Polyallylamine Modified Sulfonic Acid Catalyst Catalyse Synthesis of n-Butyl Benzoate

doi:10.19894/j.issn.1000-0518.230105

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (10): 1430-1436.DOI: 10.19894/j.issn.1000-0518.230105

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Polyallylamine Modified Sulfonic Acid Catalyst Catalyse Synthesis of n-Butyl Benzoate

Ya-Zhou YU¹, Xian-Liang ZHAO¹(), Ning-Ning TAN¹, Yang XIAO¹, Yong-Jun ZHANG²()

^1.School of Biological and Chemical Engineering，Zhejiang University of Science and Technology，Hangzhou 310023，China
^2.Zhejiang Wild Wind Pharmaceutical Co. Ltd. ，Dongyang 322100，China

Received:2023-04-13 Accepted:2023-08-21 Published:2023-10-01 Online:2023-10-13
Contact: Xian-Liang ZHAO,Yong-Jun ZHANG
About author:xlzhao@zust.edu.cn

Abstract

Abstract:

Developing polymer carrier catalysts is an important topic for effectively addressing catalyst utilization and green synthetic chemistry. As a monomer， allylamine hydrochloride is polymerized with initiation to obtain polyallylamine which is cross-linked with epichlorohydrin to obtain cross-linked polyallylamine hydrochloride. Using cross-linked polyallylamine as a carrier， a solid acid catalyst with high loading is prepared by reacting with chlorosulfonic acid.The cross-linked polyallylamine sulfonic acid catalyst is stable up to 150 ℃， indicating its excellent thermal stability. This catalyst is used to catalyze the reaction of benzoic acid and n-butanol to produce n-butyl benzoate. The optimal reaction conditions are： the molar ratio of n-butanol to benzoic acid of 2∶1， the catalyst dosage of 20 g/mol BA， reaction temperature of 120 ℃ and reaction time of 6 h. The esterification rate of benzoic acid is 95%. This catalyst can be reused up to 4 times while maintaining high catalytic performance.

Key words: Polymer supporter, Polyallylamine, Sulfonic acid, n-Butyl benzoate

CLC Number:

O643.3

Ya-Zhou YU, Xian-Liang ZHAO, Ning-Ning TAN, Yang XIAO, Yong-Jun ZHANG. Polyallylamine Modified Sulfonic Acid Catalyst Catalyse Synthesis of n-Butyl Benzoate[J]. Chinese Journal of Applied Chemistry, 2023, 40(10): 1430-1436.

Figures/Tables 9

Fig.1 Synthesis route of polyallylamine supported sulfonic acid catalyst

Fig.2 FT-IR spectra of polyallylamine resin （PPA） and polyallylamine resin supported sulfonic acid catalyst （PPA-S）

Fig.3 SEM images of polyallylamine resin （PPA）（A） and polyallylamine resin supported sulfonic acid catalyst （PPA-S）（B）

Fig.4 Thermogravimetric analysis curves of polyallylamine resin and polyallylamine resin supported sulfonic acid catalyst

Table 1 Optimization of catalyst loading for the yield of n-butyl benzoate

Entry	n（NBA）/n（BA）	BA/mol	m（catalyst）/g	Time/h	Yield/%
1	2	0.1	0.5	24	90
2	2	0.1	1.0	14	93
3	2	0.1	1.5	8	93
4	2	0.1	2.0	6	95
5	2	0.1	2.5	6	95

Table 2 Temperature effects on the yield of n-butyl benzoate

Entry	Temperature/°C	n（NBA）/n（BA）	Time/h	Yield/%
1	100	2	24	88
2	110	2	14	93
3	120	2	6	95
4	130	2	6	95

Table 3 The effect of the ratio of alcohol to acid on the synthesis of n-butyl benzoate

Entry	n（NBA）/n（BA）	Time/h	Yield/%
1	1.2	12	81
2	1.5	8	88
3	1.8	6	94
4	2.0	6	95
5	2.2	6	94

Fig.5 The recycling of catalyst

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Polyallylamine Modified Sulfonic Acid Catalyst Catalyse Synthesis of n-Butyl Benzoate

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