CN111411023A - 一种植物油多元醇及其制备方法与应用 - Google Patents
一种植物油多元醇及其制备方法与应用 Download PDFInfo
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- CN111411023A CN111411023A CN202010234093.XA CN202010234093A CN111411023A CN 111411023 A CN111411023 A CN 111411023A CN 202010234093 A CN202010234093 A CN 202010234093A CN 111411023 A CN111411023 A CN 111411023A
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- vegetable oil
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- Epoxy Compounds (AREA)
Abstract
本发明公开了一种植物油多元醇的制备方法：(1)将金属催化剂和溶有仲胺的有机溶剂体系加入反应器中，然后将葡萄糖水溶液加入所述反应器中进行还原氨解反应，得到含有多羟基化合物的混合溶液；(2)将环氧植物油和碱性催化剂溶于有机溶剂中得到含环氧植物油的混合溶液，将含环氧植物油的混合溶液与步骤(1)得到的含有多羟基化合物的混合溶液分别同时泵入微通道模块化反应装置的微结构反应器中进行反应，得到植物油多元醇。本发明还公开了上述方法制备得到的植物油多元醇及其在制备聚氨酯硬泡沫中的应用。本发明采用含有多羟基官能团的开环试剂，制备得到的植物油多元醇羟值高，粘度低，可完全替代传统石化多元醇应用于聚氨酯泡沫材料的制备。
Description
技术领域
本发明属于化工材料及其生产技术领域，具体涉及一种植物油多元醇及其制备方法与应用。
背景技术
聚氨酯是由异氰酸酯和多元醇反应而制成的一种具有氨基甲酸酯链段重复单元结构，广泛用于泡沫塑料、表面涂料、粘合剂、密封剂和复合剂材料等领域。聚氨酯材料性能优异，用途广泛制品种类多，其中以聚氨酯泡沫塑料用途最为广泛。目前，石化燃料资源的消耗和对环境问题的日益关注迫使全球研究人员使用植物油制备聚氨酯。
植物油多元醇主要应用于制备聚氨酯领域，其制备的植物油基聚氨酯材料完全符合环境保护的要求；并且由于植物油的主要成分脂肪酸甘油酯的疏水性，植物油基聚氨酯材料具有优异的理化性能，特别是具备更好的疏水性和热稳定性。因此植物油多元醇及其聚氨酯材料得到了迅速的发展。
植物油多元醇是重要的可再生资源，能够与异氰酸酯类化合物反应生成聚氨酯，是石油基多元醇的良好代替原料。近年来合成植物油多元醇的方法主要有：1)将植物油与多元醇进行醇解反应，生成多羟基化合物；2)利用臭氧氧化植物油中的不饱和双键，生成带有端位羟基的多羟基化合物；3)将植物油氧化为环氧植物油，然后通过水解、加氢、甲酯化或卤化等处理生成多羟基化合物。
上述的合成植物油多元醇的方法中，方法1)和方法3)采用较多。CN1837180A 和CN101139252A分别以菜籽油和小桐子油为原料，经醇解/环氧化/开环三步反应制备得到植物油多元醇。CN1837181A和CN10118803A分别以以菜籽油和小桐子油为原料，经环氧化/开环/醇解三步反应制备得到植物油多元醇。CN101906016A以橡胶籽油为主要原料，经环氧化/开环二步反应制备得到植物油多元醇。CN101659627A中通过环氧植物油与二醇胺之间的开环反应和酯基酰胺化反应，制备得到植物油多元醇。 CN101747184A和CN101230020A利用环氧化反应和开环反应均在酸性条件下反应，一步法制备得到植物油多元醇。
以上专利中，植物油多元醇的合成均基于双键环氧后再开环，开环试剂主要选用小分子的醇、醇胺或羧酸，但存在产物品质不高、后处理繁琐、反应中易出现交联副反应等问题，且应用于聚氨酯材料时仍需复配一定比例的石化多元醇。
发明内容
发明目的：为了解决现有制备方法制备的植物油多元醇品质不高、后处理繁琐、反应中易出现交联副反应等问题，本发明第一方面提供了一种植物油多元醇的制备方法；本发明第二方面提供了上述方法制备得到的植物油多元醇，制备出的植物油多元醇羟值高，粘度低，工艺简单，产物无需进一步精制处理；本发明第三方面提供了上述植物油多元醇在制备聚氨酯硬泡沫中的应用，可完全替代传统石化多元醇。
技术方案：本发明第一方面所述一种植物油多元醇的制备方法，包括如下步骤：
(1)将金属催化剂和溶有仲胺的有机溶液加入反应器中，向所述反应器内通入氢气，然后将葡萄糖水溶液加入所述反应器中进行还原氨解反应，得到含有式III、式Ⅳ多羟基化合物的混合溶液；
式中R为CH3或CH2CH3
(2)将环氧植物油和碱性催化剂溶于有机溶剂中得到含环氧植物油的混合溶液，将所述含环氧植物油的混合溶液与步骤(1)得到的含有式III、式Ⅳ多羟基化合物的混合溶液分别同时泵入微通道模块化反应装置的微结构反应器中进行反应，得到植物油多元醇；所述环氧植物油的碘值为10～15，环氧值为6.0％～6.7％。优选地，所得植物油多元醇的环氧值为0.25％～1.00％。
步骤(1)中葡萄糖(Ⅰ)与仲胺(Ⅱ)按照下示合成路线合成多羟基化合物(Ⅲ、Ⅳ)：
式中R为CH3或CH2CH3。
本发明生物基多元醇(植物油多元醇)反应式如下：
式中R为CH3或CH2CH3。
步骤(1)中，所述金属催化剂为Ni/SiO2-Al2O3(65wt.％)、Pt/C(1wt.％)、Pd/C(5wt.％) 或Ru/C(5wt.％)中的任意一种或几种的组合，优选为Ni/SiO2-Al2O3(65wt.％)，所述金属催化剂市售均可获得；优选为已活化的金属催化剂，优选的金属催化剂活化方法为将金属催化剂装入反应管中，并通入一定流量的氢气，在120～350℃下煅烧两小时。所述仲胺为二甲胺和二乙胺中的任意一种或两种的组合，优选为二甲胺；所述有机溶液中的溶剂为四氢呋喃、甲醇、乙醇和乙酸乙酯中任意一种或几种的组合，优选为四氢呋喃；步骤(1)中所述溶有仲胺的有机溶液的浓度为55～75wt.％，优选为60wt.％。所述葡萄糖水溶液的浓度为20～35wt.％，优选为33wt.％；所述金属催化剂的质量和所述葡萄糖的摩尔量的比值为9～31g:1mol，优选为12g:1mol。所述反应温度为110～125℃，反应压力为6.0～7.5Mpa，反应时间为2～2.5h，所述葡萄糖水溶液的加料速度为8.1～15mL/min；优选反应温度为120℃，反应压力为7.0Mpa，反应时间为2h，加料速度为10mL/min。优选地，所述反应器为釜式反应器。
步骤(2)中，所述环氧植物油为环氧花生油、环氧菜籽油、环氧棉籽油和环氧大豆油中任意一种或几种的组合；优选为按照中国专利2014104412890制备方法制备的环氧植物油。所述碱性催化剂为氢氧化钠、氢氧化钾、碳酸钠和碳酸氢钠中任意一种或几种的组合，优选为碳酸钠；所述有机溶剂为四氢呋喃、甲醇、乙醇和乙酸乙酯中任意一种或几种的组合，优选为四氢呋喃，其中步骤(1)有机溶液中的溶剂与步骤(2)中的有机溶剂相同。所述碱性催化剂与环氧植物油的质量百分比为0.02％～0.1％，优选为 0.08％；所述有机溶剂与环氧植物油的质量比为2～6:1，优选为4.3:1；所述含式III、式Ⅳ多羟基化合物的混合溶液泵入微通道模块化反应装置的流速为1.0～3.0mL/min，所述含环氧植物油的混合溶液泵入微通道模块化反应装置的流速为2.0～4.0mL/min。所述微结构反应器中的反应温度为60～100℃，优选为80℃；反应停留时间为10～15min，优选为12min；微结构反应器的体积为40～120mL。
步骤(1)中所述仲胺、葡萄糖和步骤(2)中所述环氧植物油的环氧基的摩尔比为1～1.05:1:0.5～1.0，优选为1:1:0.8。
所述微通道模块化反应装置包括通过连接管依次串联的微混合器、微结构热交换器、管状温度控制模块和微结构反应器；其中，微混合器上通过管道连接有两个精确且低动脉的进料泵，一个泵负责泵送含式III、式Ⅳ多羟基化合物的混合溶液，另一个泵负责泵送环氧植物油和碱性催化剂溶于有机溶剂得到的混合溶液。
其中，上述微混合器的型号优选为slit plate mixer LH25，微结构热交换器的型号优选为coaxial heat exchanger，微结构反应器的型号为Vapotech。
对步骤(2)微结构反应器的反应液流出液进行分液，取油相水洗至中性，再分液，取油相蒸发溶剂，得到植物油多元醇。
本发明第二方面提供上述制备方法制备得到的植物油多元醇。
本发明第三方面提供所述植物油多元醇在制备聚氨酯硬泡沫中的应用。
有益效果：(1)多羟基化合物进行开环最大的问题是因为多羟基导致的交联从而出现粘度大的问题，本发明采用中国专利2014104412890制备的环氧植物油(碘值为10～15、环氧值为6.0％～6.7％)，并通过微反应结构器协同控制得到了保留环氧值和碘值的植物油多元醇，其结构与现有的植物油多元醇有很大差异，粘度大大降低，流动性增加，有利于泡沫制作；(2)本发明采用式III、式Ⅳ多羟基化合物作为新型的开环试剂，结构中引入了碱性基团，其结构存在多个羟基，官能团度高，可以保证其开环制备的植物油多元醇产品具有较高的羟值，又可以减少交联副反应，降低产品粘度；(3)此植物油多元醇羟基位置均匀，可完全替代传统石化多元醇应用于聚氨酯硬泡，植物油多元醇可独立发泡，且无需在发泡时添加碱性催化剂，理论上越少小分子引入，泡沫孔径越均匀，绝热性能更好，稳定性越好，性能更好；(4)此外，本发明选用的催化剂用量极少，微量残余不影响多元醇的使用，产物无须进一步精制处理，工艺简单。
附图说明
图1为微通道模块化反应装置示意图。
具体实施方式
根据下述实施例，可以更好地理解本发明。然而，本领域的技术人员容易理解，实施例所描述的内容仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
本发明对所制备的植物油多元醇和聚氨酯泡沫材料的相关测定方法如下：
(1)根据GB/T 12008.3-2009测羟值；
(2)根据GB/T 12008.7-2010测粘度；
(3)根据GB/T 5532-2008测碘值；
(4)根据GB/T 6343-2009测定泡沫塑料的表观密度；
(5)根据GB/T 8813-2008测定硬质泡沫塑料的压缩强度，取发泡垂直方向截面为压缩面，压缩速率为5mm/min，取样品10％变形量时的测试值作为材料的压缩强度；
(6)根据GB/T 10294-2008测定硬质聚氨酯泡沫塑料材料导热系数；
下述实施例中，所用的微通道模块化反应装置，如图1所示，包括通过连接管依次串联的微混合器、微结构热交换器、管状温度控制模块和微结构反应器。温度由油浴锅加热控制。其中，微混合器上通过管道连接有两个精确且低动脉的进料泵，一个泵负责送含式III、式Ⅳ多羟基化合物的混合溶液(存放于储液罐A内)，另一个泵负责送环氧植物油和碱性催化剂溶于有机溶剂得到的混合溶液(存放于储液罐B内)。
实施例1
将18.5g的Ni/SiO2-Al2O3(65wt.％)和78.90g二甲胺的四氢呋喃溶液(60wt.％，二甲胺约1.05mol)加入釜式反应器中搅拌，温度升至120℃；在反应器内通入H2，使反应器内的压力保持在7.0Mpa。反应条件稳定后，在反应器内加入545g葡萄糖水溶液 (33wt.％，葡萄糖1mol)，加料速率为10mL/min，反应时间2h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将按照中国专利2014104412890的制备方法制备的191g环氧大豆油(其环氧基数目为0.8mol，碘值为10)和0.153g碳酸钠溶于1000mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为80℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.2mL/min，B的进样速率为2.5mL/min，保持反应停留时间为 12min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为426mgKOH/g，粘度为6230mPa·s，碘值为5.72，环氧值为0.29％。
实施例2
将15.5g的Ni/SiO2-Al2O3(65wt.％)和70.74g二甲胺的四氢呋喃溶液(65wt.％，二甲胺约1.02mol)加入釜式反应器中搅拌，温度升至120℃；在反应器内通入H2，使反应器内的压力保持在6.5Mpa。反应条件稳定后，在反应器内加入600g葡萄糖水溶液 (30wt.％,葡萄糖1mol)，加料速率为10mL/min，反应时间2h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将按照中国专利2014104412890的制备方法制备的232g环氧花生油(其环氧基数目为0.9mol，碘值为13)和0.186g碳酸氢钠溶于1250mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为80℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.6mL/min，B的进样速率为3.2mL/min，保持反应停留时间为10min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为417mgKOH/g，粘度为6590mPa·s，碘值为8.18，环氧值为 0.53％。
实施例3
将23.0g的Ni/SiO2-Al2O3(65wt.％)和64.40g二甲胺的四氢呋喃溶液(70wt.％，二甲胺约1mol)加入釜式反应器中搅拌，温度升至110℃；在反应器内通入H2，使反应器内的压力保持在7.0Mpa。反应条件稳定后，在反应器内加入720g葡萄糖水溶液 (25wt.％，葡萄糖1mol)，加料速率为8.5mL/min，反应时间2.5h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将按照中国专利2014104412890的制备方法制备的190g环氧菜籽油(其环氧基数目为0.75mol，碘值为15)和0.152g氢氧化钠溶于1000mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为90℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为2.0mL/min，B的进样速率为3.2mL/min，保持反应停留时间为15min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为396mgKOH/g，粘度为6020mPa·s，碘值为9.36，环氧值为 0.37％。
实施例4
将18.5g的Ni/SiO2-Al2O3(65wt.％)和75.13g二甲胺的四氢呋喃溶液(60wt.％,二甲胺约1mol)加入釜式反应器中搅拌，温度升至120℃；在反应器内通入H2，使反应器内的压力保持在7.2Mpa。反应条件稳定后，在反应器内加入545g葡萄糖水溶液(33wt.％, 葡萄糖1mol)，加料速率为10mL/min，反应时间2h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将按照中国专利2014104412890的制备方法制备的214g环氧棉籽油(其环氧基数目为0.8mol，碘值为14)和0.173g碳酸钠溶于1200mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为70℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.4mL/min，B的进样速率为3.5mL/min，保持反应停留时间为 12min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为393mgKOH/g，粘度为5920mPa·s，碘值为9.04，环氧值为0.61％。
实施例5
将180g的Pd/C(5wt.％)和78.89g二乙胺的四氢呋喃溶液(60wt.％，二乙胺约1.05mol)加入釜式反应器中搅拌，温度升至110℃；在反应器内通入H2，使反应器内的压力保持在7.0Mpa。反应条件稳定后，在反应器内加入545g葡萄糖水溶液(33wt.％,葡萄糖1mol)，加料速率为10ml/min，反应时间2.5h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将按照中国专利2014104412890的制备方法制备的240g环氧大豆油(其环氧基数目为1mol，碘值为11)和0.192g碳酸钠溶于1500mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为90℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.8mL/min，B的进样速率为4.0mL/min，保持反应停留时间为 10min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为387mgKOH/g，粘度为6310mPa·s，碘值为7.05，环氧值为0.85％。
实施例6植物油多元醇制备的聚氨酯硬泡沫的性能测试
取实施例1制备的大豆油多元醇，采用一步法自由发泡工艺，与泡沫稳定剂AK8803(南京美思德)、环己胺(江都大江化工)、异氰酸酯WANNATE PM-200(烟台万华)、发泡剂环戊烷(佛山美龙)反应进行发泡，即可制备出硬质聚氨酯泡沫，其表观密度为 39.3kg/m3，垂直压缩强度为229kPa，导热系数为20.37W/m·K。
对比例1
将47.0g的Ni/SiO2-Al2O3(65wt.％)和60g二甲胺的四氢呋喃溶液(75wt.％，二甲胺约1mol)加入釜式反应器中搅拌，温度升至125℃；在反应器内通入H2，使反应器内的压力保持在7.5Mpa。反应条件稳定后，在反应器内加入900g葡萄糖水溶液(20wt.％，葡萄糖1mol)，加料速率为15ml/min，反应时间2h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将按照中国专利2014104412890的制备方法制备的215g环氧大豆油(其环氧基数目为0.9mol，碘值为11)和0.172g碳酸钠溶于1200mL四氢呋喃溶液中，并置于储液罐B中。将储液罐A中的混合溶液和储液罐B中的原料加入釜式反应器中搅拌，温度升至125℃，其中A的进样速率为25mL/min，B的进样速率为35mL/min，反应时间为2.5h。反应完毕后，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为255mgKOH/g，粘度为16160mPa·s，碘值为7.30，环氧值为1.11％。
对比例2
将180g葡萄糖(葡萄糖1mol)溶于1000mL四氢呋喃溶液中，并置于储液罐A 中。将按照中国专利2014104412890的制备方法制备的191g环氧大豆油(其环氧基数目为0.8mol，碘值为10)和0.153g碳酸钠溶于1000mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为80℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为3.6mL/min，B的进样速率为2.7mL/min，保持反应停留时间为 12min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为238mgKOH/g，粘度为14310mPa·s，碘值为7.41，环氧值为1.83％。
对比例3
将22.14g的Ni/SiO2-Al2O3(65wt.％)和92.414g二甲胺的四氢呋喃溶液(60wt.％，二甲胺约1.23mol)加入釜式反应器中搅拌，温度升至120℃；在反应器内通入H2，使反应器内的压力保持在7.0Mpa。反应条件稳定后，在反应器内加入654g葡萄糖水溶液(33wt.％，葡萄糖1.2mol)，加料速率为15mL/min，反应时间2.5h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将200g环氧大豆油(环氧值为6.40％，碘值为4.4)和0.160g碳酸钠溶于1150mL 四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为80℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.5mL/min，B的进样速率为3.4 mL/min，保持反应停留时间为12min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为185mgKOH/g，粘度为11230mPa·s，碘值为2.44，环氧值为0。
对比例4
将18.5g的Ni/SiO2-Al2O3(65wt.％)和75.13g二甲胺的四氢呋喃溶液(60wt.％，二甲胺约1mol)加入釜式反应器中搅拌，温度升至120℃；在反应器内通入H2，使反应器内的压力保持在7.0Mpa。反应条件稳定后，在反应器内加入545g葡萄糖水溶液 (33wt.％，葡萄糖1mol)，加料速率为10mL/min，反应时间2h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A中。
将200g环氧大豆油(环氧值为6.40％，碘值为4.2)和0.162g碳酸钠溶于1100mL 四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为80℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.5mL/min，B的进样速率为3.6 mL/min，保持反应停留时间为12min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为244mgKOH/g，粘度为10880mPa·s，碘值为2.65，环氧值为0.64％。
对比例5
将25.54g的Ni/SiO2-Al2O3(65wt.％)和130.73g二甲胺的四氢呋喃溶液(60wt.％，二甲胺约1.74mol)加入釜式反应器中搅拌，温度升至120℃；在反应器内通入H2，使反应器内的压力保持在7.0Mpa。反应条件稳定后，在反应器内加入905g葡萄糖水溶液(33wt.％，葡萄糖1.66mol)，加料速率为15mL/min，反应时间2.5h。葡萄糖催化还原氨解反应完毕后，将所得的含式III、式Ⅳ多羟基化合物的混合溶液置于储液罐A 中。
将262g环氧大豆油(环氧值为6.10％，碘值为63.5)和0.212g碳酸钠溶于1400mL四氢呋喃溶液中，并置于储液罐B中。调节油浴锅温度为80℃，于微通道模块化反应装置的连续流体系中进行反应。其中A的进样速率为1.8mL/min，B的进样速率为3.6 mL/min，保持反应停留时间为12min，将反应产物静置分液，收集油相，用水洗涤至中性，再经分液，旋蒸，得植物油多元醇，其羟值为140mgKOH/g，粘度为17450mPa·s，碘值为36.43，环氧值为0。
本发明提供了一种植物油多元醇及其制备方法与应用的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (10)
1.一种植物油多元醇的制备方法，其特征在于，包括如下步骤：
(1)将金属催化剂和溶有仲胺的有机溶液加入反应器中，向所述反应器内通入氢气，然后将葡萄糖水溶液加入所述反应器中进行还原氨解反应，得到含有式III、式Ⅳ多羟基化合物的混合溶液；
式中R为CH3或CH2CH3
(2)将环氧植物油和碱性催化剂溶于有机溶剂中得到含环氧植物油的混合溶液，将所述含环氧植物油的混合溶液与步骤(1)得到的含有式III、式Ⅳ多羟基化合物的混合溶液分别同时泵入微通道模块化反应装置的微结构反应器中进行反应，得到植物油多元醇；所述环氧植物油的碘值为10～15，环氧值为6.0％～6.7％。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述金属催化剂为Ni/SiO2-Al2O3、Pt/C、Pd/C和Ru/C中的任意一种或几种的组合；所述仲胺为二甲胺和二乙胺中的任意一种或两种的组合，所述有机溶液中的溶剂为四氢呋喃、甲醇、乙醇和乙酸乙酯中任意一种或几种的组合。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述溶有仲胺的有机溶液的浓度为55～75wt.％；所述葡萄糖水溶液的浓度为20～35wt.％；所述金属催化剂的质量和所述葡萄糖的摩尔量的比值为9～31g:1mol。
4.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述反应温度为110～125℃，反应压力为6.0～7.5Mpa，反应时间为2～2.5h；所述葡萄糖水溶液的加料速度为8.1～15mL/min。
5.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述环氧植物油为环氧花生油、环氧菜籽油、环氧棉籽油和环氧大豆油中任意一种或几种的组合；所述碱性催化剂为氢氧化钠、氢氧化钾、碳酸钠和碳酸氢钠中任意一种或几种的组合；所述有机溶剂为四氢呋喃、甲醇、乙醇和乙酸乙酯中任意一种或几种的组合。
6.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述碱性催化剂与环氧植物油的质量百分比为0.02％～0.1％，所述有机溶剂与环氧植物油的质量比为2～6:1。
7.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中所述仲胺、葡萄糖和步骤(2)中所述环氧植物油的环氧基的摩尔比为1～1.05:1:0.5～1.0。
8.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述微结构反应器中的反应温度为60～100℃，反应停留时间为10～15min。
9.权利要求1～8中任意一项所述的制备方法制备得到的植物油多元醇。
10.权利要求9所述的植物油多元醇在制备聚氨酯硬泡沫中的应用。
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Application publication date: 20200714 Assignee: ZHANGJIAGANG FEIHANG TECHNOLOGY Co.,Ltd. Assignor: Nanjing Tech University Contract record no.: X2023980053254 Denomination of invention: A Plant Oil Polyol and Its Preparation Method and Application Granted publication date: 20210525 License type: Common License Record date: 20231221 |