CN107935851B - 一种单辛酸甘油酯及其制备方法 - Google Patents
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
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- B01J31/0212—Alkoxylates
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/30—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with trihydroxylic compounds
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
本发明公开了一种单辛酸甘油酯及其制备方法。所述单辛酸甘油酯是将酸性催化剂加到辛酸和碳酸二甲酯中,加入碱调节反应后得到辛酸甲酯粗品,再将复合催化剂加到辛酸甲酯粗品和甘油中反应制得。通过复合催化剂制备的单辛酸甘油酯选择性好,产物单一,而且该条件下制备的产品无色透明,显著提高了产品的品质。本发明的方法具有效率高,能耗低和酯化率高,节能环保,同时可以显著降低生产成本制备的单辛酸甘油酯产品单一,可以实现高的酯化率。
Description
技术领域
本发明属于油脂化学技术和精细化工领域,更具体地,涉及一种单辛酸甘油酯的制备方法。
背景技术
单辛酸甘油酯是由甘油和辛酸酯酯化合成的酯,其酯化摩尔比为1:1相对分子质量是218,属于单脂肪酸甘油酯的一种。单辛酸甘油酯为无色透明液体或透明塑性体,熔点40℃,无臭,稍有苦味,微溶于水,可分散于热水中。从化学结构观察,其具备有α-型和β-型两种结构,通常是两种结构的混合物,其中主要为α-型。
单甘油辛酸酯对一些化妆品中常见的细菌(如金黄色葡萄球菌、大肠杆菌、假单胞菌等)、霉菌和酵母均有较强的抑菌作用,有较广的抑菌谱,且具有较好的耐酸碱性和热稳定性。目前单辛酸甘油酯正广泛用于化妆品抗菌剂。
单辛酸甘油酯是脂肪的中间代谢物。当体内脂肪酶对单辛酸甘油酯作用时,可分解为游离脂肪酸和甘油。并且该过程不会产生代谢不良的蓄积性以及特异性反应,安全性较高,可以称之为天然来源。由于全球范围内单辛酸甘油酯用于化妆品没有限制,说明该防腐剂作为化妆品添加剂有较好的安全性,并且可以宣称“无添加”并应用于化妆品中。
目前单辛酸甘油酯的合成方法主要有直接酯化法、甘油解法、基团保护法和酶法:
直接酯化法一般采用过量甘油,在150~180℃下反应,反应时间为2~4h,所得产物为单辛酸甘油酯、二辛酸甘油酯,以及部分未反应的底物混合物,其中单辛酸甘油酯含量为50%左右,反应结束后要分离除去过量甘油和催化剂。
甘油解法是在高温下(>220℃)三辛酸甘油酯和甘油以碱为催化剂进行反应,反应时间2~3h,产物同样是单辛酸甘油酯、二辛酸甘油酯的混合物,单辛酸甘油酯的含量为45%左右,需要经分子蒸馏得到高纯度的单辛酸甘油酯。
直接酯化法和甘油解法的缺点:高温条件下反应,能耗大;高温会导致油脂中不饱和脂肪酸发生讲解,讲解产物颜色较深,影响产品色泽;副产物较多,分离提纯较困难;设备投资大,成本高。
基团保护法:甘油分子中有三个羟基,若直接与酸酯化,三个羟基均有成酯机会,将生成单甘脂及二甘酯的混合物。利用某些化合物和甘油作用,将甘油的两个羟基保护后,再与脂肪酸酯化,再在一定条件下水解得到高纯度的单甘脂。目前所采用的保护剂有硼酸、酮和醛。
基团保护法的缺点:反应步数多、反应时间长、需要用到大量,环境污染严重、成本高。
酶法常见的有溶剂体系、反向胶束体系、超临界体系、无溶剂体系等。酶法虽然克服了化学法反应条件的苛刻、能耗大、分离纯化困难以及废液污染环境等缺点,但酶法技术尚不成熟,目前仍处于实验室阶段。工业化的单辛酸甘油酯多采用化学法进行合成,技术关键在于催化剂的合理选取及反应条件的控制。
发明内容
本发明的目的是为了克服现有技术的缺陷,提供一种单辛酸甘油酯。该单辛酸甘油酯选择性好,产物单一,而且无色透明,具有良好的品质。
本发明的另一目的在于提供一种上述单辛酸甘油酯的制备方法。该方法先将辛酸与碳酸二甲酯经酸性催化剂制备成辛酸甲酯,辛酸甲酯再经一种复合催化剂与甘油进行选择性催化反应获得α-型单辛酸甘油酯,通过该方法制备的单辛酸甘油酯产品单一,效率高,能耗低和酯化率高,显著降低了成本。
本发明上述目的通过以下技术方案予以实现:
一种单辛酸甘油酯是将酸性催化剂加到辛酸和碳酸二甲酯中,加入碱调节反应后得到辛酸甲酯粗品,再将复合催化剂加到辛酸甲酯粗品和甘油中反应制得。
优选地,所述的酸性催化剂为对甲苯磺酸、浓硫酸、磷酸、磷钨酸或723型强酸性苯乙烯系阳离子交换树脂。
优选地,所述的酸性催化剂、辛酸和碳酸二甲酯的当量比为(0.02~0.2):1:(1~2)。
优选地,所述的碱为氢氧化钠、氨水、碳酸氢钠、碳酸钠或碳酸钾。
优选地,所述的复合催化剂为单丁基氧化锡与氧化物的组合物,所述氧化物为三氧化二铝、氧化钡或氧化钙中的一种以上。
更为优选地,所述的单丁基氧化锡占复合催化剂总质量的5~30wt.%,所述三氧化二铝占复合催化剂总质量的30~95wt.%,所述氧化钡占复合催化剂总质量的30~95wt.%,所述氧化钙占复合催化剂总质量的30~95wt.%。
优选地,所述的辛酸甲酯粗品和甘油的当量比为1:(2~20),所述的复合催化剂为辛酸甲酯粗品质量的0.1~5%。
上述的单辛酸甘油酯的制备方法,包括以下具体步骤:
S1.将酸性催化剂加到辛酸和碳酸二甲酯中,设定反应温度和反应时间,至气相色谱法监测辛酸反应完全,加入碱调节pH值至中性,减压蒸馏掉过量的碳酸二甲酯,得到辛酸甲酯粗品;
S2.将复合催化剂加到辛酸甲酯粗品和甘油中,调节温度和反应时间至辛酸甲酯反应完全,冷却至室温过滤,蒸除过量的甘油,得到单辛酸甘油酯。
优选地,步骤S1中所述反应温度为60~90℃,所述反应时间为6~10h。
优选地,步骤S2中所述温度为140~220℃,所述反应时间为4~10h。
与现有技术相比,本发明具有以下有益效果:
1.本发明将辛酸与碳酸二甲酯经酸性催化剂制备成辛酸甲酯,辛酸甲酯再经一种复合催化剂与甘油进行选择性催化反应获得ɑ-型单辛酸甘油酯。通过复合催化剂制备的单辛酸甘油酯选择性好,产物单一,而且该条件下制备的产品无色透明,显著提高了产品的品质。
2.本发明方法具有反应温度低,可以实现高的酯化率,反应基本是本体反应无污染,操作简便,节能环保,同时可以显著降低生产成本。
具体实施方式
下面结合具体实施例进一步说明本发明的内容,但不应理解为对本发明的限制。若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.将1.44公斤(10mol)辛酸与碳酸二甲酯1.35公斤(15mol)混合,加入98%浓硫酸100克(1mol),80℃反应7h,GC检测辛酸甲酯的含量为99.8%,加入10%的氢氧化钠水溶液调节pH值为中性,减压蒸馏掉过量的碳酸二甲酯,得到辛酸甲酯粗品。
2.将3克单丁基氧化锡和10克氧化钡加入到辛酸甲酯粗品1.58公斤(10mol)和甘油1.84公斤(20mol)中,调节温度至140℃,反应10h,气相色谱监测辛酸甲酯反应完全,冷却至室温过滤,蒸除过量的甘油,得到单辛酸甘油酯。单辛酸甘油酯采用GB 1886.57-2016的检测方法,测得单辛酸甘油酯中α单酯的含量为97.2%。
实施例2
1.将1.44公斤(10mol)辛酸与碳酸二甲酯1公斤(11.1mol)混合,加入对甲苯磺酸38克(0.2mol)90℃反应6h,GC检测辛酸甲酯的含量为99.01%,加入28%氨水溶液调节pH值为中性,减压蒸馏掉过量的碳酸二甲酯,得到辛酸甲酯粗品。
2.将3克单丁基氧化锡、4.4克氧化钡和15.6克三氧化二铝加入到辛酸甲酯粗品1.58公斤(10mol)和甘油2.76公斤(30mol)中,调节温度至220℃,反应4h,气相色谱监测辛酸甲酯反应完全,冷却至室温过滤,蒸除过量的甘油,得到单辛酸甘油酯。
所得单辛酸甘油酯采用GB 1886.57-2016的检测方法,测得单辛酸甘油酯中α单酯的含量为98.2%。
实施例3
1.将1.44公斤(10mol)辛酸与碳酸二甲酯1.19公斤(12mol)混合,加入723型强酸性苯乙烯阳离子交换树脂30克,60℃反应10h,GC检测辛酸甲酯的含量为98.3%,加入10%的氢氧化钠水溶液调节pH值为中性,减压蒸馏掉过量的碳酸二甲酯,得到辛酸甲酯粗品。
2.将单丁基氧化锡2克和氧化钙40克加入到辛酸甲酯1.58公斤(10mol)和甘油4.6公斤(50mol)中,调节温度至180℃,反应6h,GC检测辛酸甲酯反应完全,打冷至室温过滤,蒸除过量的甘油,得到单辛酸甘油酯。
所得单辛酸甘油酯采用GB 1886.57-2016的检测方法,测得单辛酸甘油酯中α单酯的含量为99.3%。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种单辛酸甘油酯的制备方法,其特征在于,包括以下具体步骤:
S1.将酸性催化剂加到辛酸和碳酸二甲酯中,设定在60~90℃反应6~10h,至气相色谱法监测辛酸反应完全,加入碱调节pH值至中性,减压蒸馏掉过量的碳酸二甲酯,得到辛酸甲酯粗品;所述的酸性催化剂为对甲苯磺酸、浓硫酸、磷酸、磷钨酸或723型强酸性苯乙烯系阳离子交换树脂;
S2.将复合催化剂加到辛酸甲酯粗品和甘油中,调节温度在140~220℃反应4~10h至辛酸甲酯反应完全,冷却至室温过滤,蒸除过量的甘油,得到单辛酸甘油酯;所述的复合催化剂为三氧化二铝、氧化钡或氧化钙中的一种以上与单丁基氧化锡的组合物。
2.根据权利要求1所述的单辛酸甘油酯的制备方法,其特征在于,步骤S1中所述酸性催化剂、辛酸和碳酸二甲酯的当量比为(0.02~0.2):1:(1~2)。
3.根据权利要求1所述的单辛酸甘油酯的制备方法,其特征在于,步骤S1中所述碱为氢氧化钠、氨水、碳酸氢钠、碳酸钠或碳酸钾。
4.根据权利要求1所述的单辛酸甘油酯的制备方法,其特征在于,所述复合催化剂中各组分占复合催化剂总质量的百分比为单丁基氧化锡5~30%,三氧化二铝30~95%,氧化钡30~95%,氧化钙30~95%。
5.根据权利要求1所述的单辛酸甘油酯的制备方法,其特征在于,步骤S2中所述辛酸甲酯粗品和甘油的当量比为1:(2~20),所述复合催化剂为辛酸甲酯粗品质量的0.1~5%。
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