耐介质液体含氟弹性体的结构与性能剖析

刘小艳; 吴福迪; 郗旻; 张寅; 郝全红

doi:10.13801/j.cnki.fhclxb.20210609.004

耐介质液体含氟弹性体的结构与性能剖析

doi: 10.13801/j.cnki.fhclxb.20210609.004

刘小艳^1, ,,
吴福迪^1,,
郗旻^2,,
张寅¹,
郝全红¹

1.
航天材料计工艺研究所，北京 100076
2.
首都航天机械公司，北京 100076

详细信息

通讯作者:
刘小艳，博士，高级工程师，研究方向为特种橡胶材料及密封技术　E-mail：xiaoxiao111555@163.com

中图分类号: TB34
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出版历程
- 收稿日期: 2021-03-29
- 修回日期: 2021-05-16
- 录用日期: 2021-05-26
- 网络出版日期: 2021-06-09
- 刊出日期: 2022-04-01

Analysis of the structure and properties of a medium resistant liquid fluoroelastomer

LIU Xiaoyan^{1
, ,},
WU Fudi^1
,,
XI Min^2
,,
ZHANG Yin¹,
HAO Quanhong¹

1.
Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China
2.
Capital Aerospace Machinery Company, Beijing 100076, China

摘要

摘要: SIFEL 3705是日本信越开发的一种可耐多种化学品及强还原性介质的液体含氟弹性体材料，在国外军事、电子、石油化工等领域获得了广泛应用。掌握该材料的结构及性能特点，可以科学指导密封选材，充分发挥材料的高性能从而满足苛刻的密封工况。本文通过FTIR、核磁共振波谱仪及差示扫描量热仪(DSC)测试分析了SIFEL 3705A及3705B预混胶的化学结构及耐低温特性；针对采用两组分预混胶混合硫化后制备的含氟弹性体，开展了DSC、动态热机械分析(DMA)、力学性能、低温回弹性、高温压缩回弹性、耐高温性能、耐化学介质性能等方面的测试分析。结果表明：SIFEL 3705A和3705B预混胶中的主胶料化学结构基本一致，为分子主链含醚键C—O—C的氟橡胶；采用两组分预混胶制备的含氟弹性体玻璃化转变温度T_g达−52.5℃，在−50℃低温环境下仍具有回弹性，弹性体力学性能及耐高温性能良好，邵尔A硬度66，拉伸强度8.98 MPa，拉断伸长率289%，5wt%质量损失时的热分解温度476.8℃；经高温130℃压缩120天后恒定压缩永久变形≤20%，具有非常优异的高温回弹性能；另外，含氟弹性体具有非常优异的耐化学介质性能，在无水乙醇及液压油中的性能变化幅度很小，在强极性偏二甲肼介质中浸泡后性能变化先较快而后基本达到平衡。根据性能剖析结果可知，信越含氟弹性体SIFEL 3705可在−50℃低温环境及强腐蚀性环境中作密封材料使用。
- 含氟弹性体 /
- SIFEL 3705 /
- FTIR /
- 核磁谱图 /
- 高温压缩永久变形 /
- 耐介质
Abstract: SIFEL 3705 is a kind of liquid fluoroelastomer developed by Shinyue company, Janpan, which can resist many chemicals and strong reducing media. It has been widely used in military, electronic, petrochemical and other fields overseas. It can scientifically guide the selection of sealing materials, give full play to the high performance of the material so as to meet the harsh sealing conditions when the structure and performance characteristics of SIFEL 3705 are mastered. The chemical structure and low temperature resistance of the liquid fluoroelastomer SIFEL 3705A and 3705B premixed were analyzed by FTIR, nuclear magnetic resonance spectroscopy (NMR) and differential scanning calorimetry (DSC) analyses. For the fluoroelastomer prepared by vulcanization of two-component premix, DSC, dynamic thermo-mechanical analysis (DMA), mechanical properties, low temperature flexibility, compression set, heat resistance and chemical medium resistance were tested and analyzed. The results show that the chemical structure of the main compound in SIFEL 3705A and 3705B premix is similar, which is fluororubber with ether bond C—O—C bond in the main chain. The glass transition temperature T_g of the fluoroelastomer is −52.5℃, and it still own resilience at −50℃. The fluoroelastomer has good mechanical properties and heat resis-tance with Shore A hardness of 66, tensile strength of 8.98 MPa, elongation at break of 289%, and initial degradation (mass loss of 5wt%) temperature as 476.8℃. The constant compression set is no more than 20% after compressing at 130℃ for 120 days. Meanwhile, the fluoroelastomer has excellent resistance to chemical media. The performance changes are unconspicuous in anhydrous ethanol and synthetic oil. The properties are changed quickly and then reach equilibrium in strong polar solvent of N, N-dimethylhydrazine. The results show that SHIN-ETSU fluoroelastomer as a sealing material is applicable for harsh environment such as low temperature of −50℃ and strong corrosive solvent.
- fluoroelastomer /
- SIFEL 3705 /
- FTIR /
- nuclear magnetic resonance spectroscopy /
- compression set /
- medium resistant

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图 1 信越SIFEL含氟弹性体化学结构

Figure 1. Chemical structure of Shin-Etsu SIFEL fluoroelastomer

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图 2 SIFEL 3705A预混胶的FTIR图谱

Figure 2. FTIR spectrum of SIFEL 3705A premix

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图 3 SIFEL 3705B预混胶的FTIR图谱

Figure 3. FTIR spectrum of SIFEL 3705B premix

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图 4 SIFEL 3705A (a) 及3705B (b) 预混胶的¹H NMR图谱

Figure 4. ¹H NMR spectra of SIFEL 3705A (a) and 3705B (b) premix

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图 5 SIFEL 3705A (a)及3705B (b)预混胶的¹⁹F NMR谱图

Figure 5. ¹⁹F NMR spectra of SIFEL 3705A (a) and 3705B (b) premix

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图 6 SIFEL 3705A及3705B预混胶的DSC曲线

Figure 6. DSC curves of SIFEL 3705A and 3705B premix

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图 7 SIFEL 3705含氟弹性体的DSC (a) 和DMA曲线 (b)

Figure 7. DSC (a) and DMA (b) curves of SIFEL 3705 fluoroelastomer

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图 8 SIFEL 3705含氟弹性体的热失重曲线

Figure 8. TG curves of SIFEL 3705 fluoroelastomer

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图 9 SIFEL 3705含氟弹性体高温下的质量变化曲线

Figure 9. Change in mass of SIFEL 3705 fluoroelastomer at high temperature

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图 10 SIFEL 3705含氟弹性体高温下拉伸强度变化曲线

Figure 10. Change in tensile strength of SIFEL 3705 fluoroelastomer at high temperatures

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图 11 SIFEL 3705含氟弹性体高温压缩永久变形随时间的变化曲线

Figure 11. Change in compression set of SIFEL 3705 fluoroelastomer at high temperatures

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图 12 SIFEL 3705含氟弹性体浸泡在介质中性能随时间的变化曲线

Figure 12. Changes in physical properties of SIFEL 3705 fluoroelastomer after immersing in solvent for different time ((a) Shore A hardness; (b) Tensile strength; (c) Elongation ratio; (d) Volume change ratio)

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表 1 SIFEL 3705含氟弹性体的物理力学性能

Table 1. Physical properties of SIFEL 3705 fluoroelastomer

Property	Value
Shore A hardness	66
Tensile strength/MPa	8.98
Elongation at break/%	289
100% tensile strength/MPa	2.89
Coefficient of cold resistance under compression	0.46 (at −40℃)
	0.38 (at −45℃)
	0.21 (at −50℃)
T_R₁₀/℃	−50
Brittle temperature/℃	−53
Note: T_R₁₀—Temperature corresponding to 10% shrinkage.

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表 2 SIFEL 3705含氟弹性体的线膨胀系数

Table 2. Coefficient of linear expansion of SIFEL 3705 fluoroelastomer

Temperature range/℃	Average coefficient/10⁻⁶℃
RT~50	225
RT~100	240
RT~150	247
RT~200	255
RT~250	268
Note: RT—Room temperature.

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