Reduction Performance and Mechanism of Liquid Terminated-carboxyl Fluoroelastomers Using NaBH4/MCl x Reduction System

doi:10.7503/cjcu20210835

Abstract

Abstract:

Using a simple one-pot method， direct transformation of liquid terminated-carboxyl fluoroelastomers（LTCFs） to the corresponding liquid terminated-hydroxyl fluoroelastomers（LTHFs） was easily realized with sodium borohydride（NaBH₄） in the presence of metal chloride（MCl _x ）. The structure and functional group content of LTCFs and LTHFs were analyzed by Fourier transform infrared spectroscopy（FTIR）， ¹H nuclear magnetic resonance（¹H NMR） spectrocopy， ¹⁹F nuclear magnetic resonance（¹⁹F NMR） spectrocopy and chemical titration. The results showed that —C=C— and carboxyl groups of LTCFs were reduced efficiently. The effect of different rare-earth chlorides（LaCl₃， CeCl₃， NdCl₃ and SmCl₃） and transition metal chlorides（MnCl₂， NiCl₂， CoCl₂ and CuCl₂） on the performances of the LTCFs reduction was discussed. The NaBH₄/SmCl₃ system was the best and the reduction rate reached 92% under optimum reaction conditions. Mechanism research showed that the stronger binding force of metal ion and carbonyl oxygen was beneficial to the reduction of LTCFs.

Key words: Liquid terminated-carboxyl fluoroelastomer, Metal chloride, NaBH₄, Carboxyl, Reduction mechanism

CLC Number:

O632.21

TrendMD:

CHANG Yunfei, LIAO Mingyi, WEN Jiaming. Reduction Performance and Mechanism of Liquid Terminated-carboxyl Fluoroelastomers Using NaBH₄/MCl _x Reduction System[J]. Chem. J. Chinese Universities, 2022, 43(6): 20210835.

Figures/Tables 9

References 30

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Reduction system	Reductive ratio（%）	Reduction system	Reductive ratio（%）
NaBH₄/LaCl₃	80	NaBH₄/MnCl₂	19
NaBH₄/CeCl₃	84	NaBH₄/CoCl₂	20
NaBH₄/NdCl₃	86	NaBH₄/NiCl₂	32
NaBH_4/SmCl₃	92	NaBH₄/CuCl₂	42

Reduction system	Reductive ratio（%）	Reduction system	Reductive ratio（%）
NaBH₄/LaCl₃	80	NaBH₄/MnCl₂	19
NaBH₄/CeCl₃	84	NaBH₄/CoCl₂	20
NaBH₄/NdCl₃	86	NaBH₄/NiCl₂	32
NaBH_4/SmCl₃	92	NaBH₄/CuCl₂	42

No.	δ	Assignment	No.	δ	Assignment
1	-63.67	—CF₂CF₂COOH	10	-103.62	—CF₂CH₂CF₂CF（CF₃）CF₂—
2	-70.67	—CH₂CF₂CF（CF₃）CF₂CH₂—	11	-108.96	—CF（CF₃）CH₂CF₂CF（CF₃）CF₂—
3	-73.71	—CF₂CH=C（CF₃）CF₂—	12	-110.51	—CF₂CH₂CF₂CF₂CF（CF₃）—
4	-75.19	—CF₂CH₂CF（CF₃）CF₂CF₂—	13	-112.53	—CF（CF₃）CH₂CF₂CF₂CH₂—
5	-80.66	—CH=CFCF（CF₃）—	14	-113.95	—CF₂CH₂CF₂CF₂CH₂—
6	-81.30	—CF=CHCF（CF₃）CF₂—	15	-116.24	—CH₂CH₂CF₂CF₂CF（CF₃）—
7	-91.62	—CF₂CH₂CF₂CH₂CF₂—	16	-118.72	—CH₂CF₂CF₂CF（CF₃）CH₂—
8	-93.56	—CF₂CH₂CF₂CH₂CF（CF₃）—	17	-181.74	—CH₂CF₂CF（CF₃）CF₂CH₂—
9	-95.64	—CH₂CH₂CF₂CH₂CF₂—	18	-184.33	—CF₂CF₂CF（CF₃）CH₂CF₂—

No.	δ	Assignment	No.	δ	Assignment
1	-63.67	—CF₂CF₂COOH	10	-103.62	—CF₂CH₂CF₂CF（CF₃）CF₂—
2	-70.67	—CH₂CF₂CF（CF₃）CF₂CH₂—	11	-108.96	—CF（CF₃）CH₂CF₂CF（CF₃）CF₂—
3	-73.71	—CF₂CH=C（CF₃）CF₂—	12	-110.51	—CF₂CH₂CF₂CF₂CF（CF₃）—
4	-75.19	—CF₂CH₂CF（CF₃）CF₂CF₂—	13	-112.53	—CF（CF₃）CH₂CF₂CF₂CH₂—
5	-80.66	—CH=CFCF（CF₃）—	14	-113.95	—CF₂CH₂CF₂CF₂CH₂—
6	-81.30	—CF=CHCF（CF₃）CF₂—	15	-116.24	—CH₂CH₂CF₂CF₂CF（CF₃）—
7	-91.62	—CF₂CH₂CF₂CH₂CF₂—	16	-118.72	—CH₂CF₂CF₂CF（CF₃）CH₂—
8	-93.56	—CF₂CH₂CF₂CH₂CF（CF₃）—	17	-181.74	—CH₂CF₂CF（CF₃）CF₂CH₂—
9	-95.64	—CH₂CH₂CF₂CH₂CF₂—	18	-184.33	—CF₂CF₂CF（CF₃）CH₂CF₂—

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Reduction Performance and Mechanism of Liquid Terminated-carboxyl Fluoroelastomers Using NaBH₄/MCl _x Reduction System

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