含乙烯基全氟聚醚-<i>b</i>-聚硅氧烷制备及其在硅橡胶中的性能

吕宁宁; 冯裕智; 文敬滨; 温萍; 路明霄; 唐旭东

含乙烯基全氟聚醚-b-聚硅氧烷制备及其在硅橡胶中的性能

1.
天津科技大学　化工与材料学院, 天津 300457
2.
中石油(上海)新材料研究院, 上海 200122

详细信息

通讯作者:
唐旭东，博士，教授，博士生导师，研究方向为高分子复合材料　E-mail: tangxd@tust.edu.cn

中图分类号: TQ333.93; TB332
计量
- 文章访问数: 56
- HTML全文浏览量: 36
- 被引次数: 0
出版历程
- 收稿日期: 2024-03-18
- 修回日期: 2024-05-20
- 录用日期: 2024-05-25
- 网络出版日期: 2024-06-17

Preparation of vinyl-containing perfluoropolyether-b-polysiloxane and its properties in silicone rubber

1.
College of Chemical Engineering and Materials, Tianjing University of Science and Technology, Tianjin 300457, China
2.
Research Institute of Advanced Materials, petrochina (Shanghai), Shanghai 200122, China

摘要

摘要: 耐溶剂性能差是制约硅橡胶发展与应用的重要因素之一，氟改性是解决该问题的有效手段之一。通过叔丁醇钾引发环硅氧烷阴离子开环制备了多乙烯基聚硅氧烷(Vi-PSi)，与全氟聚醚硅氧烷反应制备含乙烯基全氟聚醚-b-聚硅氧烷嵌段共聚物(PFPE-b-PMVS)，采用FT IR、¹H NMR确定了其结构，并研究了PFPE-b-PMVS对甲基乙烯基硅橡胶(MVQ)力学性能、硫化性能、耐溶剂性能和热稳定性的影响。结果表明，随着PFPE-b-PMVS含量的增加，高温硫化交联后，改性MVQ的拉伸强度先增加后降低，当PFPE-b-PMVS添加量为2%时，拉伸强度和断裂伸长率可达11.38 MPa和396%；焦烧时间(t₁₀)和正硫化时间(t₉₀)随着PFPE-b-PMVS的增加而降低；耐溶剂性能随PFPE-b-PMVS添加量的增加吸附量降低，当PFPE-b-PMVS添加量为20%时，在对二甲苯溶剂中，吸附溶剂比未改性MVQ降低83.22%；热失重10%温度随PFPE-b-PMVS用量增加而降低。
- 全氟聚醚 /
- 聚硅氧烷 /
- 改性硅橡胶 /
- 耐溶剂性能 /
- 力学性能
Abstract: Poor solvent resistance is one of the important factors restricting the development and application of silicone rubber, and fluorine modification is one of the effective means to solve this problem. Vinyl-containing polysiloxane (Vi-PSi) was prepared by potassium tert-butanol induced cyclosiloxane anionic ring-opening, and Vinyl-containing perfluoropolyether-b-polysiloxane block copolymer (PFPE-b-PMVS) was grafted with perfluoroether siloxane. Its structure was determined by FT IR and ¹H NMR. The effects of PFPE-b-PMVS on mechanical properties, vulcanization properties, solvent resistance and thermal stability of methyl vinyl silicone rubber (MVQ) were studied. The results show that with the increase of PFPE-b-PMVS content, the tensile strength of modified MVQ increases first and then decreases after high temperature vulcanization crosslinking. When the addition of PFPE-b-PMVS is 2%, the tensile strength and elongation at break can reach 11.38 MPa and 396%. The coke time (t₁₀) and positive vulcanization time (t₉₀) decreased with the increase of PFPE-b-PMVS. The solvent resistance decreased with the increase of PFPE-b-PMVS. When the PFPE-b-PMVS added amount was 20%, the adsorption solvent in p-xylene solvent was 83.22% lower than that in unmodified MVQ. The 10% thermogravimetric temperature decreased with the increase of the dosage of PFPE-b-PMVS.
- Perfluoropolyether /
- Polysiloxane /
- Modified silicone rubber /
- Solvent resistance /
- Mechanical property

HTML全文

图 1 硅醇封端Vi-PSi(a)、全氟聚醚硅氧烷(b)和PFPE-b-PMVS(c)的FTIR谱图

Figure 1. FTIR spectra of Silanol-sealed Vi-PSi (a), Per-fluoropolyether siloxane (b), and PFPE-b-PMVS (c)

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图 2 全氟聚醚硅氧烷(a)和PFPE-b-PMVS(b)的¹H NMR谱图

Figure 2. ¹H NMR spectra of Perfluoropolyether siloxane(a) and PFPE-b-PMVS(b)

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图 3 改性MVQ的拉伸性能和硬度

(a) MVQ(I)；(b) MVQ(II)；(c) MVQ(III)；(d)改性MVQ的硬度

Figure 3. The tensile properties and hardness of modified MVQ

(a) MVQ(I); (b) MVQ(II); (c) MVQ(III); (d) Hardness of modified MVQ

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图 4 改性MVQ的耐溶剂性能

(a)乙醇；(b)丙酮；(c)对二甲苯；(d)10#航空液压油

Figure 4. Solvent resistance of modified MVQ

(a) Ethyl alcohol; (b) Acetone; (c) Para-xylene; (d) 10# Aviation hydraulic oil

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图 5 改性MVQ的体积变化

Figure 5. Volume change of modified MVQ

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图 6 改性MVQ的高温拉伸性能

Figure 6. The high temperature tensile properties of modified MVQ

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图 7 改性MVQ的DSC曲线

Figure 7. DSC curve of modified MVQ

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图 8 改性剂PFPE-b-PMVS的TGA和DTG曲线(a)和改性MVQ的TGA曲线(b)

Figure 8. TGA and DTG curves (a) of PFPE-b-PMVS and TGA curves (b) of modified MVQ

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图 9 改性MVQ的XPS曲线

Figure 9. DSC curve of modified MVQ

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图 10 MVQ(III-2%)的EDS图谱

Figure 10. EDS spectrum of MVQ (III-2%)

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表 1 改性硅橡胶(MVQ)的配方表

Table 1. Formula table of modified methyl vinyl silicone rubber (MVQ)

Sample	IV/g	I/g	II/g	III/g
MVQ	161.5	0	0	0
MVQ(I-1%)	161.5	1	0	0
MVQ(I-2%)	161.5	2	0	0
MVQ(I-3%)	161.5	3	0	0
MVQ(II-1%)	161.5	0	1	0
MVQ(II-2%)	161.5	0	2	0
MVQ(II-3%)	161.5	0	3	0
MVQ(III-1%)	161.5	0	0	1
MVQ(III-2%)	161.5	0	0	2
MVQ(III-3%)	161.5	0	0	3
MVQ(III-4%)	161.5	0	0	4
MVQ(III-10%)	161.5	0	0	10
MVQ(III-20%)	161.5	0	0	20
Notes: IV—mixed silicone rubber, I - vinyl silicone oil, II—Perfluoropolyether allyl ether(PFPE-Ally) and III—Vinyl-containing perfluoropolyether-b-polysiloxane block copolymer (PFPE-b-PMVS).

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表 2 改性MVQ的硫化性能

Table 2. The vulcanization properties of modified MVQ

Sample	t₁₀/s	t₉₀/s	ML/ (dN·m)	MH/ (dN·m)	(MH-ML)/ (dN·m)
MVQ	120	1207	1.02	27.78	26.76
MVQ(I-1%)	88	1056	0.86	27.02	26.16
MVQ(I-2%)	79	916	0.72	27.13	26.41
MVQ(I-3%)	52	797	0.67	27.35	26.68
MVQ(II-1%)	67	645	0.97	26.34	25.37
MVQ(II-2%)	63	666	0.89	26.25	25.36
MVQ(II-3%)	60	645	0.81	26.07	25.26
MVQ(III-1%)	83	690	0.92	27.13	26.21
MVQ(III-2%)	80	643	0.88	27.08	26.2
MVQ(III-3%)	76	638	0.83	27.15	26.32
MVQ(III-4%)	72	597	0.78	26.87	26.09
MVQ (III-10%)	68	544	1.19	29.69	28.5
MVQ (III-20%)	62	505	1.27	29.36	28.09
Notes: MH and ML are the maximum and minimum torque values, re-spectively；t₁₀ for scorching time and t₉₀ for positive vulcanization time.

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