NaBH4/Ziegler-Natta Rare Earth Catalyst Reduction System for Reduction of Liquid Terminated-carboxyl Fluoroelastomers

doi:10.7503/cjcu20230133

Abstract

Abstract:

Sodium borohydride/Ziegler-Natta rare earth catalyst reduction system（NaBH₄/Ziegler-Natta） was used to reduce liquid terminated-carboxyl fluoroelastomers（LTCFs）. LTCFs were efficiently converted to the corresponding liquid terminated-hydroxyl fluoroelastomers（LTHFs） via a simple one-pot method. The reductive rate of LTHFs was analyzed by chemical titration. The structures of LTCFs and LTHFs were analyzed by Fourier transform infrared spectroscopy（FTIR）， ¹H nuclear magnetic resonance（¹H NMR） spectroscopy and ¹⁹F nuclear magnetic resonance（¹⁹F NMR） spectrocopy. The results show that —C=C— and carboxyl groups of LTCFs were reduced to —C—C— and —OH efficiently at ambient temperature and the reduction rate reached 90% under optimum reaction conditions.

Key words: Liquid terminated-carboxyl fluoroelastomer, Ziegler-Natta rare earth catalyst, NaBH₄, Carboxyl, Reduction mechanism

CLC Number:

O632.21

TrendMD:

CHANG Yunfei, LIAO Mingyi, YUAN Gaofei. NaBH₄/Ziegler-Natta Rare Earth Catalyst Reduction System for Reduction of Liquid Terminated-carboxyl Fluoroelastomers[J]. Chem. J. Chinese Universities, 2023, 44(10): 20230133.

Figures/Tables 10

References 36

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Sample	n（R₀COOH）/mmoL	n（NaBH₄）/mmoL	n（Ce）/mmoL	n（Al）/mmoL	Time/h	Temperature/℃	Reductive ratio（%）
1	2.80	2.80	0.14	0.23	6	50	21
2	2.80	5.60	0.28	0.46	6	50	42
3	2.80	8.40	0.42	0.69	6	50	71
4	2.80	11.20	0.56	0.92	6	50	90
5	2.80	14.00	0.70	1.15	6	50	90
6	2.80	11.20	0.28	0.46	6	50	63
7	2.80	11.20	0.42	0.69	6	50	83
8	2.80	11.20	0.70	1.15	6	50	90
9	2.80	11.20	0.56	0.92	0.5	50	75
10	2.80	11.20	0.56	0.92	1	50	80
11	2.80	11.20	0.56	0.92	2	50	90
12	2.80	11.20	0.56	0.92	2	15	60
13	2.80	11.20	0.56	0.92	2	30	76
14	2.80	11.20	0.56	0.92	2	70	89
15	2.80	11.20	0.56	0.92	2	90	82

Sample	n（R₀COOH）/mmoL	n（NaBH₄）/mmoL	n（Ce）/mmoL	n（Al）/mmoL	Time/h	Temperature/℃	Reductive ratio（%）
1	2.80	2.80	0.14	0.23	6	50	21
2	2.80	5.60	0.28	0.46	6	50	42
3	2.80	8.40	0.42	0.69	6	50	71
4	2.80	11.20	0.56	0.92	6	50	90
5	2.80	14.00	0.70	1.15	6	50	90
6	2.80	11.20	0.28	0.46	6	50	63
7	2.80	11.20	0.42	0.69	6	50	83
8	2.80	11.20	0.70	1.15	6	50	90
9	2.80	11.20	0.56	0.92	0.5	50	75
10	2.80	11.20	0.56	0.92	1	50	80
11	2.80	11.20	0.56	0.92	2	50	90
12	2.80	11.20	0.56	0.92	2	15	60
13	2.80	11.20	0.56	0.92	2	30	76
14	2.80	11.20	0.56	0.92	2	70	89
15	2.80	11.20	0.56	0.92	2	90	82

Reduction system	Molar ratio	Time/h	Temperature/℃	Reductive ratio（%）	Reference
—COOH/I₂	1/1.3	8	70	91	［25］
—COOH/ZnCl₂	1/2	6	90	72	［26］
—COOH/AlCl₃	1/2	6	90	64
—COOH/CaCl₂	1/2	6	90	44
—COOH/CoCl₂	1/2	6	90	20
—COOH/LaCl₃	1/2	6	90	80	［27］
—COOH/CeCl₃	1/2	6	90	84
—COOH/NdCl₃	1/2	6	90	86
—COOH/SmCl₃	1/2	6	90	92
—COOH/Ce， Al	1/0.53	2	50	90	This paper

Reduction system	Molar ratio	Time/h	Temperature/℃	Reductive ratio（%）	Reference
—COOH/I₂	1/1.3	8	70	91	［25］
—COOH/ZnCl₂	1/2	6	90	72	［26］
—COOH/AlCl₃	1/2	6	90	64
—COOH/CaCl₂	1/2	6	90	44
—COOH/CoCl₂	1/2	6	90	20
—COOH/LaCl₃	1/2	6	90	80	［27］
—COOH/CeCl₃	1/2	6	90	84
—COOH/NdCl₃	1/2	6	90	86
—COOH/SmCl₃	1/2	6	90	92
—COOH/Ce， Al	1/0.53	2	50	90	This paper

No.	δ	Assignment	No.	δ	Assignment
1	-63.67	—CF₂CF₂ COOH	10	-103.62	—CF₂CH₂CF ₂ CF（CF₃）CF₂—
2	-70.67	—CH₂CF₂CF（CF₃ ）CF₂CH₂—	11	-108.96	—CF（CF₃）CH₂CF ₂ CF（CF₃）CF₂—
3	-73.71	—CF₂CH=C（CF₃ ）CF₂—	12	-110.51	—CF₂CH₂CF ₂ CF₂CF（CF₃）—
4	-75.19	—CF₂CH₂CF（CF₃ ）CF₂CF₂—	13	-112.53	—CF（CF₃）CH₂CF ₂ CF₂CH₂—
5	-80.66	—CH=CFCF（CF₃ ）—	14	-113.95	—CF₂CH₂CF ₂ CF₂CH₂—
6	-81.30	—CF=CHCF（CF₃ ）CF₂—	15	-116.24	—CH₂CH₂CF ₂ CF₂CF（CF₃）—
7	-91.62	—CF₂CH₂CF₂ CH₂CF₂—	16	-118.72	—CH₂CF ₂ CF₂CF（CF₃）CH₂—
8	-93.56	—CF₂CH₂CF₂ CH₂CF（CF₃）—	17	-181.74	—CH₂CF₂CF（CF₃）CF₂CH₂—
9	-95.64	—CH₂CH₂CF₂ CH₂CF₂—	18	-184.33	—CF₂CF₂CF（CF₃）CH₂CF₂—

NaBH₄/Ziegler-Natta Rare Earth Catalyst Reduction System for Reduction of Liquid Terminated-carboxyl Fluoroelastomers

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