain modified MC M-41.
0.0411g modified MC M-41 is scattered in the 11ml N-Methyl pyrrolidone (NMP), it was uniformly dispersed in ultrasonic 11 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid.
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) adds in the above-mentioned mesopore molecular sieve dispersion liquid, stirs, and waits to dissolve the back to wherein slowly adding 0.80g 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 20 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
0.07g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 0.5ml NMP, this solution is added in above-mentioned polyamic acid/mesoporous molecular sieve hybrid solution, continue down to stir 9 hours at 25 ℃, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid;
Benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtaining the MCM-41 mass content is 3% heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, and wherein the mass ratio of Polybenzoxazine in the resin combination and polyimide is 5/95.Directly surface brush last layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.45 under the 100kHz.The room temperature storage modulus of hybrid material is 4.2GPa, and second-order transition temperature is 316 ℃.
Comparative Examples 10
Under the protection of rare gas element, with 0.50g 4,4 '-diamines yl diphenyl ether (ODA) stirs in adding in the 11ml N-Methyl pyrrolidone (NMP), waits to dissolve the back to wherein slowly adding 0.80g3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After reinforced the finishing, 20 ℃ were reacted 15 hours down under the protection of rare gas element, obtained the nmp solution of polyamic acid;
0.07g dihydroxyphenyl propane-aniline type benzoxazine compound (BZ) is dissolved among the 0.5ml NMP, and this solution is added in the above-mentioned polyamic acid, continues down to stir 5 hours at 30 ℃, obtains the nmp solution of benzoxazine compound-polyamic acid;
The nmp solution of benzoxazine compound-polyamic acid is taken shape on the stainless steel plate, through 100 ℃/1 hour, after two sections curing in 280 ℃/2 hours, obtain heat curing-type Polybenzoxazine-polyimide resin composition, wherein the mass ratio of Polybenzoxazine and polyimide is 5/95.Directly surface brush one layer thickness is about 0.5 micron elargol layer thereon, treat the elargol completely solidified after, carry out the dielectric properties test, specific inductivity is 3.80 under the 100kHz.The room temperature storage modulus of hybrid material is 3.1GPa, and second-order transition temperature is 316 ℃.
By the contrast of the concrete numerical value of material property in embodiment and the Comparative Examples, illustrate in an amount of mesopore molecular sieve introducing heat curing-type Polybenzoxazine-polyimide resin composition matrix, can access the hybrid material of excellent combination property.Compare with pure heat curing-type Polybenzoxazine-polyimide resin composition matrix, the specific inductivity of hybrid material can reduce 0.1-0.6, and the room temperature storage modulus can improve 10-70% simultaneously, and second-order transition temperature remains unchanged or raising is arranged slightly.But when the mass content of mesopore molecular sieve is higher than 15%, take place owing to reunite, it is uneven that it is disperseed in the oil/fat composition matrix, so the performance of hybrid material can present downtrending.

Claims (12)

1. heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material, it is characterized in that: this hybrid material is made up of heat curing-type Polybenzoxazine-polyimide resin composition and mesopore molecular sieve, wherein said heat curing-type Polybenzoxazine-polyimide resin composition is made up of Polybenzoxazine and polyimide, and the mass content of described mesopore molecular sieve in hybrid material is 0.5～15%.
2. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 1/mesoporous molecular sieve hybrid material, it is characterized in that: in described heat curing-type Polybenzoxazine-polyimide resin composition, the mass ratio of Polybenzoxazine and polyimide is 1/99～99/1.
3. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 1 and 2/mesoporous molecular sieve hybrid material, it is characterized in that: the monomer of described Polybenzoxazine is a benzo oxazinyl compound, and wherein benzo oxazinyl compound is selected from one or more in diamines type benzo oxazinyl compound or the bisphenol type benzo oxazinyl compound.
4. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 3/mesoporous molecular sieve hybrid material is characterized in that:
Described diamines type benzo oxazinyl compound has formula (I) structure:
Figure F2009100325318C0000011
R 3Be hydrogen, methyl or allyl group,
Y is-(CH 2) 6-,-(CH 2) 8-,-(CH 2) 10-,-(CH 2) 12-,
Figure F2009100325318C0000012
Figure F2009100325318C0000013
Described bisphenol type benzo oxazinyl compound has formula (II) structure:
Figure F2009100325318C0000014
R 1Be hydrogen, methyl or ethynyl, cyano group or alkynes third alkoxyl group,
R 2Be hydrogen or allyl group,
X is-CH 2-,-O-,-C (CH 3) 2-or-SO 2-.
5. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 1 and 2/mesoporous molecular sieve hybrid material, it is characterized in that: described polyimide is made up of dicarboxylic anhydride monomer and diamine monomer, and the monomeric mol ratio of diamine monomer and dicarboxylic anhydride is 1: 1.02～1.20.
6. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 5/mesoporous molecular sieve hybrid material is characterized in that: described dicarboxylic anhydride monomer is pyromellitic acid anhydride or 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride; Described diamine monomer is 4,4 '-diamines yl diphenyl ether or p-phenylenediamine.
7. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 1/mesoporous molecular sieve hybrid material, it is characterized in that: the median size of described mesopore molecular sieve is 50～1000nm, the aperture is 2～30nm, and specific surface area is 500～2000m 2/ g, pore volume is 0.7～1.2cm 3/ g.
8. according to claim 1 or 7 described heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid materials, it is characterized in that: described mesopore molecular sieve is through silane coupler modified mesopore molecular sieve or without silane coupler modified mesopore molecular sieve.
9. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 8/mesoporous molecular sieve hybrid material, it is characterized in that: described silane coupling agent is a Union carbide A-162, methyltrimethoxy silane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane.
10. heat curing-type Polybenzoxazine-polyimide resin composition according to claim 9/mesoporous molecular sieve hybrid material, it is characterized in that: described silane coupling agent is a Union carbide A-162, vinyltrimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-[(2,3)-epoxy third oxygen] propyl trimethoxy silicane.
11. a method for preparing claim 1,2,4,6 or 7 described heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid materials is characterized in that:
The mass ratio of Polybenzoxazine and polyimide, may further comprise the steps less than 50/50 o'clock more than or equal to 1/99 in heat curing-type Polybenzoxazine-polyimide resin composition:
(1) mesopore molecular sieve is scattered in the organic solvent, it was uniformly dispersed in ultrasonic 1.5～20 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
(2) under the protection of rare gas element, diamine monomer is added in the above-mentioned mesopore molecular sieve dispersion liquid, stir, wait to dissolve the back to wherein slowly adding the dicarboxylic anhydride monomer; After reinforced the finishing, 10～35 ℃ were reacted 12～24 hours down under the protection of rare gas element, obtained polyamic acid/mesoporous molecular sieve hybrid solution;
(3) benzoxazine compound is dissolved in organic solvent, obtain benzoxazine compound solution, this solution is added in polyamic acid/mesoporous molecular sieve hybrid solution, continue to stir 5～15 hours down, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 10～35 ℃;
(4) with benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid after carrying out segmentation under 100～320 ℃ and solidifying, obtain heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material;
When Polybenzoxazine in heat curing-type Polybenzoxazine-polyimide resin composition and polyimide mass ratio are 50/50～99/1, may further comprise the steps:
(a) mesopore molecular sieve is scattered in the organic solvent, it was uniformly dispersed in ultrasonic 1.5～20 hours under the room temperature, obtain the mesopore molecular sieve dispersion liquid;
(b) benzoxazine compound is added in the mesopore molecular sieve dispersion liquid, continue down to stir 12～24 hours, obtain benzoxazine compound/mesopore molecular sieve mixing liquid at 10～35 ℃;
(c) under the protection of rare gas element, diamine monomer is added in the organic solvent, stir, wait to dissolve the back to wherein slowly adding the dicarboxylic anhydride monomer; After reinforced the finishing, 10～35 ℃ were reacted 12～24 hours down under the protection of rare gas element, obtained polyamic acid solution; This solution is joined in benzoxazine compound/mesopore molecular sieve mixing liquid, continue down to stir 5～15 hours, obtain benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid at 10～35 ℃;
(d) with benzoxazine compound-polyamic acid/mesopore molecular sieve mixing liquid after carrying out segmentation under 100～250 ℃ and solidifying, obtain heat curing-type Polybenzoxazine-polyimide resin composition/mesoporous molecular sieve hybrid material.
12. preparation method according to claim 11, it is characterized in that: step (1), (3), (a) or (c) described in organic solvent be N respectively independently, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).
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Application publication date: 20110105