CN100489033C - Thermostable composition of low dielectric loss and its preparing process - Google Patents

Thermostable composition of low dielectric loss and its preparing process Download PDF

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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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barium titanate
heat
dielectric loss
low dielectric
composition
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CN1970628A (en
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顾嫒娟
晁芬
梁国正
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Suzhou University
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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

一种低介电损耗的耐热组合物及其制备方法 A heat-resistant composition with low dielectric loss and its preparation method

技术领域 technical field

本发明涉及一种兼具介电常数可调和低介电损耗的耐热有机/无机二元组合物,属于介电复合材料制备技术领域。The invention relates to a heat-resistant organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss, belonging to the technical field of dielectric composite material preparation.

背景技术 Background technique

为满足电性能设计及使用的要求,现代工业对兼具介电常数可调和低介电损耗的耐热材料的需求越来越大。由于单一品种的材料很难兼顾工艺性和使用性能的要求,开发兼具有有机聚合物优良机械性能、工艺性以及无机物优异介电性能的有机/无机复合材料已成为当前介电材料领域的研究热点。In order to meet the requirements of electrical performance design and use, modern industry has an increasing demand for heat-resistant materials with adjustable dielectric constant and low dielectric loss. Since it is difficult to meet the requirements of manufacturability and performance for a single variety of materials, the development of organic/inorganic composite materials that have both the excellent mechanical properties and manufacturability of organic polymers and the excellent dielectric properties of inorganic substances has become the current focus in the field of dielectric materials. Research hotspots.

近年来,关于有机/无机复合电介质材料的研究很多,所选用的有机聚合物基体主要有聚偏氟乙烯、偏氟乙烯(VDF)—三氟乙烯(TrFE)共聚物、聚四氟乙烯、聚酰亚胺树脂和环氧树脂等,选用的陶瓷一般为钛酸钡(BaTiO3)、钛酸铅(PbTiO3)和锆钛酸铅等。例如董丽杰等采用热压法制备了PbTiO3/PVDF复合材料,当PbTiO3的质量百分数在70%时,复合材料介电常数最大(77.6),此时介电损耗为0.1左右;Bhattacharya以聚偏氟乙烯—三氟乙烯为树脂基体时发现在PbTiO3体积分数分别为21和40%时两种复合材料的介电常数分别为9和34;朱宝库等人将聚酰胺酸溶液与硅烷偶联剂处理的粒度为100nm的钛酸钡(BaTiO3)粒子进行溶液共混制备介电复合材料,在BaTiO3粒子的体积分数达50%时,介电常数可达35,介电损耗为0.0082(10kHz),而且在相当大的温度和频率范围内保持稳定;Kuo等人将BaTiO3加入到环氧树脂中,获得了介电常数为50左右的复合材料。In recent years, there have been many studies on organic/inorganic composite dielectric materials. The selected organic polymer matrices mainly include polyvinylidene fluoride, vinylidene fluoride (VDF)-trifluoroethylene (TrFE) copolymer, polytetrafluoroethylene, poly Imide resin and epoxy resin, etc. The ceramics used are generally barium titanate (BaTiO 3 ), lead titanate (PbTiO 3 ) and lead zirconate titanate. For example, Dong Lijie prepared PbTiO 3 /PVDF composite material by hot pressing method. When the mass percentage of PbTiO 3 is 70%, the dielectric constant of the composite material is the largest (77.6), and the dielectric loss is about 0.1 at this time; When vinyl fluoride-trifluoroethylene was used as the resin matrix, it was found that the dielectric constants of the two composite materials were 9 and 34 when the volume fraction of PbTiO 3 was 21 and 40%, respectively; Zhu Baoku et al. coupled polyamic acid solution with silane Barium titanate (BaTiO 3 ) particles with a particle size of 100nm were prepared by solution blending to prepare a dielectric composite material. When the volume fraction of BaTiO 3 particles reaches 50%, the dielectric constant can reach 35 and the dielectric loss is 0.0082 ( 10kHz), and it is stable in a considerable range of temperature and frequency; Kuo et al. added BaTiO 3 to epoxy resin to obtain a composite material with a dielectric constant of around 50.

从已有文献中可以看到(1)所选用的无机填料粒度均较小(十几微米~纳米),原料的成本较高;(2)所得到的复合材料的介电损耗较高(均高于树脂基体),对研发高稳定性的产品不利;(3)不能采用简单的有机/无机二元复合方法来获得兼具介电常数可调和低介电损耗特性的材料,需要辅助于掺杂等手段。It can be seen from the existing literature that (1) the particle size of the selected inorganic fillers is small (more than ten microns to nanometers), and the cost of raw materials is relatively high; (2) the dielectric loss of the obtained composite material is relatively high (average higher than the resin matrix), which is unfavorable for the development of high-stability products; (3) the simple organic/inorganic binary compound method cannot be used to obtain materials with both adjustable dielectric constant and low dielectric loss characteristics, and it is necessary to assist in doping miscellaneous means.

氰酸酯(CE)树脂是20世纪60年代末开发的一类综合性能优异的高性能热固性树脂。与目前大量使用的环氧树脂、双马来酰亚胺和酚醛树脂相比,CE具有更加优异的介电性能,表现在介电损耗极低(0.002~0.006),而且介电性能对温度及电磁波频率的变化都显示出特有的稳定性。与其它工程热塑性树脂(如聚酰亚胺树脂、聚苯醚、聚苯并环丁烯树脂等)相比,CE树脂工艺性优良、成本低廉,具有更高的性价比。在包括微电子、航空、航天等工业在内的尖端领域中,特别是在对介电性能、湿热性能和力学性能都要求很高的场合下,CE是最具竞争力的树脂品种。因此,申请人考虑以氰酸酯树脂为基础,制备出一种新的低介电损耗的耐热组合物。Cyanate ester (CE) resin is a kind of high-performance thermosetting resin with excellent comprehensive properties developed in the late 1960s. Compared with epoxy resin, bismaleimide and phenolic resin, which are widely used at present, CE has more excellent dielectric properties, which is manifested in extremely low dielectric loss (0.002-0.006), and the dielectric properties have no effect on temperature and Changes in the frequency of electromagnetic waves show a unique stability. Compared with other engineering thermoplastic resins (such as polyimide resin, polyphenylene ether, polybenzocyclobutene resin, etc.), CE resin has excellent manufacturability, low cost and higher cost performance. In cutting-edge fields including microelectronics, aviation, aerospace and other industries, especially in the occasions that require high dielectric properties, hygrothermal properties and mechanical properties, CE is the most competitive resin variety. Therefore, the applicant considered to prepare a new heat-resistant composition with low dielectric loss based on cyanate resin.

发明内容 Contents of the invention

本发明目的是提供一种同时兼具有介电常数可调性能的低介电损耗的耐热组合物;并提供这种耐热组合物的制备方法。The purpose of the present invention is to provide a heat-resistant composition with low dielectric loss and adjustable dielectric constant; and to provide a preparation method for the heat-resistant composition.

为达到上述目的,本发明采用的技术方案是:一种低介电损耗的耐热组合物,按重量计,由40~99.9%的氰酸酯和0.1~60%钛酸钡组成,所述钛酸钡的粒度在600目~150目之间。In order to achieve the above object, the technical solution adopted by the present invention is: a heat-resistant composition with low dielectric loss, which is composed of 40-99.9% cyanate and 0.1-60% barium titanate by weight. The particle size of barium titanate is between 600 mesh and 150 mesh.

上述技术方案中,所述钛酸钡选自未经表面处理的钛酸钡、经过表面处理的钛酸钡或者其组合物,所述表面处理是将偶联剂溶解于有机溶液中,而后倒入预先烘干的钛酸钡,用高速均质搅拌机搅拌均匀,晾置,烘干,由此获得经表面处理的钛酸钡。In the above technical scheme, the barium titanate is selected from barium titanate without surface treatment, barium titanate with surface treatment or a combination thereof, and the surface treatment is to dissolve the coupling agent in an organic solution, and then pour Put in the pre-dried barium titanate, stir evenly with a high-speed homogeneous mixer, let it air, and dry it to obtain surface-treated barium titanate.

所述氰酸酯选自双酚A型、双酚E型、双酚F型、双酚M型、双环戊二烯型双酚型中的一种或其组合物。氰酸酯树脂产品已经商品化,因此,上述种类的氰酸酯树脂均可以采用任意一种商品化的氰酸酯树脂产品。The cyanate is selected from one of bisphenol A type, bisphenol E type, bisphenol F type, bisphenol M type, dicyclopentadiene type bisphenol type or a combination thereof. Cyanate resin products have been commercialized. Therefore, any commercial cyanate resin products can be used for the above-mentioned types of cyanate resins.

本发明的低介电损耗的耐热组合物的制备方法是,将氰酸酯和钛酸钡按所述重量比混合、在100℃熔融后,升温至130~160℃进行预固化,至钛酸钡无明显沉降,即获得所述低介电损耗的耐热组合物。The preparation method of the low dielectric loss heat-resistant composition of the present invention is to mix cyanate ester and barium titanate according to the weight ratio, melt at 100°C, and then heat up to 130-160°C for pre-curing, until titanium There is no obvious precipitation of barium acid, that is, the heat-resistant composition with low dielectric loss is obtained.

经过预固化以后,钛酸钡可以在氰酸酯树脂中均匀分布,此后,即可以进行固化,获得所需的耐热材料。After pre-curing, the barium titanate can be evenly distributed in the cyanate resin, and then it can be cured to obtain the desired heat-resistant material.

所述的偶联剂为硅烷类偶联剂或钛酸酯类偶联剂。The coupling agent is a silane coupling agent or a titanate coupling agent.

其中,所述的预固化时间随钛酸钡含量的增加或预固化温度的提高而减小,优选的方案为,所述的预固化时间在0.5~8小时之间。Wherein, the pre-curing time decreases with the increase of the barium titanate content or the increase of the pre-curing temperature, and the preferred solution is that the pre-curing time is between 0.5 and 8 hours.

由于上述技术方案运用,本发明与现有技术相比具有下列优点:Due to the use of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art:

1.本发明采用具有优异介电性能的氰酸酯为基体树脂,构成与钛酸钡的二元复合的有机/无机组合物,不仅具有介电常数高且可以调节的特性(2~16),而且介电损耗极低(<0.002);1. The present invention uses cyanate ester with excellent dielectric properties as matrix resin to form a binary composite organic/inorganic composition with barium titanate, which not only has a high dielectric constant but also can be adjusted (2-16) , and the dielectric loss is extremely low (<0.002);

2.本发明的钛酸钡采用600目~150目之间的粒度,现有技术中,在二元组合物中采用的钛酸钡为纳米尺度,本发明采用粒度较大的钛酸钡,获得了低介电损耗的组合物,原因是粒度较大的BaTiO3对CE分子的运动有明显的阻碍作用,这种阻碍作用随着BaTiO3含量的增加而加大,从而导致组合物的介电损耗明显低于纯CE树脂,且随BaTiO3含量的增加而降低,这是本领域技术人员所意想不到的,因此,本发明克服了偏见,具有创造性;同时,由于BaTiO3的粒径较大(在600目~150目之间),组合物还具有成本较低、原材料易得的特点。2. The barium titanate of the present invention adopts a particle size between 600 mesh and 150 mesh. In the prior art, the barium titanate used in the binary composition is nanoscale. The present invention adopts the larger barium titanate particle size, The composition with low dielectric loss is obtained, because the BaTiO 3 with larger particle size has obvious hindering effect on the movement of CE molecules, and this hindering effect increases with the increase of BaTiO 3 content, resulting in a dielectric Electric loss is significantly lower than pure CE resin, and decreases with the increase of BaTiO3 content, which is unexpected by those skilled in the art. Therefore, the present invention overcomes the prejudice and has creativity; meanwhile, because the particle size of BaTiO3 is relatively small Large (between 600 mesh and 150 mesh), the composition also has the characteristics of low cost and easy availability of raw materials.

3.本发明采用简单浇铸的方法,以氰酸酯为树脂基体,BaTiO3为功能填料,获得了一种兼具介电常数可调和低介电损耗的耐热有机/无机二元组合物,制备工艺简单。3. The present invention adopts a simple casting method, uses cyanate ester as the resin matrix, and BaTiO3 as the functional filler, and obtains a heat-resistant organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss. The preparation process is simple.

附图说明 Description of drawings

附图1是本发明实施例一的组合物的介电常数与频率的关系曲线图;Accompanying drawing 1 is the relation graph of the dielectric constant and the frequency of the composition of the embodiment of the present invention;

附图2是本发明实施例二至实施例七的组合物及比较例1的介电常数与BaTiO3含量的关系曲线图(1KHz下);Accompanying drawing 2 is the dielectric constant of the composition of the present invention embodiment 2 to embodiment 7 and comparative example 1 and BaTiO Content relational graph (under 1KHz);

附图3是本发明实施例二至实施例七的组合物及比较例1的介电损耗正切与BaTiO3含量的关系曲线图(1KHz下)。Accompanying drawing 3 is the relationship curve (under 1KHz) of dielectric loss tangent and BaTiO3 content of the composition of embodiment 2 to embodiment 7 of the present invention and comparative example 1.

具体实施方式 Detailed ways

下面结合实施例对本发明作进一步描述:The present invention will be further described below in conjunction with embodiment:

实施例一:Embodiment one:

按表1中所列A1,将双酚A型二氰酸酯(BADCy)和BaTiO3(400目)按配比量混合,混合物在100℃油浴中加热熔融后,升温至150℃预固化4小时,BaTiO3无明显沉降,即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。According to A1 listed in Table 1, bisphenol A type dicyanate (BADCy) and BaTiO 3 (400 mesh) were mixed according to the proportion, and the mixture was heated and melted in an oil bath at 100°C, and then heated to 150°C for pre-curing 4 hours, BaTiO 3 has no obvious sedimentation, that is, an organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss is obtained.

将组合物注入在预热(150℃)后的模具中,于100~105℃的真空干燥箱中真空脱气30分钟,按160℃/2h+180℃/2h+200℃/2h工艺进行固化,按230℃/5h的工艺进行后处理,即得到BADCy/BaTiO3复合材料。测试1Hz~10GHz范围内的介电常数,其值如附图1所示。可以看出,材料的介电常数在整个测试频率范围内稳定。Inject the composition into a preheated (150°C) mold, degas it in a vacuum oven at 100-105°C for 30 minutes, and cure it according to the process of 160°C/2h+180°C/2h+200°C/2h , according to the process of 230 ℃ / 5h post-treatment, that is, get BADCy/BaTiO 3 composite material. Test the dielectric constant in the range of 1 Hz to 10 GHz, and its value is shown in Figure 1. It can be seen that the dielectric constant of the material is stable over the entire test frequency range.

实施例二~七:Embodiment two~seven:

按表1中所列A1~A7配方,将双酚A型二氰酸酯(BADCy)和BaTiO3(400目)按配比量混合,混合物在100℃油浴中加热熔融后,升温至150℃预固化一定时间至BaTiO3无明显沉降(如表1所示),即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。According to the formulas A1 to A7 listed in Table 1, mix bisphenol A dicyanate (BADCy) and BaTiO 3 (400 mesh) according to the proportion, heat and melt the mixture in an oil bath at 100°C, and then heat up to 150°C Pre-curing for a certain period of time until BaTiO 3 has no obvious sedimentation (as shown in Table 1), an organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss can be obtained.

将组合物注入在预热(150℃)后的模具中,于100~105℃的真空干燥箱中真空脱气30min,按160℃/2h+180℃/2h+200℃/2h工艺进行固化,按230℃/5h的工艺进行后处理,即得到BADCy/BaTiO3复合材料。各试样在1KHz下的介电性能如附图2和附图3所示。可以看到,材料的介电常数随体系中BaTiO3含量的增加而增大,当BaTiO3含量在0~60wt%范围变化时,材料的介电常数在2—16范围可调。此外,复合材料的介电损耗显著低于纯CE树脂。Inject the composition into a preheated (150°C) mold, degas it in a vacuum oven at 100-105°C for 30 minutes, and cure it according to the process of 160°C/2h+180°C/2h+200°C/2h. According to the process of 230 ℃ / 5h for post-treatment, the BADCy/BaTiO 3 composite material is obtained. The dielectric properties of each sample at 1KHz are shown in Figure 2 and Figure 3 . It can be seen that the dielectric constant of the material increases with the increase of the content of BaTiO 3 in the system. When the content of BaTiO 3 changes in the range of 0-60wt%, the dielectric constant of the material is adjustable in the range of 2-16. In addition, the dielectric loss of the composite is significantly lower than that of the pure CE resin.

表1  配方和在150°预固化时间Table 1 Formulation and pre-curing time at 150°

Figure C200610098112D00061
Figure C200610098112D00061

比较例1Comparative example 1

将BADCy在100℃油浴中加热熔融后,升温至150℃预固化4h后,注入预热(150℃)后的模具中,于100~105℃的真空干燥箱中真空脱气30min,按160℃/2h+180℃/2h+200℃/2h工艺进行固化,按230℃/5h的工艺进行后处理,即得到纯BADCy固化树脂。其在1KHz下的介电性能如附图2和附图3所示。Heat and melt BADCy in an oil bath at 100°C, heat up to 150°C for pre-curing for 4 hours, inject it into a preheated (150°C) mold, degas it in a vacuum oven at 100-105°C for 30 minutes, press 160 ℃/2h+180℃/2h+200℃/2h for curing, followed by 230℃/5h for post-treatment to obtain pure BADCy cured resin. Its dielectric properties at 1KHz are shown in Figure 2 and Figure 3 .

实施例八~九:Embodiment eight to nine:

将35g BADCy和15g BaTiO3(400目)混合,混合物在100℃油浴中加热熔融后,升温至130℃预固化8h至BaTiO3无明显沉降,即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。Mix 35g of BADCy and 15g of BaTiO 3 (400 mesh), heat and melt the mixture in an oil bath at 100°C, then raise the temperature to 130°C for 8 hours to pre-cure until BaTiO 3 has no obvious sedimentation, and then obtain a dielectric constant adjustable and low dielectric Lost organic/inorganic binary composition.

将组合物注入在150℃预热后的模具中,在100~105℃的真空干燥箱中真空脱气30min,分别按160℃/2h+180℃/2h+200℃/2h工艺进行固化,最后分别按220℃/1h或220℃/1h+230℃/4h的工艺进行后处理。所得样品的介电性能数据如表2所示。可以看出,在材料的固化程度约为100%时,材料的介电常数可以通过改变材料的后处理工艺实现。此外,材料的介电损耗正切值随后处理程度的加大而进一步降低。The composition is injected into a mold preheated at 150°C, degassed in a vacuum oven at 100-105°C for 30 minutes, and cured according to the process of 160°C/2h+180°C/2h+200°C/2h, and finally Post-treatment is carried out according to the process of 220°C/1h or 220°C/1h+230°C/4h respectively. The dielectric properties of the obtained samples are shown in Table 2. It can be seen that when the curing degree of the material is about 100%, the dielectric constant of the material can be realized by changing the post-treatment process of the material. In addition, the dielectric loss tangent of the material decreases further with subsequent processing.

表2 后处理工艺对材料介电性能的影响(1KHz下)Table 2 Effect of post-treatment process on dielectric properties of materials (under 1KHz)

Figure C200610098112D00071
Figure C200610098112D00071

实施例十~十一:Embodiment ten to eleven:

用5克丙酮稀释0.4克硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH-550),然后加入20克BaTiO3(400目),均匀混合后晾置,待大部分丙酮挥发后,在70℃烘6h,即获得了表面带有Si-O-Si化学键的处理过的BaTiO3Dilute 0.4 grams of silane coupling agent γ-aminopropyltriethoxysilane (KH-550) with 5 grams of acetone, then add 20 grams of BaTiO 3 (400 mesh), mix evenly and let it dry, and wait for most of the acetone to volatilize , baked at 70°C for 6h, the treated BaTiO 3 with Si-O-Si chemical bonds on the surface was obtained.

将25克BADCy和20g表面处理后的BaTiO3(400目)充分混合均匀,混合物在100℃油浴中加热熔融后,升温至150℃预固化1h,即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。Mix 25g of BADCy and 20g of surface-treated BaTiO 3 (400 mesh) thoroughly and evenly. After the mixture is heated and melted in an oil bath at 100°C, the temperature is raised to 150°C for pre-curing for 1 hour, and the dielectric constant and low dielectric constant are obtained. Organic/inorganic binary compositions for electrical losses.

将组合物注入在150℃预热后的模具中,在100~105℃的真空干燥箱中真空脱气30min,按160℃/2h+180℃/2h+200℃/2h工艺固化后,分别按220℃/1h或220℃/1h+230℃/4h工艺后处理,制得样品。所得样品的介电性能数据如表3所示。可以看出,在材料的固化程度约为100%时,材料的介电常数可以通过改变材料的表面物理化学性质实现,即偶联剂能够显著改善BaTiO3粒子在氰酸酯基体中的分散效果,从而提高材料的介电常数,而材料的介电损耗正切值不受影响。Inject the composition into a mold preheated at 150°C, degas it in a vacuum oven at 100-105°C for 30 minutes, and cure it according to the process of 160°C/2h+180°C/2h+200°C/2h. 220°C/1h or 220°C/1h+230°C/4h process post-treatment to prepare samples. The dielectric properties of the obtained samples are shown in Table 3. It can be seen that when the curing degree of the material is about 100%, the dielectric constant of the material can be realized by changing the physical and chemical properties of the surface of the material, that is, the coupling agent can significantly improve the dispersion effect of BaTiO3 particles in the cyanate matrix , thereby increasing the dielectric constant of the material, while the dielectric loss tangent of the material is not affected.

表3 BaTiO3(400目)表面处理对材料介电性能的影响Table 3 Effect of BaTiO 3 (400 mesh) surface treatment on dielectric properties of materials

Figure C200610098112D00081
Figure C200610098112D00081

实施例十二:Embodiment 12:

将20g BADCy、10g双酚E型氰酸酯和25g BaTiO3(600目)混合,混合物在100℃油浴中加热熔融后,升温至160℃预固化1.5h至BaTiO3无明显沉降,即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。将组合物注入在预热(150℃)后的模具中,于100~105℃的真空干燥箱中真空脱气30分钟,按160℃/2h+180℃/2h+200℃/2h工艺进行固化,按230℃/5h的工艺进行后处理,即得到BADCy/BaTiO3复合材料。所得样品在1KHz下的介电常数和介电损耗正切值分别为10.0573和0.0015。Mix 20g of BADCy, 10g of bisphenol E cyanate and 25g of BaTiO 3 (600 mesh), heat and melt the mixture in an oil bath at 100°C, then raise the temperature to 160°C for pre-curing for 1.5h until the BaTiO 3 has no obvious sedimentation, and you can get An organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss. Inject the composition into a preheated (150°C) mold, degas it in a vacuum oven at 100-105°C for 30 minutes, and cure it according to the process of 160°C/2h+180°C/2h+200°C/2h , according to the process of 230 ℃ / 5h post-treatment, that is, get BADCy/BaTiO 3 composite material. The dielectric constant and dielectric loss tangent of the obtained sample at 1KHz were 10.0573 and 0.0015, respectively.

实施例十三:Embodiment thirteen:

用5克异丙基醇溶解0.4克钛酸酯类偶联剂三(二辛基焦磷酰氧基)钛酸异丙酯,然后加入20克BaTiO3(150目),均匀混合,晾置,待大部分异丙基醇挥发后,在85℃烘6h,即获得了经表面处理的BaTiO3(150目)。Dissolve 0.4 g of titanate coupling agent tris(dioctylpyrophosphoryloxy) isopropyl titanate with 5 g of isopropyl alcohol, then add 20 g of BaTiO 3 (150 mesh), mix evenly, and let it dry , after most of the isopropyl alcohol volatilized, it was baked at 85° C. for 6 hours to obtain surface-treated BaTiO 3 (150 mesh).

将20g双环戊二烯双酚型氰酸酯、15g双酚E型氰酸酯和15g经表面处理的BaTiO3(150目)混合,混合物在100℃油浴中加热熔融后,升温至140℃预固化5h至BaTiO3无明显沉降,即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。Mix 20g of dicyclopentadiene bisphenol-type cyanate, 15g of bisphenol E-type cyanate and 15g of surface-treated BaTiO 3 (150 mesh), heat and melt the mixture in an oil bath at 100°C, then heat up to 140°C Pre-curing for 5 hours until BaTiO 3 has no obvious sedimentation, that is, an organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss is obtained.

将组合物注入在150℃预热后的模具中,在100~105℃的真空干燥箱中真空脱气30min,按160℃/2h+180℃/2h+200℃/2h工艺固化后,按220℃/1h+230℃/4h工艺后处理,制得样品。所得样品在1KHz下的介电常数和介电损耗正切值分别为8.4573和0.002。Inject the composition into a mold preheated at 150°C, degas it in a vacuum oven at 100-105°C for 30 minutes, and cure it according to the process of 160°C/2h+180°C/2h+200°C/2h, then press 220 ℃/1h+230℃/4h process post-treatment to prepare samples. The dielectric constant and dielectric loss tangent of the obtained sample at 1KHz were 8.4573 and 0.002, respectively.

实施例十四:Embodiment 14:

将30g双酚A型二氰酸酯(BADCy)和10g经硅烷偶联剂KH-550处理的BaTiO3(240目)混合,混合物在100℃油浴中加热熔融后,升温至150℃预固化4小时,BaTiO3无明显沉降,即得到兼具介电常数可调和低介电损耗的有机/无机二元组合物。Mix 30g of bisphenol A dicyanate (BADCy) and 10g of BaTiO 3 (240 mesh) treated with silane coupling agent KH-550, heat and melt the mixture in an oil bath at 100°C, then heat up to 150°C for pre-curing After 4 hours, BaTiO 3 did not settle significantly, that is, an organic/inorganic binary composition with adjustable dielectric constant and low dielectric loss was obtained.

将组合物注入在预热(150℃)后的模具中,于100~105℃的真空干燥箱中真空脱气30分钟,按160℃/2h+180℃/2h+200℃/2h工艺进行固化,按230℃/5h的工艺进行后处理,即得到BADCy/BaTiO3复合材料。所得样品在1KHz下的介电常数和介电损耗正切值分别为8.4573和0.001。Inject the composition into a preheated (150°C) mold, degas it in a vacuum oven at 100-105°C for 30 minutes, and cure it according to the process of 160°C/2h+180°C/2h+200°C/2h , according to the process of 230 ℃ / 5h post-treatment, that is, get BADCy/BaTiO 3 composite material. The dielectric constant and dielectric loss tangent of the obtained sample at 1KHz were 8.4573 and 0.001, respectively.

Claims (6)

1、一种低介电损耗的耐热组合物,其特征在于:按重量计,由40~99.9%的氰酸酯和0.1~60%钛酸钡组成,所述钛酸钡的粒度在600目~150目之间;所述耐热组合物的介电损耗值小于0.002。1. A heat-resistant composition with low dielectric loss, characterized in that: by weight, it consists of 40-99.9% cyanate and 0.1-60% barium titanate, and the particle size of the barium titanate is 600 between mesh and 150 mesh; the dielectric loss value of the heat-resistant composition is less than 0.002. 2、根据权利要求1所述的低介电损耗的耐热组合物,其特征在于:所述钛酸钡选自未经表面处理的钛酸钡、经过表面处理的钛酸钡或者其组合物,所述表面处理是将偶联剂溶解于有机溶液中,而后倒入预先烘干的钛酸钡,用高速均质搅拌机搅拌均匀,晾置,烘干。2. The heat-resistant composition with low dielectric loss according to claim 1, characterized in that: the barium titanate is selected from barium titanate without surface treatment, barium titanate with surface treatment or a combination thereof , the surface treatment is to dissolve the coupling agent in the organic solution, then pour into the pre-dried barium titanate, stir evenly with a high-speed homogeneous mixer, let it air, and dry. 3、根据权利要求1所述的低介电损耗的耐热组合物,其特征在于:所述氰酸酯选自双酚A型、双酚E型、双酚F型、双酚M型、双环戊二烯型双酚型中的一种或其组合物。3. The heat-resistant composition with low dielectric loss according to claim 1, characterized in that: the cyanate is selected from bisphenol A type, bisphenol E type, bisphenol F type, bisphenol M type, One of dicyclopentadiene type bisphenol types or a combination thereof. 4、权利要求1所述的低介电损耗的耐热组合物的制备方法,其特征在于:将氰酸酯和钛酸钡按所述重量比混合、在100℃熔融后,升温至130~160℃进行预固化,至钛酸钡无明显沉降,即获得所述低介电损耗的耐热组合物。4. The preparation method of the heat-resistant composition with low dielectric loss according to claim 1, characterized in that: mix cyanate ester and barium titanate according to the weight ratio, melt at 100°C, and heat up to 130- Pre-curing is performed at 160° C. until the barium titanate has no obvious sedimentation, that is, the heat-resistant composition with low dielectric loss is obtained. 5、根据权利要求4所述的低介电损耗的耐热组合物的制备方法,其特征在于:所述钛酸钡选自未经表面处理的钛酸钡、经过表面处理的钛酸钡或者其组合物,所述表面处理是将偶联剂溶解于有机溶液中,而后倒入预先烘干的钛酸钡,用高速均质搅拌机搅拌均匀,晾置,烘干;所述偶联剂为硅烷类偶联剂或钛酸酯类偶联剂。5. The method for preparing the heat-resistant composition with low dielectric loss according to claim 4, characterized in that: the barium titanate is selected from barium titanate without surface treatment, barium titanate with surface treatment or Its composition, the surface treatment is to dissolve the coupling agent in the organic solution, then pour into the pre-dried barium titanate, stir evenly with a high-speed homogeneous mixer, let it air, and dry; the coupling agent is Silane coupling agent or titanate coupling agent. 6、根据权利要求4所述的低介电损耗的耐热组合物的制备方法,其特征在于:所述的预固化时间在0.5~8小时之间。6. The method for preparing the heat-resistant composition with low dielectric loss according to claim 4, characterized in that: the pre-curing time is between 0.5 and 8 hours.
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