两步酯化法合成皮革加脂剂及其应用性能研究

doi:10.19677/j.issn.1004-7964.2020.03.002

皮革科学与工程 ›› 2020, Vol. 30 ›› Issue (3): 7-14.doi: 10.19677/j.issn.1004-7964.2020.03.002

两步酯化法合成皮革加脂剂及其应用性能研究

霍文凯^1,2, 周继博^1,2, 廖学品^1,2,*, 石碧^1,2

1.制革清洁技术国家工程实验室（四川大学）,四川成都 610065;
2.四川大学皮革化学与工程教育部重点实验室（四川大学）,四川成都 610065

收稿日期:2019-12-24 出版日期:2020-06-28 上线日期:2020-05-26
通讯作者: *E-mail:xpliao@scu.edu.cn。
作者简介:霍文凯,硕士生,hwk895226@126.com。
基金资助:
国家重点研发计划(2017YFB0308500)

Synthesis of Leather Fatliquor Using Two-step Esterification Reaction and its Application Properties

HUO Wenkai^1,2, ZHOU Jibo^1,2, LIAO Xuepin^1,2,*, SHI Bi^1,2

1.Nationa Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065, China;
2.Key Laboratory of Leather Chemistry and Engineering of Ministry of Education, Sichuan University, Chengdu 610065, China

Received:2019-12-24 Published:2020-06-28 Online:2020-05-26

摘要/Abstract

摘要： 以马来酸酐(MAH)为起始材料,依次与二乙二醇乙醚、十八醇进行反应,然后经过磺化制得一种新型加脂剂MADO-SUL。通过单因素实验确定了最佳反应条件,第一步酯化反应生成中间产物MADG的反应温度为90 ℃,时间为5 h,马来酸酐与二乙二醇乙醚反应摩尔比为1∶1;第二步酯化反应生成MADO的反应温度为190 ℃,时间为7 h,MADG与十八醇反应摩尔比为1∶1,催化剂亚磷酸用量为反应体系总质量的0.5%;磺化反应温度为80 ℃,时间为5 h,MADO与亚硫酸钠反应摩尔比为1∶1。通过傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(¹H-NMR)表征分析了MADO-SUL的结构,并将MADO-SUL应用于牛皮蓝湿革加脂实验,同时与市售加脂剂SF做对比。结果表明,MADO-SUL加脂性能良好,MADO-SUL加脂后坯革的二氯甲烷萃取物含量为3.224 %,挥发性有机物（VOCs）含量为92.484 μgC/g。市售加脂剂加脂后坯革的二氯甲烷萃取物含量为5.485%,挥发性有机物（VOCs）含量为173.348 μgC/g,均高于MADO-SUL。

关键词: 马来酸酐, 二乙二醇乙醚, 十八醇, 加脂剂, VOCs

Abstract: A new leather-making fatliquoring agent MADO-SUL was prepared using maleic anhydride (MAH) as starting material. It was reacted in order with diethylene glycol diethyl ether, stearyl alcohol and sodium sulfite respectively, which involved two-step esterification and a sulfonation reaction. A series of single factor experiments were carried out to explore the optimum synthesis conditions. It was found that the optimum synthesis temperature of MADG, the product of first esterification, was 90 ℃ and the reaction time was 5 h with the molar ratio of maleic anhydride to diethylene glycol diethyl ether to be 1∶1. Additionally, the product of second esterification reaction was named MADO and the optimum reaction temperature was 190 ℃, the reaction time was 7 h and the molar ratio of MADG to stearyl alcohol was 1∶1. Furthermore, phosphorous acid was selected as catalyst and its dosage was 0.5% of total reaction system on weight basis. As for sulfonation reaction, its optimum temperature was 80 ℃, the optimum time was 5 h, and the molar ratio of MADO to sodium sulfite was 1∶1. The structure of MADO-SUL was analyzed by FT-IR and ¹H-NMR. Moreover, MADO-SUL was applied to fatliquoring experiment of cowhide blue wet leather and compared with commercial fatliquoring agent SF. It was found that the prepared MADO-SUL exhibited promising performances, and the dichloromethane extracted content of leather fatliquored by MADO-SUL was 3.224% and the content of volatile organic compounds (VOCs) was 92.484 μgC/g, both lower than that of leather fatliquored by commercial fatliquoring agent, which were 5.4855% and 173.348 μgC/g, respectively.

Key words: maleic anhydride, diethylene glycol ether, stearyl alcohol, fatliquor, VOCs

中图分类号:

TS529.4

霍文凯, 周继博, 廖学品, 石碧. 两步酯化法合成皮革加脂剂及其应用性能研究[J]. 皮革科学与工程, 2020, 30(3): 7-14.

HUO Wenkai, ZHOU Jibo, LIAO Xuepin, SHI Bi. Synthesis of Leather Fatliquor Using Two-step Esterification Reaction and its Application Properties[J]. Leather Science and Engineering, 2020, 30(3): 7-14.

参考文献

[1] Alam S, Siddiq A M, Javid M, et al.Surface and Physicochemical Properties Studies of Six Commercial Fatliquors[J]. Materials Focus, 2017, 6(1): 34-40.
[2] Sizeland K H, Wells H C, Kelly S J R, et al. The influence of water, lanolin, urea, proline, paraffin and fatliquor on collagen D-spacing in leather[J]. RSC Advances, 2017, 7(64): 40658-40663.
[3] Lyu B, Wang Y F, Gao D, et al.Intercalation of modified zanthoxylum bungeanum maxin seed oil/stearate in layered double hydroxide: Toward flame retardant nanocomposites[J]. Journal of environmental management, 2019, 238: 235-242.
[4] 王学川,郝东艳,李季,等.线性超支化磷酸酯盐聚合物复合加脂剂的制备及应用[J].皮革科学与工程,2019,29(05):10-15.
[5] Sardari A, Alvani A A S, Ghaffarian S R. Preparation of castor oil-based fatliquoring agent via a Pickering emulsion method for use in leather coating[J]. Journal of Coatings Technology and Research, 2019, 16(6): 1765-1772.
[6] HAQ M I U L, Rasheed A, Adnan A, et al. Synthesis, Characterization and Application of Sulphited Castor Maleic Adduct as an Effective Leather Fatliquor[J]. Journal of the Society of Leather Technologists and Chemists, 2016, 100(5): 263-270.
[7] Lyu B, Wang H D, Ma J, et al.Preparation and application of castor oil/nano-TiO₂ composite fatliquoring agent via a Pickering emulsion method[J]. Journal of cleaner production, 2016, 126: 711-716.
[8] Sahu B, Rathinam A, Javid M A, et al.Preparation of fatliquor having antifungal activity using the oil of Citrullus colocynthis for application in leather processing[J]. Industrial crops and products, 2017, 108: 553-557.
[9] Du J, Shi L, Peng B.Amphiphilic acrylate copolymer fatliquor for ecological leather: Influence of molecular weight on performances[J]. Journal of Applied Polymer Science, 2016, 133(20).
[10] 杜金霞. 丙烯酸长链酯单体和两亲聚合物的合成及其结构与复鞣加脂性能的关系[D].四川大学,2016.
[11] 张鑫. 以甘油、不同类型长链饱和脂肪酸为主要起始原料制备高耐光结合型加脂剂[D].温州大学,2018.
[12] Sun Y, Zhang L, Zhou J, et al.Synthesis and properties of dihydroxyoleic acid methyl ester ethoxylates[J]. Journal of Dispersion Science and Technology, 2019, 40(9): 1272-1279.
[13] NKWOR A, UKOHA P, Will W, et al.Fatliquoring potentials of sulphonated Hura crepitans L seed oil[J]. Revista de Pielarie Incaltaminte, 2019, 19(2): 99.
[14] Yamak H B, Tamer Y, Yıldırım H.The effect of maleic acid diesters type on the stability of vinyl acetate emulsion polymers[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2016, 497: 233-241.
[15] 周华龙,何有节.皮革化工材料学[M].北京:科学出版社,2010.
[16] 韩冰,耿涛,李秋小,等.甲基二乙醇胺双脂肪酸酯的合成与表征[J].精细化工,2014,31(3):332-336.
[17] 邹灯旺. 双子型结构加脂剂的制备与性能研究[D].温州大学,2017.
[18] 中华人民共和国国家发展和改革委员会.QB/T2710-2005皮革物理和机械试验抗张强度和伸长率的测定[S].北京:中国轻工业出版社,2005.
[19] 中华人民共和国国家发展和改革委员会.QB/T2711-2005皮革物理和机械试验撕裂力的测定:双边撕裂[S].北京:中国轻工业出版社,2005.
[20] 罗晓明,丁绍兰,周庆芳.皮革理化分析[M].北京:中国轻工业出版社,2013.
[21] 孙霞,黄新霞,沈云,等.顶空-气相色谱法检测皮革中挥发性有机物[J].中国皮革,2014,43(11):40-43.
[22] 周继博. 无甲醛氨基树脂复鞣剂的合成及应用研究[D].四川大学,2019.
[23] 方丽俊,刘福胜.β-(3,5-二叔丁基-4-羟基苯基)-丙酸十八碳醇酯的合成[J].应用化工,2014,43(01):105-107+110.
[24] 崔凯,邹祥龙,兰云军.马来酸酐-丙烯酸二元共聚物的合成研究[J].精细化工,2010,27(02):179-181.
[25] 邹祥龙,兰云军,柴玉叶.HBSS型琥珀酸(混合)双酯磺酸钠盐加脂剂的合成[J].精细化工,2008,25(12):1225-1228.
[26] Zhang M, Zhang Y, Chen M, et al.A high-performance and low-cost soy flour adhesive with a hydroxymethyl melamine prepolymer[J]. Polymers, 2018, 10(8): 909.
[27] Banu H.T. andS.J.J.o.w.p.e. Meenakshi, Synthesis of a novel quaternized form of melamine-formaldehyde resin for the removal of nitrate from water. 2017. 16: p. 81-89.
[28] Banu H T, Meenakshi S.Synthesis of a novel quaternized form of melamine-formaldehyde resin for the removal of nitrate from water[J]. Journal of water process engineering, 2017, 16: 81-89.
[29] 常建华,董琦功.波谱原理及解析[M].北京:科学出版社,2012.
[30] 乔换灵. 二元醇联结的Gemini脂肪醇磷酸酯制备及加脂性能[D].陕西科技大学,2019.
[31] 孙燕情. 基于妥尔油改性的皮革加脂剂的合成及性能研究[D].陕西科技大学,2017.
[32] Zhao Q, Li Y, Chai X, et al.Interaction of inhalable volatile organic compounds and pulmonary surfactant: Potential hazards of VOCs exposure to lung[J]. Journal of hazardous materials, 2019, 369: 512-520.
[33] 唐其文,吴艳.挥发性有机物VOCs监测方法及治理研究[J].环境与发展,2018,30(06):159-161.
[34] 程逸超,杨金龙,朱均均,等.疏水性离子液体[C4mim][PF6]对木质纤维预水解液的脱毒作用[J].林产化学与工业,2017,37(05):45-52.

两步酯化法合成皮革加脂剂及其应用性能研究

Synthesis of Leather Fatliquor Using Two-step Esterification Reaction and its Application Properties

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 3

编辑推荐

Metrics

本文评价

[1]	王璐瑶, 陈向, 王雨璐, 张佳星, 贾欣宇, 蒋弟勇, 陈慧. 氧化亚硫酸化菜籽油加脂剂的制备及性能研究[J]. 皮革科学与工程, 2024, 34(1): 75-82.
[2]	宁国强, 周继博, 廖学品, 石碧. 基于环烷烃的皮革加脂剂的制备及应用性能研究[J]. 皮革科学与工程, 2022, 32(2): 72-78.
[3]	陈志坤, 罗涛, 彭必雨, 张春晓. 典型抗氧化剂对大豆磷脂加脂剂性能的影响[J]. 皮革科学与工程, 2021, 31(4): 27-34.