CN100489033C - Thermostable composition of low dielectric loss and its preparing process - Google Patents
Thermostable composition of low dielectric loss and its preparing process Download PDFInfo
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- CN100489033C CN100489033C CNB2006100981120A CN200610098112A CN100489033C CN 100489033 C CN100489033 C CN 100489033C CN B2006100981120 A CNB2006100981120 A CN B2006100981120A CN 200610098112 A CN200610098112 A CN 200610098112A CN 100489033 C CN100489033 C CN 100489033C
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Abstract
The invention discloses a heat-proof composition with low-dielectric consumption, which consists of 40-99.9% cyanate and 0.1-60% barium titanate, wherein the grain size of barium titanate is between 150 and 600 order. The making method comprises the following steps: blending cyanate and barium titanate to fuse at 100 deg.c; heating to 130-160 deg.c to presolidify until the barium titanate doesn't sediment obviously; obtaining the composition with dielectric constant between 2 and 6 adjustably through changing the content of barium titanate , physical chemical property and subsequent disposing technique of composition.
Description
Technical field
The present invention relates to a kind of heat-resisting organic/inorganic binary composition that has dielectric-constant adjustable and low-dielectric loss concurrently, belong to the dielectric composite material preparing technical field.
Background technology
Be the requirement satisfy the electrical property design and to use, modern industry is increasing to the demand of the heat-stable material that has dielectric-constant adjustable and low-dielectric loss concurrently.Because the material of single variety is difficult to take into account the requirement of manufacturability and use properties, exploitation has become the research focus in current dielectric materials field with the organic/inorganic composite material of the excellent dielectric properties of organic polymer excellent mechanical properties, manufacturability and inorganics.
In recent years, research about the organic/inorganic composite dielectric material is a lot, selected organic polymer matrix mainly contains polyvinylidene difluoride (PVDF), vinylidene (VDF)-trifluoro-ethylene (TrFE) multipolymer, tetrafluoroethylene, polyimide resin and Resins, epoxy etc., and the pottery of selecting for use is generally barium titanate (BaTiO
3), lead titanate (PbTiO
3) and Pb-based lanthanumdoped zirconate titanates etc.For example employing pressure sintering such as Dong Li outstanding person has prepared PbTiO
3/ PVDF matrix material is worked as PbTiO
3Mass percent at 70% o'clock, matrix material specific inductivity maximum (77.6), this moment dielectric loss be about 0.1; When being resin matrix with polyvinylidene difluoride (PVDF)-trifluoro-ethylene, Bhattacharya finds at PbTiO
3Volume fraction be respectively 21 and the specific inductivity of 40% o'clock two kind of matrix material be respectively 9 and 34; People such as Zhu Baoku are the barium titanate (BaTiO of 100nm with the granularity of polyamic acid solution and silane coupling agent processing
3) particle carries out solution blending and prepare dielectric composite material, at BaTiO
3The volume fraction of particle reaches at 50% o'clock, and specific inductivity can reach 35, and dielectric loss is 0.0082 (10kHz), and keeps stable in sizable temperature and range of frequency; People such as Kuo are with BaTiO
3Join in the Resins, epoxy, obtained specific inductivity and be about 50 matrix material.
Can see (1) selected mineral filler granularity all less (tens microns～nanometer) from existing document, the cost of raw material is higher; (2) dielectric loss of resulting matrix material higher (all being higher than resin matrix), unfavorable to the product of research and development high stability; (3) can not adopt simple organic/inorganic binary complex method to obtain to have concurrently the material of dielectric-constant adjustable and low-dielectric loss characteristic, need aid in means such as doping.
Cyanate (CE) resin is the high-performance thermosetting resin of a class excellent combination property of late 1960s exploitation.Compare with Resins, epoxy, bismaleimides and the resol of a large amount of uses at present, CE has excellent more dielectric properties, show dielectric loss extremely low (0.002～0.006), and dielectric properties all demonstrate distinctive stability to the variation of temperature and wave frequency.Compare with other engineering thermoplastic resin (as polyimide resin, polyphenylene oxide, polyphenyl and cyclobutene resin etc.), CE resin manufacturability is good, with low cost, has higher cost performance.In the leading-edge field that comprises industry such as microelectronics, Aeronautics and Astronautics, particularly under to all exigent occasion of dielectric properties, damp and hot performance and mechanical property, CE is the most competitive resin kind.Therefore, the applicant considers based on cyanate ester resin, prepares a kind of heat-resistant composition of new low-dielectric loss.
Summary of the invention
The object of the invention provides the heat-resistant composition of a kind of while with the low-dielectric loss of dielectric-constant adjustable performance; And provide the preparation method of this heat-resistant composition.
For achieving the above object, the technical solution used in the present invention is: a kind of heat-resistant composition of low-dielectric loss, and by weight, cyanate by 40～99.9% and 0.1～60% barium titanate are formed, and the granularity of described barium titanate is between 600 orders～150 orders.
In the technique scheme, described barium titanate is selected from not surface treated barium titanate, surface treated barium titanate or its composition, described surface treatment is that coupling agent is dissolved in the organic solution, then pour the barium titanate of oven dry in advance into, stir with the high speed homogenization stirrer, hang, oven dry obtains surface treated barium titanate thus.
Described cyanate is selected from a kind of or its composition in bisphenol A-type, bisphenol E-type, Bisphenol F type, bis-phenol M type, the dicyclopentadiene type bisphenol type.The commercialization of cyanate resin fat prod, therefore, the cyanate ester resin of mentioned kind all can adopt any one commercial cyanate resin fat prod.
The preparation method of the heat-resistant composition of low-dielectric loss of the present invention is, with cyanate and barium titanate by described weight ratio mix, after 100 ℃ of fusions, be warming up to 130～160 ℃ and carry out Procuring, do not have obvious sedimentation to barium titanate, promptly obtain the heat-resistant composition of described low-dielectric loss.
Through after the Procuring, barium titanate can be in cyanate ester resin uniform distribution, after this, promptly can be cured, obtain required heat-stable material.
Described coupling agent is silane coupling agent or titante coupling agent.
Wherein, the described Procuring time reduces with the increase of barium titanate content or the raising of Procuring temperature, and preferred scheme is that the described Procuring time is between 0.5～8 hour.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. to adopt the cyanate with excellent dielectric properties be matrix resin in the present invention, constitutes the binary compound organic/inorganic composition with barium titanate, not only has the characteristic (2～16) that specific inductivity is high and can regulate, and dielectric loss extremely low (＜0.002);
2. barium titanate of the present invention adopts the granularity between 600 orders～150 orders, in the prior art, the barium titanate that adopts in binary composition is a nanoscale, and the present invention adopts the bigger barium titanate of granularity, obtained the composition of low-dielectric loss, reason is the bigger BaTiO of granularity
3Motion to the CE molecule has tangible inhibition, and this inhibition is along with BaTiO
3The increase of content and strengthening, thus cause the dielectric loss of composition to be starkly lower than pure CE resin, and with BaTiO
3The increase of content and reducing, this is that those skilled in the art institute is beyond thought, therefore, the present invention has overcome prejudice, and is creative; Simultaneously, because BaTiO
3Particle diameter big (between 600 orders～150 orders), composition also has the characteristics that cost is lower, starting material are easy to get.
3. the present invention adopts the method for simple casting, is resin matrix with the cyanate, BaTiO
3Be functional stuffing, obtained a kind of heat-resisting organic/inorganic binary composition that has dielectric-constant adjustable and low-dielectric loss concurrently, preparation technology is simple.
Description of drawings
Accompanying drawing 1 is the specific inductivity of composition of the embodiment of the invention one and the graph of relation of frequency;
Accompanying drawing 2 is the composition of the embodiment of the invention two to embodiment seven and the specific inductivity and the BaTiO of comparative example 1
3The graph of relation of content (under the 1KHz);
Accompanying drawing 3 is composition and the dielectric loss tangent of comparative example 1 and graph of relation (under the 1KHz) of BaTiO3 content of the embodiment of the invention two to embodiment seven.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
Press listed A1 in the table 1, with bisphenol A-type two cyanates (BADCy) and BaTiO
3(400 order) pressed proportional quantity and mixed, and mixture behind the heating and melting, is warming up to 150 ℃ of Procuring 4 hours, BaTiO in 100 ℃ of oil baths
3Do not have obvious sedimentation, promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.
Composition is infused in the mould after the preheating (150 ℃), vacuum outgas is 30 minutes in 100～105 ℃ vacuum drying oven, be cured by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, carry out aftertreatment, promptly obtain BADCy/BaTiO by the technology of 230 ℃/5h
3Matrix material.Specific inductivity in test 1Hz～10GHz scope, it is worth as shown in Figure 1.As can be seen, the specific inductivity of material is stable in whole test frequency scope.
Embodiment two～seven:
Press listed A1 in the table 1～A7 prescription, with bisphenol A-type two cyanates (BADCy) and BaTiO
3(400 order) pressed proportional quantity and mixed, and mixture behind the heating and melting, is warming up to 150 ℃ of Procuring certain hours to BaTiO in 100 ℃ of oil baths
3Do not have obvious sedimentation (as shown in table 1), promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.
Composition is infused in the mould after the preheating (150 ℃), vacuum outgas 30min in 100～105 ℃ vacuum drying oven, be cured by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, carry out aftertreatment, promptly obtain BADCy/BaTiO by the technology of 230 ℃/5h
3Matrix material.The dielectric properties of each sample under 1KHz are shown in accompanying drawing 2 and accompanying drawing 3.Can see that the specific inductivity of material is with BaTiO in the system
3BaTiO is worked as in the increase of content and increasing
3Content is when 0～60wt% range, and the specific inductivity of material is adjustable in 2-16 scopes.In addition, the dielectric loss of matrix material significantly is lower than pure CE resin.
Table 1 prescription and 150 ° of Procuring times
Comparative example 1
With BADCy in 100 ℃ of oil baths behind the heating and melting, after being warming up to 150 ℃ of Procuring 4h, mould after the injection preheating (150 ℃), vacuum outgas 30min in 100～105 ℃ vacuum drying oven, be cured by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, technology by 230 ℃/5h is carried out aftertreatment, promptly obtains pure BADCy cured resin.Its dielectric properties under 1KHz are shown in accompanying drawing 2 and accompanying drawing 3.
Embodiment eight～nine:
With 35g BADCy and 15g BaTiO
3(400 order) mixes, and mixture behind the heating and melting, is warming up to 130 ℃ of Procuring 8h to BaTiO in 100 ℃ of oil baths
3Do not have obvious sedimentation, promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.
Composition is infused in 150 ℃ of moulds after the preheating, vacuum outgas 30min in 100～105 ℃ vacuum drying oven, be cured by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology respectively, carry out aftertreatment by the technology of 220 ℃/1h or 220 ℃/1h+230 ℃/4h respectively at last.The dielectric properties data of gained sample are as shown in table 2.As can be seen, be about at 100% o'clock in the state of cure of material, the specific inductivity of material can be realized by the aftertreatment technology that changes material.In addition, the dielectric loss tangent value of material subsequently degree of treatment increasing and further reduce.
Table 2 aftertreatment technology is to dielectric material Effect on Performance (under the 1KHz)
Embodiment ten～11:
With 5 gram acetone diluted, 0.4 gram silane coupling agent γ-An Bingjisanyiyangjiguiwan (KH-550), add 20 gram BaTiO then
3(400 order) hangs behind the uniform mixing, treat the volatilization of most of acetone after, at 70 ℃ of baking 6h, promptly obtained the BaTiO that the surface has the processing of Si-O-Si chemical bond
3
With the BaTiO after 25 gram BADCy and the 20g surface treatment
3(400 order) thorough mixing is even, and mixture behind the heating and melting, is warming up to 150 ℃ of Procuring 1h in 100 ℃ of oil baths, promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.
Composition is infused in 150 ℃ of moulds after the preheating, vacuum outgas 30min in 100～105 ℃ vacuum drying oven, after solidifying by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, by 220 ℃/1h or 220 ℃/1h+230 ℃/4h technology aftertreatment, make sample respectively.The dielectric properties data of gained sample are as shown in table 3.As can be seen, be about at 100% o'clock in the state of cure of material, the specific inductivity of material can realize that promptly coupling agent can significantly improve BaTiO by the Surface Physical Chemistry character that changes material
3The dispersion effect of particle in the cyanate matrix, thereby the specific inductivity of raising material, and the dielectric loss tangent of material value is unaffected.
Table 3 BaTiO
3(400 order) surface treatment is to the dielectric material Effect on Performance
Embodiment 12:
With 20g BADCy, 10g bisphenol E-type cyanate and 25g BaTiO
3(600 order) mixes, and mixture behind the heating and melting, is warming up to 160 ℃ of Procuring 1.5h to BaTiO in 100 ℃ of oil baths
3Do not have obvious sedimentation, promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.Composition is infused in the mould after the preheating (150 ℃), vacuum outgas is 30 minutes in 100～105 ℃ vacuum drying oven, be cured by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, carry out aftertreatment, promptly obtain BADCy/BaTiO by the technology of 230 ℃/5h
3Matrix material.Specific inductivity and the dielectric loss tangent value of gained sample under 1KHz is respectively 10.0573 and 0.0015.
Embodiment 13:
With 5 gram isopropyl alcohol dissolvings, 0.4 gram titante coupling agent isopropyl tri (dioctylpyrophosphato)titanate, add 20 gram BaTiO then
3(150 order), uniform mixing hangs, treat the volatilization of most of isopropyl alcohol after, at 85 ℃ of baking 6h, promptly obtained surface treated BaTiO
3(150 order).
With 20g dicyclopentadiene bisphenol type cyanate, 15g bisphenol E-type cyanate and the surface treated BaTiO of 15g
3(150 order) mixes, and mixture behind the heating and melting, is warming up to 140 ℃ of Procuring 5h to BaTiO in 100 ℃ of oil baths
3Do not have obvious sedimentation, promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.
Composition is infused in 150 ℃ of moulds after the preheating, and vacuum outgas 30min in 100～105 ℃ vacuum drying oven after solidifying by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, by 220 ℃/1h+230 ℃/4h technology aftertreatment, makes sample.Specific inductivity and the dielectric loss tangent value of gained sample under 1KHz is respectively 8.4573 and 0.002.
Embodiment 14:
The BaTiO that 30g bisphenol A-type two cyanates (BADCy) and 10g are handled through silane resin acceptor kh-550
3(240 order) mixes, and mixture behind the heating and melting, is warming up to 150 ℃ of Procuring 4 hours, BaTiO in 100 ℃ of oil baths
3Do not have obvious sedimentation, promptly obtain having concurrently the organic/inorganic binary composition of dielectric-constant adjustable and low-dielectric loss.
Composition is infused in the mould after the preheating (150 ℃), vacuum outgas is 30 minutes in 100～105 ℃ vacuum drying oven, be cured by 160 ℃/2h+180 ℃/2h+200 ℃/2h technology, carry out aftertreatment, promptly obtain BADCy/BaTiO by the technology of 230 ℃/5h
3Matrix material.Specific inductivity and the dielectric loss tangent value of gained sample under 1KHz is respectively 8.4573 and 0.001.
Claims (6)
1, a kind of heat-resistant composition of low-dielectric loss is characterized in that: by weight, cyanate by 40～99.9% and 0.1～60% barium titanate are formed, and the granularity of described barium titanate is between 600 orders～150 orders; The dielectric loss value of described heat-resistant composition is less than 0.002.
2, the heat-resistant composition of low-dielectric loss according to claim 1, it is characterized in that: described barium titanate is selected from not surface treated barium titanate, surface treated barium titanate or its composition, described surface treatment is that coupling agent is dissolved in the organic solution, then pour the barium titanate of oven dry in advance into, stir with the high speed homogenization stirrer, hang oven dry.
3, the heat-resistant composition of low-dielectric loss according to claim 1 is characterized in that: described cyanate is selected from a kind of or its composition in bisphenol A-type, bisphenol E-type, Bisphenol F type, bis-phenol M type, the dicyclopentadiene type bisphenol type.
4, the preparation method of the heat-resistant composition of the described low-dielectric loss of claim 1, it is characterized in that: with cyanate and barium titanate by described weight ratio mix, after 100 ℃ of fusions, be warming up to 130～160 ℃ and carry out Procuring, do not have obvious sedimentation to barium titanate, promptly obtain the heat-resistant composition of described low-dielectric loss.
5, the preparation method of the heat-resistant composition of low-dielectric loss according to claim 4, it is characterized in that: described barium titanate is selected from not surface treated barium titanate, surface treated barium titanate or its composition, described surface treatment is that coupling agent is dissolved in the organic solution, then pour the barium titanate of oven dry in advance into, stir with the high speed homogenization stirrer, hang oven dry; Described coupling agent is silane coupling agent or titante coupling agent.
6, the preparation method of the heat-resistant composition of low-dielectric loss according to claim 4 is characterized in that: the described Procuring time is between 0.5～8 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101921479B (en) * | 2010-08-11 | 2012-04-04 | 苏州大学 | Cyanate resin base composite material and preparation method thereof |
| CN107814551B (en) * | 2017-10-31 | 2019-11-05 | 福州大学 | A kind of high energy storage and power density dielectric material and preparation method thereof |
| CN107746206B (en) * | 2017-10-31 | 2019-09-10 | 福州大学 | A kind of High-energy-storage density dielectric material and preparation method thereof |
| CN107586060B (en) * | 2017-10-31 | 2019-11-08 | 福州大学 | A kind of High-energy-storage density dielectric material and preparation method thereof |
| CN108395670B (en) * | 2018-03-12 | 2020-07-10 | 航天特种材料及工艺技术研究所 | Preparation method of high-temperature-resistant equivalent medium core layer |
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Assignee: Guangzhou Cable Plant Co., Ltd. Assignor: Soochow University Contract record no.: 2010440001210 Denomination of invention: Thermostable composition of low dielectric loss and its preparing process Granted publication date: 20090520 License type: Exclusive License Open date: 20070530 Record date: 20100819 |
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