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CN108117536B - 一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法 - Google Patents

一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法 Download PDF

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CN108117536B
CN108117536B CN201611090708.6A CN201611090708A CN108117536B CN 108117536 B CN108117536 B CN 108117536B CN 201611090708 A CN201611090708 A CN 201611090708A CN 108117536 B CN108117536 B CN 108117536B
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高艳安
王宇
王畅
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Abstract

本发明提供一种1，2‑丙二醇与二氧化碳合成碳酸丙烯酯的方法，该方法以碱性离子液体为催化剂、乙腈为溶剂，按照催化剂与1，2‑丙二醇的摩尔比为0.01‑0.04，溶剂与1，2‑丙二醇的质量比4‑8进行配料，在反应温度150‑180℃，CO2的压力1‑10MPa条件下，反应时间24小时。本发明的特点是：反应原料廉价易得，工艺过程简单；碱性离子液体催化剂催化效果高，原料1，2‑丙二醇的收率最高达67.2％。

Description

一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法
技术领域
本发明属于一种合成碳酸丙烯酯的方法，具体涉及一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法。
背景技术
二氧化碳是主要的温室气体，同时也是地球上分布最广，储量最丰富的碳资源。因此，近几十年来，人们对二氧化碳的研究不断深入，将二氧化碳用于合成具有高附加值的化工产品成为了目前的研究热点。无论从环境保护的角度，还是从经济发展的角度，将二氧化碳转化成为高附加值的化工产品都具有重要的研究意义。
碳酸丙烯酯(PC)是一种性质稳定、高沸点、低毒性的极性有机溶剂，也是重要的有机化学品，在有机合成中发挥着重要的作用。
碳酸丙烯酯可用作电池的电解质溶剂、燃料的添加剂、烯烃和芳烃的萃取剂等，也是高能电池和电容器的良好介质。在高分子领域，常作为聚合物的溶剂和增塑剂来使用，同时也是合成聚碳酸脂和聚氨酯的中间体。近年来，碳酸丙烯酯还被用于与甲醇进行酯交换反应制备碳酸二甲酯(DMC)。
在DMC的制备过程中，不可避免地产生大量副产物1，2-丙二醇，因此有必要为1,2-丙二醇寻找新的利用途径，实现1,2-丙二醇的有效综合利用，从而降低DMC的生产成本。更重要的是，利用二氧化碳与1,2-丙二醇直接合成碳酸丙烯酯，不仅1,2-丙二醇被循环使用，还充分地利用了二氧化碳温室气体，因此，本发明具有重要的科学意义和应用价值。
由二氧化碳和1,2-丙二醇合成碳酸丙烯酯的反应，由于受热力学的限制，反应条件十分苛刻，1,2-丙二醇收率较低。因此，有必要研究和开发新型的催化剂高效催化1,2-丙二醇的转化，提高反应收率。
发明内容
本发明的目的是提供了一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法，采用碱性离子液体作为催化剂，以乙腈作为溶剂，由二氧化碳和1,2-丙二醇高效合成碳酸丙烯酯。
本发明一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法包括如下步骤：
以乙腈为反应溶剂，乙腈与1，2-丙二醇的质量比为4-8：1，加入催化剂，催化剂的用量为催化剂与1，2-丙二醇的摩尔比为0.01-0.04：1，注入CO2压力至1～10MPa，控制反应温度为150-180℃，反应时间24小时。
如上所述的催化剂是碱性离子液体。
所述碱性离子液体包括：(1)氢氧化1-甲基-3-丁基咪唑，(2)咪唑化1-甲基-3-丁基咪唑盐，(3)咪唑化四丁基磷盐，(4)咪唑化四丁基氨盐，(5)1-甲基-3-丁基咪唑N，N-二甲基-3-氨基-1-丙烷磺酸盐，(6)四丁基磷N，N-二甲基-3-氨基-1-丙烷磺酸盐。
离子液体的结构式对应如下：
Figure BDA0001166931090000021
本发明的优点如下：
1)充分地利用了二氧化碳温室气体和生产碳酸二甲酯的副产物1，2-丙二醇。
2)碱性离子液体催化性能好，大大提高了1，2-丙二醇的转化率和碳酸丙烯酯的产率，为有效地通过二氧化碳和1，2-丙二醇制备碳酸丙烯酯提供了一条新的路线。
具体实施方式
实施例1
催化剂为氢氧化1-甲基-3-丁基咪唑
称取2.5g 1，2-丙二醇和10g乙腈溶剂(溶剂与1，2-丙二醇质量比为4)，催化剂0.051g(3.29×10-4mol)一并加入到25mL高压釜的玻璃套管中，高压釜密封后，用二氧化碳气流缓慢吹扫5min，然后充入0.5MPa二氧化碳，在150℃搅拌30min至温度稳定，然后调整二氧化碳压力为1MPa，。反应24h后，反应釜自然冷却至室温，缓慢放出二氧化碳，即可制得碳酸丙烯酯。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为35.4％。
实施例2
催化剂为氢氧化1-甲基-3-丁基咪唑
反应条件、制备步骤与实施例1相同，不同之处在于乙腈质量为20g(溶剂与1，2-丙二醇质量比为8)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为38.1％。
实施例3
催化剂为氢氧化1-甲基-3-丁基咪唑
反应条件、制备步骤与实施例1相同，不同之处在于催化剂质量为0.204g(催化剂与1，2-丙二醇摩尔比为4)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为38.3％。
实施例4
催化剂为氢氧化1-甲基-3-丁基咪唑
反应条件、制备步骤与实施例1相同，不同之处在于CO2压力调整为10MPa。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为37.1％。
实施例5
催化剂为氢氧化1-甲基-3-丁基咪唑
反应条件、制备步骤与实施例1相同，不同之处在于反应温度为180℃。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为40.4％。
实施例6
催化剂为咪唑化1-甲基-3-丁基咪唑
反应条件、制备步骤与实施例2相同，不同之处在于催化剂为咪唑化1-甲基-3-丁基咪唑盐(0.068g,3.29×10-4mol)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为42.5％。
实施例7
催化剂为咪唑化四丁基磷盐
反应条件、制备步骤与实施例2相同，不同之处在于催化剂为咪唑化四丁基磷盐(0.107g,3.29×10-4mol)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为28.2％。
实施例8
催化剂为咪唑化四丁基氨盐
反应条件、制备步骤与实施例2相同，不同之处在于催化剂为咪唑化四丁基氨盐(1.02g,3.29×10-4mol)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为58.6％。
实施例9
催化剂为1-甲基-3-丁基咪唑N，N-二甲基-3-氨基-1-丙烷磺酸盐
反应条件、制备步骤与实施例2相同，不同之处在于催化剂为1-甲基-3-丁基咪唑N，N-二甲基-3-氨基-1-丙烷磺酸盐(0.1g,3.29×10-4mol)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为67.2％。
实施例10
催化剂为四丁基磷N，N-二甲基-3-氨基-1-丙烷磺酸盐
反应条件、制备步骤与实施例2相同，不同之处在于催化剂为四丁基磷N，N-二甲基-3-氨基-1-丙烷磺酸盐(0.134g,3.29×10-4mol)。用10mL乙醚萃取后加入内标，取少量样品进行气相色谱分析，碳酸丙烯酯的内标收率为43.7％。

Claims (1)

1.一种1，2-丙二醇与二氧化碳合成碳酸丙烯酯的方法，其特征在于步骤如下：以乙腈为反应溶剂，以乙腈与1，2-丙二醇的质量比为4～8：1配料，加入催化剂，催化剂与1，2-丙二醇的摩尔比为0.01～0.04：1，注入CO2压力至1～10MPa，控制反应温度为150-180℃，反应时间24小时；所述的催化剂为碱性离子液体，所述碱性离子结构式为：
Figure FDA0002586775570000011
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