CN105016970A - 一种氨基酸功能化杂多类离子液体催化α-蒎烯水合反应的方法 - Google Patents
一种氨基酸功能化杂多类离子液体催化α-蒎烯水合反应的方法 Download PDFInfo
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- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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Abstract
本发明涉及一种α-蒎烯一步催化水合反应的方法,具体的说是采用氨基酸功能化杂多类离子液体催化α-蒎烯水合反应制备松油醇的方法,属于林产化学品制备技术领域。本发明利用氨基酸功能化杂多类离子液体结构中的羧基作为α-蒎烯水合反应的催化活性基团,实现了在无其他辅助催化剂条件下,α-蒎烯一步水合反应清洁制备松油醇。催化剂溶于水相而不溶于α-蒎烯相,以液-液两相方式催化水合反应,反应结束后静置,油水两相自然分层,上层为水合产物相,无需水洗工艺;下层为溶于水的催化剂相,无需处理,可直接循环使用。本发明避免了均相酸催化剂的使用和含酸废水的产生,是α-蒎烯一步水合反应的环境友好工艺。
Description
技术领域
本发明涉及一种α-蒎烯水合反应制备松油醇的方法,具体的说是采用氨基酸功能化杂多类离子液体催化α-蒎烯水合反应制备松油醇的方法,属于林产化学品制备技术领域。
背景技术
松节油是一种宝贵的生物质资源,也是世界上产量最大、价格最便宜的精油,其深加工工艺是林产化学的研发热点。松节油的主要组分α-蒎烯的含量占80%以上,是生产许多高附加值精细化工产品的重要原料。α-蒎烯在酸性催化条件下水合反应,可生成性质稳定、具有持久紫丁香香气的松油醇,作为调香物、印染剂、洗涤剂、消毒剂和浮选剂等,广泛用于香皂、印刷、选矿等行业(程芝.天然树脂生产工艺学[M].北京:中国林业出版社,1996,20-25)。最新研究表明,松油醇也可同聚乙烯一起用来合成功能性聚合物(K Satoh,H Sugiyama,MKamigaito.Biomass-derived heat-resistant alicyclic hydrocarbon polymers:poly(terpenes)and theirhydrogenated derivatives.Green Chemistry,2006,8(10):878-882)。
工业上现采用硫酸等液体无机酸为催化剂经两步法合成松油醇,存在三废处理量大,腐蚀设备,环境污染严重等诸多缺点。研究者发现,氯乙酸、三氯乙酸等有机酸可高效的催化α-蒎烯水合反应一步法制取松油醇,其结构中的羧基基团是起关键性作用的催化活性基团(Roman Aguirre M,Dela Torre Saenz L,Wilber Antunez Flores,et al.Synthesis of terpineol fromα-pinene by homogeneous acid catalysis[J].Catalysis Today,2005,107-108:310-314;吴端桂.松节油低温水合制α-松油醇的研究[J].工程与装备,2006(5):6-10)。氯乙酸系列催化剂在水相和α-蒎烯相中皆具有良好的相溶性,虽催化效果突出,但后处理时,催化剂和产物分离性差,需水洗工艺,不可避免的出现大量酸性废水,且催化剂损失严重,重复使用性差。
具有非均相反应特征的固体酸催化剂一度被认为是液体酸的理想替代品。固体超强酸(于世涛,刘福胜,解从霞,等.SO4 2-/SiO2-ZrO2复合固体超强酸催化α-蒎烯水合反应[J].精细化工,2004,21(3):178-180,184;王亚明,刘天成,周梅村,等.固体超强酸MoO3/ZrO2催化松节油合成松油醇的研究[J].林产化学与工业,2004,24(B08):57-60)、微孔及介孔分子筛(YuShitao,Liu Fusheng,Li Lu,et al.Preparation of modified mesoporous molecular sieves and theircatalytic properties for rosin and turpentine reactions[J]Mesoporous Materials,2009,1-33;Wijayati N,Pranowo H D,Jumina Triyono,et al.Characterization of ZHY and TCA/ZHY catalystsfor hydration ofα-pinene[J].International Journal of Chemical Engineering and Applications,2013,4(4):178-182)、离子交换树脂(李冬梅,赵振东,毕良武,等.松节油合成高纯α-松油醇的研究[J].现代化工,2008,28(增刊2):345-348)、改性粘土及氧化物(Comelli Nora,Avila MariaCecilia,Volzone Cristina,et al.Hydration ofα-pinene catalyzed by acid clays[J].From CentralEuropean Journal of Chemistry,2013,11(5):689-697;Maria C vila,Nora A Comelli,RodríguezCastellón E,etal.Study of solid acid catalysis for the hydration ofα-pinene[J].Journal ofMolecular Catalysis A:chemical,2010,322(1-2):106-112)、负载杂多酸(Castanheiro J E,RamosA M,Fonseca I,et al.The acid-catalysed reaction ofα-pinene over molybdophos-phoric acidimmobilised in dense polymeric membranes[J].Catalysis Today,2003,82(1-4):187-193)等常见固体酸催化剂皆被用于α-蒎烯的水合反应制备松油醇。这些固体酸催化剂虽然具有易分离和回收利用的优势,但在提高化学转化的有效性方面又显能力不足,不同程度地存在易失活、酸位分布不均匀、制备重现性差等缺点。最重要的是,为有效催化α-蒎烯的水合反应,上述固体酸催化剂在使用过程中皆需负载氯乙酸、三氯乙酸等催化活性组分,或直接使用氯乙酸做辅助催化剂,同样存在活性组分容易流失、循环使用能力差的问题,并未真正的实现催化工艺的环境友好。
酸功能化离子液体兼具了液体酸的较高酸强度、密度较大的酸性位和分布均匀等优点,以及易分离、可循环使用等固体酸的特性,并成功应用于多种酸催化反应中。人们发现[HSO3-PMIM]H2PO4(季开慧,刘仕伟,于世涛,等.磺烷基咪唑磷酸盐-氯乙酸复合催化体系在α-蒎烯水合反应中的应用[J].林产化学与工业,2007(06):77-80)、[PEOIM-SO3H]H2PO4(刘仕伟,李露,于世涛,等.温控特性的酸功能化离子液体合成及其在α-蒎烯水合反应中的应用[J].催化学报,2011,32(3):468-471)、[AC-18n]HSO4(戚春杰,李露,刘仕伟,等.十八胺聚氧乙烯醚类离子液体催化合成松油醇[J].青岛科技大学学报(自然科学版),2012,33(4):345-351、Lu Li,Yue Liu,Shitao Yu,et al.,Hydration ofα-pinene homogenous catalyzed by acidicpolyether-modifiedammonium salt ionic liquid in“microreactor”.Research on ChemicalIntermediates,2015,41:2407-2414)等酸功能化离子液体在α-蒎烯水合反应中显示出了良好的催化及分离性能。然而,上述离子液体催化体系亦皆需引入氯乙酸为辅助催化剂,而离子液体催化剂单独使时则催化活性较低。既能溶于水也能溶于α-蒎烯的氯乙酸虽然有助于催化体系呈现出良好的催化效果,但其流失和循环使用问题仍未得到解决。
综上所述,研制高效环保的α-蒎烯一步水合反应制备松油醇的环境友好催化工艺研究具有重要意义,而目前工业化及文献报道的工艺皆无法避免液体酸的使用,也即并未实现环境友好工艺。
发明内容
为解决现有α-蒎烯一步水合反应技术中皆需有机液体酸辅助催化,未达到环境友好目标的问题,本发明提出一种采用氨基酸功能化杂多离子液体催化α-蒎烯一步水合反应的方法。该方法工艺简单,催化剂制备方便,无需其他有机酸辅助催化,催化剂溶于水相与产物相分层,循环使用性能良好。
本发明的技术方案如下:
按物质的量比n(α-蒎烯):n(水):n(催化剂)=60:300:1的比例,称取水和催化剂,加入反应烧瓶,机械搅拌升温至80℃,加入α-蒎烯,保温反应8h后,静置冷却至室温,溶于水相的催化剂自行与产物相分层,分别回收催化剂(水)相和产物相。催化剂相无需处理,直接循环使用。
上述技术方案中所述的催化剂为氨基酸功能化杂多类离子液体催化剂[Asp]3PW12O40、[Gly]3PW12O40、[Lys]3PW12O40其中的一种,其制备方法为:
将磷钨酸水溶液与三倍物质的量的氨基酸(天冬氨酸,谷氨酸,赖氨酸)水溶液在反应瓶中混合,磁力搅拌,于60℃下反应12h,旋蒸除去剩余水分,80℃干燥2h,得到氨基酸功能化杂多类离子液体催化剂固体。
本发明与现有的α-蒎烯水合反应技术相比较,具有如下优点:
1、将羧基活性基团通过氨基酸引入到杂多类离子液体催化剂的结构中,催化反应过程中无需氯乙酸等均相有机酸辅助催化剂,属环境友好工艺;
2、本发明所提供的氨基酸杂多类离子液体催化剂,溶于水相而不溶于α-蒎烯相,在α-蒎烯水合反应过程中为液-液两相催化,反应结束后静置,油水两相自然分层,上层为水合产物相,无需水洗,与工业上硫酸催化法以及氯乙酸辅助催化法相比大大减少了废水的产生;下层为溶于水的催化剂相,无需处理,可直接循环使用。
具体实施方法
下面结合具体实施例对本发明方法进一步说明,但并不是对本发明的限定。
实施例1
取1.20g天冬氨酸和8.64g磷钨酸分别溶于适量去离子水中,在反应瓶中混合,磁力搅拌,于60℃下反应12h,旋蒸除去剩余水分,80℃干燥2h,得到氨基酸功能化杂多类离子液体催化剂[Asp]3PW12O40紫灰色固体。
取1mmol[Asp]3PW12O40催化剂溶于0.3mol去离子水中,充分搅拌下升温至80℃,加入0.06molα-蒎烯反应8h。反应完毕后静置,冷却至室温,产物相与溶于水的催化剂相分层,分出上层产物,用无水硫酸镁干燥,气相色谱分析测定其组成,所得催化结果见表1。
实施例2
取0.68g甘氨酸和8.64g磷钨酸分别溶于适量去离子水中,在反应瓶中混合,磁力搅拌,于60℃下反应12h,旋蒸除去剩余水分,80℃干燥2h,得到氨基酸功能化杂多类离子液体催化剂[Gly]3PW12O40白色固体。
取1mmol[Gly]3PW12O40催化剂溶于0.3mol去离子水中,充分搅拌下升温至80℃,加入0.06molα-蒎烯反应8h。反应完毕后静置,冷却至室温,产物相与溶于水的催化剂相分层,分出上层产物,用无水硫酸镁干燥,气相色谱分析测定其组成,所得催化结果见表1。
实施例3
取1.32g赖氨酸和8.64g磷钨酸分别溶于适量去离子水中,在反应瓶中混合,磁力搅拌,于60℃下反应12h,旋蒸除去剩余水分,80℃干燥2h,得到氨基酸功能化杂多类离子液体催化剂[Lys]3PW12O40白色固体。
取1mmol[Lys]3PW12O40催化剂溶于0.3mol去离子水中,充分搅拌下升温至80℃,加入0.06molα-蒎烯反应8h。反应完毕后静置,冷却至室温,产物相与溶于水的催化剂相分层,分出上层产物,用无水硫酸镁干燥,气相色谱分析测定其组成,所得催化结果见表1。
表1氨基酸功能化杂多类离子液体催化α-蒎烯水合反应性能
实施例4-8
向实施例1中回收的溶解于水中的催化剂相中补加2g去离子水,升温至80℃,加入0.06molα-蒎烯反应8h。反应完毕后静置,冷却至室温,产物相与溶于水的催化剂相分层,分出上层产物,用无水硫酸镁干燥,气相色谱分析测定其组成。循环使用实验进行五次,所得催化结果见表2。
表2[Asp]3PW12O40催化α-蒎烯水合反应的循环使用性能
对比例1
取0.06molα-蒎烯和5.4mL去离子水在反应瓶中搅拌升温至80℃,加入0.003mol对比离子液体催化剂[AC1820]HSO4和0.003mol氯乙酸,反应8h。反应完毕后静置,冷却至室温,用无水硫酸镁干燥上层产物,气相色谱分析测定其组成,所得催化结果α-蒎烯转化率为93.5%,α-松油醇选择性为57.3%。
对比例2
取0.06molα-蒎烯和5.4mL去离子水在反应瓶中搅拌升温至80℃,加入0.003mol对比离子液体催化剂[AC1820]HSO4,反应8h。反应完毕后静置,冷却至室温,用无水硫酸镁干燥上层产物,气相色谱分析测定其组成,所得催化结果α-蒎烯转化率为1.0%,α-松油醇选择性为54.6%。
Claims (1)
1.一种一步催化α-蒎烯水合反应的方法,其特征在于:采用氨基酸功能化杂多类离子液体[Asp]3PW12O40、[Gly]3PW12O40、[Lys]3PW12O40其中的一种,在无其他辅助催化剂条件下,按物质的量比n(α-蒎烯):n(水):n(催化剂)=60:300:1的比例,在反应温度80℃下,反应8h,由α-蒎烯一步水合反应制备松油醇;催化剂溶于水相而不溶于α-蒎烯相,以液-液两相方式催化水合反应,反应结束后静置,油水两相自然分层,分别回收上层水合产物相和下层溶于水中的催化剂相,产物相无需水洗,催化剂相无需处理,直接循环使用。
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