低介电耐温改性空心SiO<sub>2</sub>填充含氟聚芳醚腈复合材料的制备及性能

杨威; 詹迎青; 奉庆萤; 孙傲; 董洪雨

doi:10.13801/j.cnki.fhclxb.20210707.002

低介电耐温改性空心SiO₂填充含氟聚芳醚腈复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20210707.002

杨威^1,,
詹迎青^{1, 2, ,},
奉庆萤^1,,
孙傲^1,,
董洪雨^1,

1.
西南石油大学　化学化工学院，成都 610500
2.
西南石油大学　油气藏地质及开发工程国家重点实验室，成都 610500

基金项目: 国家自然科学青年基金(51903215)

详细信息

通讯作者:
詹迎青，博士(后)，副教授，硕士生导师，研究方向为特种功能高分子材料　E-mail：201599010032@swpu.edu.cn

中图分类号: TB33
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出版历程
- 收稿日期: 2021-05-10
- 修回日期: 2021-06-20
- 录用日期: 2021-06-30
- 网络出版日期: 2021-07-07
- 刊出日期: 2022-03-23

Preparation and properties of low dielectric and temperature-resistant poly (aryl ether nitrile) composites filled with modified hollow SiO₂

YANG Wei^1
,,
ZHAN Yingqing^{1, 2
, ,},
FENG Qingying^1
,,
SUN Ao^1
,,
DONG Hongyu^1
,

1.
College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
2.
State Key Lab of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China

摘要

摘要: 开发低介电常数、低介电损耗和同时兼具耐温、高力学强度的聚合物介电材料对于满足5G领域的高性能介电材料具有重要的研究意义。采用含氟1H,1H,2H,2H-全氟取代癸基三乙氧基硅烷(PTES)对空心SiO₂纳米粒子(HS)进行表面改性，并基于含氟聚芳醚腈共聚物(PEN-F)，分别以流延法和相转换法制备了两种PTES改性HS填充的PEN-F复合材料(HS@PTES/PEN-F)。采用FTIR和¹H NMR证实了PEN-F共聚物的成功合成；通过FTIR、TGA和XPS等技术手段表征了PTES改性的HS结构和形貌；同时研究了HS@PTES/PEN-F复合材料的介电性能、力学强度和热稳定性等。研究结果表明，经PTES改性后的HS纳米粒子在PEN-F基体树脂中具有较好的分散性与界面相容性。在介电性能方面，当改性SiO₂纳米粒子填充含量为7wt%时，通过流延法制备的HS@PTES/PEN-F复合膜在1 kHz时介电常数达2.88，介电损耗为0.0198；通过相转换法制备的HS@PTES/PEN-F复合膜在1 kHz时介电常数达1.19，介电损耗为0.0043。在力学性能方面，以相转换法为例，改性SiO₂纳米粒子填充含量为5wt%时，其拉伸强度和弹性模量分别达到10.34 MPa和365.32 MPa。此外，HS@PTES/PEN-F复合膜的玻璃化转变温度可达到160℃，具有较好的热稳定性。
- 含氟聚芳醚腈 /
- SiO₂ /
- 介电材料 /
- 耐温 /
- 低损耗
Abstract: The development of polymer dielectric materials with low dielectric constant, low dielectric loss, temperature resistance and high mechanical strength is of great significance to meet the requirements of high performance dielectric materials in 5G field. The hollow SiO₂ nanoparticles (HS) were modified by 1H, 2H, 2H-perfluorooctyltriethoxysilane (PTES), and two kinds of low dielectric poly (aryl ether nitrile) composites (HS@PTES/PEN-F) were prepared by solution casting and phase conversion methods based on fluorinated poly (aryl ether nitrile) copolymer (PEN-F). The successful synthesis of fluorinated poly (aryl ether nitrile) copolymer was confirmed by FTIR and ¹H NMR; the structure and morphology of PTES modified HS were characterized by FTIR, TGA and XPS. At the same time, the dielectric properties, mechanical strength and thermal stability of the HS@PTES/PEN-F composites were studied. The results show that the HS modified by PTES exhibit good dispersion and interface compa-tibility in the PEN-F matrix resin. In terms of dielectric properties, when the content of modified SiO₂ nanoparticles reaches 7wt%, the dielectric constant and the dielectric loss of the HS@PTES/PEN-F composite film prepared by solution casting method are 2.88 and 0.0198 at 1 kHz; the dielectric constant and dielectric loss of the HS@PTES/PEN-F composite film prepared by phase conversion method are 1.19 and 0.0043, respectively. In the aspect of mechanical properties, taking the phase conversion method as an example, when the content of modified SiO₂ nanoparticles reaches 5wt%, the tensile strength and elasticity modulus increase to 10.34 MPa and 365.32 MPa, respectively. In addition, the glass transition temperature of HS@PTES/PEN-F composite film can reach 160℃, which shows good thermal stability.
- fluorinated poly (aryl ether nitrile) /
- SiO₂ /
- dielectric materials /
- temperature resistance /
- low dielectric loss

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图 1 相转换法的制备过程

Figure 1. Preparation process of phase conversion method

PEN-F—Fluorinated poly (aryl ether nitrile); NMP—N-methyl pyrrolidone

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图 2 PEN-F的核磁氢谱(a)和FTIR图谱(b)

Figure 2. ¹H NMR (a) and FTIR spectrum (b) of PEN-F

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图 3 HS的改性过程(a)、PTES的分子结构(b)、HS@PTES的微观形貌(c)以及PTES、HS和HS@PTES的FTIR图谱(d)

Figure 3. Modification process of HS (a), molecular structure of PTES (b), morphology of HS@PTES (c) and FTIR spectra of PTES, HS and HS@PTES (d)

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图 4 改性后HS@PTES的TEM图像

Figure 4. TEM images of the HS@PTES

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图 5 HS和HS@PTES的TG测试(a)及HS@PTES的XPS图谱(b)

Figure 5. TG test of HS and HS@PTES (a) and XPS spectrum of HS@PTES (b)

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图 6 流延法制备HS@PTES/PEN-F复合膜的拉伸强度(a)、弹性模量(b)和断裂伸长率(c)随HS@PTES填充含量的变化曲线

Figure 6. Change curves of tensile strength (a), elasticity modulus (b) and elongation at break (c) along with the filling content of HS@PTES of the HS@PTES/PEN-F composite film prepared by solution casting method

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图 7 相转换法制备不同HS@PTES含量HS@PTES/PEN-F复合膜的拉伸强度(a)、弹性模量(b)及断裂伸长率(c)

Figure 7. Tensile strength (a), elasticity modulus (b) and elongation at break (c) of the HS@PTES/PEN-F prepared by phase conversion method

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图 8 流延法(a)和相转换法(b) HS@PTES/PEN-F膜的断面SEM图像以及不同比例HS@PTES的流延法和相转换法HS@PTES/PEN-F膜的实物(c)

Figure 8. Cross-sectional SEM images of HS@PTES/PEN-F composite films prepared by solution casting method (a) and phase conversion method (b), as well as digital photos of HS@PTES/PEN-F composite films with different HS@PTES contents (c)

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图 9 流延法制备的HS@PTES含量为1wt% (a)、5wt% (c)和7wt% (e)的HS@PTES/PEN-F复合膜和相转换法制备的HS@PTES含量为1wt% (b)、5wt% (d)和7wt% (f)的HS@PTES/PEN-F复合膜截面微观形貌

Figure 9. Cross-sectional SEM images of HS@PTES/PEN-F composite films prepared by solution casting method with the HS@PTES loading content of 1wt% (a), 5wt% (c) and 7wt% (e), and prepared by phase conversion method with the HS@PTES loading content of 1wt% (b), 5wt% (d) and 7wt% (f)

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图 10 流延法制备HS@PTES/PEN-F膜的介电常数(a)和介电损耗(b)以及相转换法制备HS@PTES/PEN-F膜的介电常数(c)和介电损耗(d)

Figure 10. Dielectric constant (a) and dielectric loss (b) of the HS@PTES/PEN-F composite films prepared by solution casting method, dielectric constant (c) and dielectric loss (d) of the HS@PTES/PEN-F composite films prepared by phase conversion method

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图 11 1 kHz频率下流延法(a)和相转换法(b) HS@PTES/PEN-F膜的介电常数和损耗随HS@PTES的含量变化曲线

Figure 11. Changes of dielectric constant and dielectric loss of HS@PTES/PEN-F composite films with various loading contents of HS@PTES prepared by solution casting method (a) and phase conversion method (b) under 1 kHz frequency

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图 12 相转换法HS@PTES/PEN-F膜的DSC曲线

Figure 12. DSC curves of HS@PTES/PEN-F films prepared by phase conversion method

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表 1 含氟1H,1H,2H,2H-全氟取代癸基三乙氧基硅烷(PTES)改性空心SiO₂(HS)填充的含氟聚芳醚腈复合材料(HS@PTES/PEN-F)铸膜液中各组分的比例

Table 1. Proportion of components in casting solution of fluorinated poly (aryl ether nitrile) composites filled with 1H, 2H, 2H-perfluorooctyltriethoxysilane (PTES) modified hollow silica (HS@PTES/PEN-F)

Sample	HS@PTES/g	PEN-F/g	NMP/mL	HS@PTES content/wt%
PEN-F	0	1.300	8.7	0
1wt%HS@PTES/PEN-F	0.013	1.287	8.7	1
3wt%HS@PTES/PEN-F	0.039	1.261	8.7	3
5wt%HS@PTES/PEN-F	0.065	1.235	8.7	5
7wt%HS@PTES/PEN-F	0.091	1.209	8.7	7

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表 2 相关聚合物介电材料性能比较

Table 2. Performance comparison of related polymer dielectric materials

Sample	K (1 kHz)	tanδ (1 kHz)	Tensile strength/MPa	T_g/℃	Ref.
PI/POSS	2.56	0.012	62	—	[23]
PE/SiO₂	2.2	0.005	5.6	104	[24]
F-GO/F-PI	2.09	0.0019	300	—	[25]
PEN/SiO₂	1.71	0.0047	50	175	[26]
PI/SiO₂	1.32	0.006	—	—	[27]
HS@PTES/PEN-F	2.88	0.0198	101	—	This work
HS@PTES/PEN-F	1.19	0.0043	10.34	160	This work
Notes: K—Dielectric constant; tanδ—Dielectric loss; T_g—Glass transition temperature; PI—Polyimide; POSS—Polysesquisiloxane; PE—Polyethylene; F-GO—Fluorinated graphene oxide; F-PI—Fluorinated polyimidel.

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