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RSC Advances · 2020 ·Vol. 10 ·期 18 ·10932-10938 · IF 3.119

Reduction of liquid terminated-carboxyl fluoroelastomers using NaBH4/SmCl3

Yunfei Chang,Mingyi Liao,Xueyan Li

Using a simple one-pot method, the reduction of liquid terminated-carboxyl fluoroelastomers (LTCFs) by sodium borohydride and samarium chloride (NaBH4/SmCl3) was successfully realized and liquid terminated-hydroxyl fluoroelastomers (LTHFs) were obtained. The structure and functional group content of LTCFs and LTHFs were analyzed by FTIR, 1H-NMR, 19F-NMR and chemical titration. The results showed that –CC– and carboxyl groups of LTCFs were reduced efficiently, the reduction rate reached 92% under optimum reaction conditions. Compared with other frequently-used metal chlorides, SmCl3 with a high coordination number could increase the reduction activity of NaBH4 more effectively and the reduction mechanism was explored.

研究领域: 材料化学 · 有机化学
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RSC Advances · 2022 ·Vol. 12 ·期 5 ·3108-3118 · IF 4.036

Structure, preparation and properties of liquid fluoroelastomers with different end groups

Jiayu Duan,Chen Yang,Hailan Kang,Long Li,Feng Yang,Qinghong Fang,Wenchi Han,Donghan Li

In order to design and prepare liquid fluoroelastomers with different end groups, and reveal the relationship between the molecular chain structure and properties, we studied on the oxidation degradation method and functional group conversion method to prepare carboxyl-terminated and hydroxyl-terminated liquid fluoroelastomers, respectively. The reaction mechanisms were also deduced. Furthermore, the curing system was created for liquid fluoroelastomers, and systematically analyzed their properties. The sequence type and content of the –CC– and oxygen-containing groups in the samples were measured and characterized by attenuated total reflectance/Fourier transform infrared (ATR-FTIR) spectroscopy, 1H nuclear magnetic resonance (1H-NMR), 19F-NMR spectroscopy and chemical titration, the molecular weights of liquid fluoroelastomers were measured by gel permeation chromatography (GPC). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to examine the thermal properties, while a viscometer was used to measure the dynamic viscosity of the liquid fluoroelastomers. Then the mechanical and surface properties of the cured samples were examined by universal testing machine and contact angle measurement instrument, respectively. The results show that carboxyl-terminated liquid fluoroelastomer with 2.71 wt% carboxyl terminal groups can be prepared by oxidation degradation method. When lithium aluminium hydride (LiAlH4) was used as the reducing agent, it can efficiently convert carboxyl group to hydroxyl group with a conversion rate of more than 95%. In addition, it can be seen that the dynamic viscosity of the liquid fluoroelastomers were all decreased with the increase of temperature, and it is similar to about 10 Pa s at 70 °C. Compared with carboxyl-terminated liquid fluoroelastomers, hydroxyl-terminated liquid fluoroelastomers has higher curing reactivity, higher glass transition temperature (Tg) and thermal decomposition temperature (Td), and better mechanical properties of cured samples. The two types of liquid fluoroelastomers with distinct end groups presented distinct hydrophilicity.

CAS / MDL: 56-37-1 16853-85-3
研究领域: 材料科学 · 化学工程
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POLYMER SCIENCE SERIES B · 2024 · IF 1

Preparation, Curing and Properties of Liquid Amine-Terminated Fluoroelastomers

Gaofei Yuan,Liao Mingyi,Chang Yunfei

Abstract A two-step nucleophilic substitution mechanism was used and described to prepare liquid amine-terminated fluoroelastomers (LTAFs) by using liquid hydroxy-terminated fluoroelastomers (LTHFs) as raw materials, benzenesulfonyl chloride as an activator, and hexanediamine as an amine source. A reaction time of 24 h at 18°C and a molar ratio of groups –NH 2 /–OH = 6.00 is an optimal condition for obtaining LTAFs with a yield of amino groups of 51%. The resulting LTAFs has a higher viscosity and lower thermal stability than LTHFs, while the molecular weight and distribution, as well as the glass transition temperature, remain essentially similar. Aziridine cured LTAFs has the best comprehensive mechanical properties and excellent chemical solvent resistance.

研究领域: 材料科学 · 化学工程
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POLYMER DEGRADATION AND STABILITY · 2018 · IF 3.193

Study on the dehydrofluorination of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) copolymer

Donghan Li,Mingyi Liao

This study evaluates the dehydrofluorination of fluoroelastomer (poly(VDF-co-HFP) copolymer) which was dissolved by organic solvent and reacted with different concentrations of KOH and different amount of phase transfer catalyst (PTC) at 20–60 °C.The structures, sequence types and contents of double bonds of samples were analyzed and investigated by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy(ATR-FTIR), 1 H nuclear magnetic resonance (NMR), 19 F NMR spectroscopy and chemical titration method. The results revealed that dehydrofluorination of the studied fluoroelastromers could be carried out at room temperature in alkaline environments, wherein the temperature and alkali concentration were the great factors. And the dehydrofluorination of poly(VDF-co-HFP) copolymer conformed mainly to Zaitsev's rule and partially to Hofmann's rule. The double bonds (–C=C–) would generate in five positions of molecular chains and contents could be controlled. With increase of alkali concentration or reaction temperature, there would be dehydrofluorination accompanied with oxidation reaction whereby some –C=C– converted to hydroxyl groups . Finally, the mechanism of reaction was also deduced.

CAS / MDL: 56-37-1
研究领域: 材料化学 · 高分子科学
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Nature Communications · 2022 ·Vol. 13 ·期 1 ·1-11 · IF 17.694

Tough, stable and self-healing luminescent perovskite-polymer matrix applicable to all harsh aquatic environments

Liu Yuncong,Chen Tao,Jin Zhekai,Li Mengxue,Zhang Dongdong,Duan Lian,Zhao Zhiguo,Wang Chao

Gelatinous underwater invertebrates such as jellyfish have organs that are transparent, luminescent and self-healing, which allow the creatures to navigate, camouflage themselves and, indeed, survive in aquatic environments. Artificial luminescent materials that can mimic such functionality can be used to develop aquatic wearable/stretchable displays and water-resistant devices. Here, a luminescent composite that is simultaneously transparent, tough and can autonomously self-heal in both dry and wet conditions is reported. A tough, self-healable fluorine elastomer with dipole–dipole interactions is synthesized as the polymer matrix. It exhibits excellent compatibility with metal halide perovskite quantum dots. The composite possesses a toughness of 19 MJ m −3 , maximum strain of 1300% and capability to autonomously self-heal underwater. Notably, the material can withstand extremely harsh aqueous conditions, such as highly salty, acidic (pH = 1) and basic (pH = 13) environment for more than several months with almost no decay in mechanical performance or optical properties.

研究领域: 材料科学 · 聚合物科学 · 纳米技术 · 光电子学
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