CN111423573B - 一种聚氨酯多元醇及其制备方法与应用 - Google Patents
一种聚氨酯多元醇及其制备方法与应用 Download PDFInfo
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- CN111423573B CN111423573B CN202010326078.8A CN202010326078A CN111423573B CN 111423573 B CN111423573 B CN 111423573B CN 202010326078 A CN202010326078 A CN 202010326078A CN 111423573 B CN111423573 B CN 111423573B
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Abstract
本发明公开了一种聚氨酯多元醇及其制备方法与应用。聚氨酯多元醇的制备方法为:(1)将2,3‑环氧丁烷和酸性催化剂溶于惰性溶剂中,得到溶液A;将二缩三乙二醇溶于惰性溶剂中,得到溶液B;将环氧植物油溶于惰性溶剂中,得到溶液C;(2)将溶液A、B分别同时泵入第一微混合器,混合后通入第一微反应器,反应;(3)在步骤(2)进行的同时,将溶液C和第一微反应器流出液分别同时泵入第二微混合器,混合后,通入第二微反应器,反应,分离,得到植物油多元醇;(4)将植物油多元醇溶于惰性溶剂中,得到溶液D;将环氧丙烷和碱性催化剂溶于惰性溶剂中,得到溶液E;将溶液D与溶液E分别同时泵入釜式反应器中反应,得到聚氨酯多元醇。
Description
技术领域
本发明涉及一种聚氨酯多元醇及其制备方法和应用,该聚氨酯多元醇可用于聚氨酯弹性体的制备。
背景技术
聚氨酯是由异氰酸酯与多元醇反应而制成的一种具有氨基甲酸酯链段重复结构单元的聚合物。聚氨酯制品分为发泡制品和非发泡制品两大类。发泡制品有软质、硬质、半硬质聚氨酯泡沫塑料;非发泡制品包括涂料、粘合剂、合成皮革、弹性体和弹性纤维等。聚氨酯材料性能优异,用途广泛,制品种类多,其中尤以聚氨酯泡沫塑料的用途最为广泛。
聚氨酯中所用的多元醇主要有三类,一种是以多元醇或有机胺为起始剂通过与环氧乙烷、环氧丙烷或环氧丁烷聚合得到的聚合物,称为聚醚多元醇:另一种改性接枝聚醚多元醇,是以聚醚多元醇为基础,然后用乙烯基单体在多元醇中经本体聚合反应而制得,称为聚合物多元醇,常与聚醚多元醇配合使用;第三种是由四氢呋喃开环聚合的多元醇。但是,随着石化资源储量日益减少,石化产品价格持续上涨且购买不便,直接影响到产品的生产。因此,寻求一种新的资源,使产品更经济、环保,同时减少对石化产品的依赖,是近年来多元醇的一个重要研究方向。
传统的弹性体聚醚多元醇都是用甘油、二甘醇、丙二醇等多羟基化合物作为起始剂,环氧丙烷、环氧乙烷作为链增长剂,里面含有98%以上是石油衍生物。目前,人们希望减少对石油的依赖,改善环境。生物质多元醇与石油类多元醇相比,能耗降低23%,非可再生资源消耗降61%,温室气体排放减少36%,以其替代石油基多元醇生产聚氨酯已成为聚氨酯材料发展的重要方向。大豆油作为最廉价丰富的植物油,通过分子改性制成大豆油基多元醇,可用于聚氨酯合成,由此生产的聚氨酯产品不仅安全卫生,还表现出更好的机械性能、热稳定性和耐化学品性。
以植物油为可再生原料,利用其结构中的双键实现羟基官能团的转化从而开发生物基聚氨酯多元醇是常用的方法,植物油价格低廉且来源稳定,其结构中甘油三酯及其长链基团可以实现石化多元醇的替代,然而目前该领域主要存在的问题包括因原料组分繁杂和官能团转化过程中极易导致的交联副反应,导致管能团无法有效转化、交联产生分子量分布宽、产品粘度大导致发泡应用受到限制等问题,并且因为植物油与很多醇试剂反应存在多相体系,传质效率低,反应对条件剧烈程度和时间的需求以及过程中存在不可控的副反应存在着矛盾,极大影响了其产品品质从而限制了其市场潜力,同时因产品结构不清晰及过程不可控导致构效关系总结还不够,因此,本领域的研究仍然有很多工作有待进行,较多技术瓶颈有待突破,开发新结构、采用新反应模式实现反应过程有效控制和结构精准构建,是后续研发的重点和难点,但同时,植物油聚氨酯多元醇产品的开发具有广阔的市场前景,一定突破技术瓶颈,将为生物基材料开发打破突破口,有望成为新经济增长点。
发明申请CN109369871A公开了一种应用于慢回弹聚氨酯软泡沫材料中的聚氨酯多元醇的制备方法,该方法是将三-(1-吖丙啶基)氧化膦和其他的二醇和卤醇制备得到羟基化合物,然后在催化剂的作用下,将羟基化合物和环氧植物油进行开环反应得植物油多元醇。其中,卤醇分子间易发生交叉副反应,且副产物中存在氯元素,亦会对环境产生污染。因此,需要开发一种聚氨酯多元醇新的制备工艺路径,以解决其存在的问题。
发明内容
发明目的:本发明所要解决的技术问题是针对现有技术的不足,提供一种聚氨酯多元醇,以克服目前制备聚氨酯多元醇对石化资源依赖性,绿色可再生的环氧植物油资源被引入;基于结构模拟和设计,同时尽可能制造同官能团活性差异分子,尽可能减少发生交联和降低官能度利用率,兼顾经济效应,采用廉价试剂构建高品质植物油聚氨酯多元醇;同时对于现有环氧植物油开环反应过程不可控,导致产品自身交联、粘度高的问题而提出的一种采用连续法制备聚氨酯多元醇的方法。
本发明还要解决的技术问题是提供上述聚氨酯多元醇的制备方法。
本法最后要解决的技术问题是提供上述聚氨酯多元醇的应用。
为解决上述问题,本发明公开了一种聚氨酯多元醇的制备方法,其包括如下步骤:
(1)将2,3-环氧丁烷和酸性催化剂溶于惰性溶剂中,得到溶液A;将二缩三乙二醇溶于惰性溶剂中,得到溶液B;将环氧植物油溶于惰性溶剂中,得到溶液C;
(2)将溶液A和溶液B分别同时泵入微通道反应装置中的第一微混合器,混合后通入第一微反应器,反应,得到含有羟基化合物的反应液;
(3)在步骤(2)进行的同时,将溶液C和第一微反应器流出液分别同时泵入微通道反应装置中的第二微混合器,混合后,通入第二微反应器,进行开环反应,得到含有植物多元醇的反应液,分离,得到植物油多元醇;
(4)将步骤(3)得到的植物油多元醇溶于惰性溶剂中,得到溶液D;将环氧丙烷和碱性催化剂溶于惰性溶剂中,得到溶液E;将溶液D与溶液E分别同时泵入釜式反应器中,进行加成聚合反应,得到聚氨酯多元醇。其中,其采取泵入时控制流速控制反应物浓度的措施以有效避免交联的发生。
步骤(1)中,所述的酸性催化剂为硫酸、盐酸、磷酸、氟硼酸、氯化铝和氯化铁中的任意一种或几种组合,优选为氟硼酸。
步骤(1)和步骤(4)中,所述的惰性溶剂为二氯甲烷、氯仿、四氯化碳、二氯乙烷和二甲苯中的任意一种或几种组合,优选为二氯乙烷。
步骤(1)中,溶液A中,2,3-环氧丁烷和酸性催化剂的摩尔比为(1.0~1.25):(0.1~0.2),优选1:0.16;2,3-环氧丁烷的浓度为2.20~4.50mmol/mL。
步骤(1)中,溶液B中,二缩三乙二醇的浓度为1.20~3.0mmol/mL。
步骤(1)中,溶液C中,所述的环氧植物油为按照CN104292187A所公开的方法制备得到的环氧大豆油或环氧棉籽油,其环氧值为6.0~6.7(即每100g环氧树脂中环氧含量为6.0g~6.7g);环氧植物油的浓度为0.15~0.40mmol/mL(环氧大豆油浓度=(环氧大豆油物质的量)/(环氧大豆油体积+溶剂体积))。
步骤(2)中,所述的微通道反应装置包括第一进料泵、第二进料泵、第三进料泵、第一微混合器、第二微混合器,第一微反应器、第二微反应器和接收器;其中,第一进料泵和第二进料泵通过管道以并联的方式连接到第一微混合器上,第一微混合器与第一微反应器串联,第一微反应器出料口与第三进料泵以并联的方式连接到第二微混合器上,第二微混合器依次与第二微反应器、接收器串联,所述的连接为通过管道连接;温度由油浴锅加热控制;所述的泵为精确且低脉动的泵。
其中,第一微混合器、第二微混合器的型号优选为slit plate mixer LH25;第一微反应器、第二微反应器型号优选为Vapotech;第一微反应器、第二微反应器均连有背压阀以防止气化。
步骤(2)中,溶液A和溶液B的泵入速率比为1:0.6~3.5;反应的温度为70~100℃(优选80℃),反应的停留时间为5~10min(优选7min)。
优选地,所述的第一微反应器的体积为2~20mL(优选8mL),溶液A泵入第一微混合器的流速为0.2~1.0mL/min(优选0.5mL/min),溶液B泵入第一微混合器的流速为0.2~1.0mL/min(优选0.5mL/min)。
步骤(3)中,控制第一微反应器流出液和溶液C的泵入速率比为1:0.5~2.0;优选地,在控制该速率的同时,使得二缩三乙二醇与环氧植物油的摩尔比为3.2~3.75:1;反应的温度为80~140℃(优选120℃),反应的停留时间为5~15min(优选10min)。
优选地,所述的第二微反应器的体积为4~60mL(优选20mL);溶液C泵入第二微混合器的流速为0.4~2.0mL/min(优选1.0mL/min)。
步骤(3)中,所述的分离为将第二微通道反应器流出液静置分层,收集油相,水洗至中性,再经分液,旋蒸得到植物油多元醇。
步骤(4)中,溶液D中,植物多元醇的浓度为0.10~0.25mmol/mL;溶液E中,环氧丙烷的浓度为3.0~6.50mmol/mL,环氧丙烷与步骤(1)所述环氧植物油中环氧基团的摩尔比为5~15:1(优选10:1);碱性催化剂与步骤(1)所述环氧植物油的质量百分比为0.02%~0.1%(优选0.8%)。
其中,植物油多元醇浓度=(植物油多元醇物质的质量)/(植物油多元醇体积+溶剂体积);其中,植物油多元醇的质量是根据原料中环氧植物油的用量推算得到的。
步骤(4)中,所述的碱性催化剂为碳酸铯、碳酸钠、碳酸钾、氢氧化钠、氢氧化钾、碳酸氢钠、碳酸镁、三乙胺、吡啶和甲醇钠中的任意一种或几种组合,优选为碳酸铯。
步骤(4)中,溶液D和溶液E的泵入速率比为1.5~6.5:1;所述的反应为在80~150℃(优选130℃)下反应2.5~3h。
优选地,溶液D泵入釜式反应器的流速为10.0~50.0mL/min,溶液E泵入釜式反应器的流速为10.0~50.0mL/min。
步骤(4)反应结束后,将釜式反应器中的产物静置分层,收集油相,进行酸洗中和,洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,即得聚氨酯多元醇;其中,所述的酸为盐酸,硫酸,磷酸中的任意一种或几种,优选为盐酸,盐酸质量百分浓度为5%。
上述方法制备得到的聚氨酯多元醇也在本发明的保护范围之内。
上述聚氨酯多元醇在制备聚氨酯弹性体中的应用也在本发明的保护范围之内。
其中,所述聚氨酯弹性体的制备方法参考现有技术,优选方法如下:在氮气保护下,采用预聚体法制备聚氨酯弹性体,将本发明制备的植物油多元醇与水、硅油、开孔剂、催化剂A-33、催化剂A-1、催化剂T-12混合,加入4,4’-二苯基甲烷二异氰酸酯,在70~90℃下反应1.5~2.5h后,用二正丁胺法测定反应体系中游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注于90~120℃的平板钢制模具中,并进行硫化,在80~100℃烘箱中老化20~30h。其中,所述植物油多元醇、水、硅油、开孔剂、催化剂A-33、催化剂A-1、催化剂T-12的质量比为1:0.015~0.025:0.005~0.015:0.015~0.025:0.002~0.004:0.0005~0.0015:0.00005~0.00007。所述植物油多元醇与4,4’-二苯基甲烷二异氰酸酯的质量比为1:0.7~1.05。
有益效果:与现有技术相比,本发明具有如下优势:
(1)本发明采用微通道技术,制备得到了低粘度的聚氨酯多元醇,该品质好、色泽浅,无需与石化聚醚多元醇混合,即可完全替代传统聚醚多元醇,用于聚氨酯弹性体的制备。
(2)本发明工艺简单,操作方便,能耗低,副反应少,反应效率高,过程稳定可控,所得的产物无需进一步处理,有工程放大潜力。
附图说明
图1为本发明的示意图。
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。
本发明对所制备的聚氨酯多元醇和聚氨酯弹性体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 24451-2009测拉伸强度;
(4)根据GB6344-2008测伸长率;
(5)根据GB6669-2008测压缩永久变形参数;
(6)根据GB6670-2008测回弹性能;
(7)根据GB10808-2006测撕裂强度。
实施例1
(1)聚氨酯多元醇的制备
取25.2g 2,3-环氧丁烷和12.30g氟硼酸水溶液(40wt.%)溶于85mL二氯乙烷得到混合溶液A,取52.5g二缩三乙二醇溶于190mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于300mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、0.9mL/min、1.0mL/min、1.0mL/min;微通道反应装置的第一微通道反应器体积为10mL,反应温度为80℃,反应停留时间为7min;微通道反应装置的第二微通道反应器体积为20mL,反应温度为120℃,反应停留时间为10min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于600mL二氯乙烷得到溶液D,取235.8g环氧丙烷和0.2g碳酸铯水溶液(40wt.%)溶于800mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为3h,其中溶液D和E的流速分别为40mL/min、15mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为41mg KOH/g,粘度为710mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
实施例2
(1)聚氨酯多元醇的制备
取25.2g 2,3-环氧丁烷和12.30g氟硼酸水溶液(40wt.%)溶于85mL二氯乙烷得到混合溶液A,取48.0g二缩三乙二醇溶于180mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.418mol)溶于370mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、1.0mL/min、1.0mL/min、1.30mL/min;微通道反应装置的第一微通道反应器体积为12mL,反应温度为80℃,反应停留时间为8min;微通道反应装置的第二微通道反应器体积为30mL,反应温度为120℃,反应停留时间为13min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于550mL二氯乙烷得到溶液D,取194.0g环氧丙烷和0.15g碳酸铯水溶液(40wt.%)溶于750mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为2.5h,其中溶液D和E的流速分别为48mL/min、15mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为47mgKOH/g,粘度为620mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
实施例3
(1)聚氨酯多元醇的制备
取29.7g 2,3-环氧丁烷和14.50g氟硼酸水溶液(40wt.%)溶于100mL二氯乙烷得到混合溶液A,取56.25g二缩三乙二醇溶于230mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于350mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.4mL/min、0.9mL/min、1.2mL/min、1.5mL/min;微通道反应装置的第一微通道反应器体积为12mL,反应温度为80℃,反应停留时间为9min;微通道反应装置的第二微通道反应器体积为35mL,反应温度为120℃,反应停留时为12min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于600mL二氯乙烷得到溶液D,取188.6g环氧丙烷和0.25g碳酸铯水溶液(40wt.%)溶于700mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为3h,其中溶液D和E的流速分别为35mL/min、10mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为37mgKOH/g,粘度为770mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
实施例4
(1)聚氨酯多元醇的制备
取27.72g 2,3-环氧丁烷和12.70g氟硼酸水溶液(40wt.%)溶于90mL二氯乙烷得到混合溶液A,取52.5g二缩三乙二醇溶于170mL二氯乙烷得到溶液B,取100g环氧棉籽油(环氧基团为0.375mol)溶于370mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、0.9mL/min、1.0mL/min、1.50mL/min;微通道反应装置的第一微通道反应器体积为12mL,反应温度为80℃,反应停留时间为8min;微通道反应装置的第二微通道反应器体积为30mL,反应温度为120℃,反应停留时间为12min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于550mL二氯乙烷得到溶液D,取217.8g环氧丙烷和0.20g碳酸铯水溶液(40wt.%)溶900mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为2.5h,其中溶液D和E的流速分别为35mL/min、15mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为35mgKOH/g,粘度为810mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g棉籽基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得棉籽油基聚氨酯弹性体。
实施例5
(1)聚氨酯多元醇的制备
取23.04g 2,3-环氧丁烷和11.24g氟硼酸水溶液(40wt.%)溶于80mL二氯乙烷得到混合溶液A,取48.0g二缩三乙二醇溶于180mL二氯乙烷得到溶液B,取100g环氧棉籽油(环氧基团为0.381mol)溶于390mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、1.0mL/min、1.0mL/min、1.30mL/min;微通道反应装置的第一微通道反应器体积为12mL,反应温度为80℃,反应停留时间为8min;微通道反应装置的第二微通道反应器体积为25mL,反应温度为120℃,反应停留时间为10min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于600mL二氯乙烷得到溶液D,取177.2g环氧丙烷和0.15g碳酸铯水溶液(40wt.%)溶于580mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为3h,其中溶液D和E的流速分别为15mL/min、50mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为40mgKOH/g,粘度为690mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g棉籽基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得棉籽油基聚氨酯弹性体。
实施例6
(1)聚氨酯多元醇的制备
取25.2g 2,3-环氧丁烷和12.30g氟硼酸水溶液(40wt.%)溶于85mL二氯乙烷得到混合溶液A,取52.5g二缩三乙二醇溶于85mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于165mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、0.5mL/min、1.0mL/min、1.0mL/min;微通道反应装置的第一微通道反应器体积为8mL,反应温度为80℃,反应停留时间为7min;微通道反应装置的第二微通道反应器体积为20mL,反应温度为120℃,反应停留时间为10min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于270mL二氯乙烷得到溶液D,取235.8g环氧丙烷和0.2g碳酸铯水溶液(40wt.%)溶于800mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为3h,其中溶液D和E的流速分别为30mL/min、15mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为45mg KOH/g,粘度为690mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
对比例1
(1)聚氨酯多元醇的制备
取31.5g 2,3-环氧丁烷和15.37g氟硼酸水溶液(40wt.%)溶于125mL二氯乙烷得到混合溶液A,取52.5g二缩三乙二醇溶于200mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于350mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入釜式反应器中搅拌,其中溶液A和B的流速分别为8mL/min、15mL/min,反应温度为80℃,反应时间为1.5h。反应完毕后,将溶液C加入釜式反应器中,其中溶液C的流速为30mL/min,温度升至120℃,反应时间为2.5h。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于550mL二氯乙烷得到溶液D,取188.6g环氧丙烷和0.25g碳酸铯水溶液(40wt.%)溶于700mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为120℃,反应时间为3h,其中溶液D和E的流速分别为30mL/min、10mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为74mgKOH/g,粘度为2120mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
对比例2
(1)聚氨酯多元醇的制备
取25.34g 2,3-环氧丁烷和12.29g氟硼酸水溶液(40wt.%)溶于100mL二氯乙烷得到混合溶液A,取48.0g二缩三乙二醇溶于150mL二氯乙烷得到溶液B,取100g环氧棉籽油(环氧基团为0.375mol)溶于350mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入釜式反应器中搅拌,其中溶液A和B的流速分别为10mL/min、16mL/min,反应温度为80℃,反应时间为1.5h。反应完毕后,将溶液C加入釜式反应器中,其中溶液C的流速为25mL/min,温度升至120℃,反应时间为2.5h。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于550mL二氯乙烷得到溶液D,取188.6g环氧丙烷和0.25g碳酸铯水溶液(40wt.%)溶于700mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为120℃,反应时间为3h,其中溶液D和E的流速分别为30mL/min、10mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为83mgKOH/g,粘度为2610mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g棉籽基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得棉籽基聚氨酯弹性体。
对比例3
(1)聚氨酯多元醇的制备
聚氨酯多元醇的制备方法同实施例1,不同的是对比例3仅在羟基化合物和环氧植物油进行开环反应后得到植物油多元醇就结束反应。
取25.2g 2,3-环氧丁烷和12.30g氟硼酸水溶液(40wt.%)溶于85mL二氯乙烷得到混合溶液A,取52.5g二缩三乙二醇溶于190mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于300mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、0.9mL/min、1.0mL/min、1.0mL/min;微通道反应装置的第一微通道反应器体积为10mL,反应温度为80℃,反应停留时间为7min;微通道反应装置的第二微通道反应器体积为20mL,反应温度为120℃,反应停留时间为10min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇,其羟值为140mgKOH/g,粘度为1770mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆油多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
对比例4
聚氨酯多元醇的制备方法同实施例1,不同的是对比例4仅在将2,3-环氧丁烷换成1,2-环氧丁烷合成羟基化合物。
(1)聚氨酯多元醇的制备
取25.2g 1,2-环氧丁烷和12.30g氟硼酸水溶液(40wt.%)溶于85mL二氯乙烷得到混合溶液A,取52.5g二缩三乙二醇溶于190mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于300mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、0.9mL/min、1.0mL/min、1.0mL/min;微通道反应装置的第一微通道反应器体积为10mL,反应温度为80℃,反应停留时间为7min;微通道反应装置的第二微通道反应器体积为20mL,反应温度为120℃,反应停留时间为10min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于600mL二氯乙烷得到溶液D,取235.8g环氧丙烷和0.2g碳酸铯水溶液(40wt.%)溶于800mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为3h,其中溶液D和E的流速分别为40mL/min、15mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为54mg KOH/g,粘度为3210mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
对比例5
聚氨酯多元醇的制备方法同实施例1,不同的是对比例5将二缩三乙二醇换成丙二醇合成羟基化合物。
(1)聚氨酯多元醇的制备
取25.2g 2,3-环氧丁烷和12.30g氟硼酸水溶液(40wt.%)溶于85mL二氯乙烷得到混合溶液A,取26.63g 1,3-丙二醇溶于100mL二氯乙烷得到溶液B,取100g环氧大豆油(环氧基团为0.406mol)溶于300mL二氯乙烷得到溶液C。将混合溶液A和溶液B分别同时泵入第一微混合器,充分混合后通入第一微通道反应器进行反应,得到包含羟基化合物的反应流出液,将包含羟基化合物的反应流出液与溶液C分别同时泵入第二微混合器,充分混合后通入第二微通道反应器进行开环反应,得到包含植物油多元醇的反应流出液。其中溶液A、B、第一微反应器流出液和C的流速分别为0.5mL/min、0.5mL/min、1.0mL/min、1.0mL/min;微通道反应装置的第一微通道反应器体积为8mL,反应温度为80℃,反应停留时间为8min;微通道反应装置的第二微通道反应器体积为20mL,反应温度为120℃,反应停留时间为10min。反应结束后的产物导入分离器,静置分层,收集油相,水洗至中性,再经分液,旋蒸,得到植物油多元醇。将所得的植物油多元醇溶于600mL二氯乙烷得到溶液D,取235.8g环氧丙烷和0.2g碳酸铯水溶液(40wt.%)溶于800mL二氯乙烷得到溶液E。将溶液D和溶液E分别同时泵入釜式反应釜中搅拌,反应温度为130℃,反应时间为3h,其中溶液D和E的流速分别为40mL/min、15mL/min。反应结束后的产物静置分层,收集油相,用5wt.%HCl中和洗至pH=6.5~7.5,分液,将有机相旋蒸,干燥,得到聚氨酯多元醇,其羟值为62mg KOH/g,粘度为970mPa·s。
(2)聚氨酯弹性体的制备
在氮气保护下,采用预聚体法制备聚氨酯弹性体,将100g大豆基聚氨酯多元醇与1.5g水、1.0g硅油、2g开孔剂、0.3g催化剂A-33、0.1g催化剂A-1、0.006g催化剂T-12混合,加入4,4’二苯基甲烷二异氰酸酯100g,在80℃下反应2h后,用二正丁胺法测定游离的NCO含量,按扩链系数0.95加入1,4-丁二醇,搅拌混合均匀后浇注100℃的平板钢制模具中,并进行硫化,在90℃烘箱中老化24h,即可制得大豆油基聚氨酯弹性体。
对比例6
按照CN109369871A 一种聚氨酯多元醇及其制备方法和应用实施例2的方法制备聚氨酯多元醇,其羟值为75mg KOH/g,粘度为950mPa·s。将所制备得到的聚氨酯多元醇按照实施例1的方法制备聚氨酯弹性体。
实施例1-6及对比例1-6制备得到的聚氨酯多元醇的性能指标见表1,制备得到的聚氨酯弹性体性能指标见表2。
表1聚氨酯多元醇性能指标
表2聚氨酯弹性体性能指标
本发明提供了一种聚氨酯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 (6)
1.一种聚氨酯多元醇的制备方法,其特征在于,包括如下步骤:
(1)将2,3-环氧丁烷和酸性催化剂溶于惰性溶剂中,得到溶液A;将二缩三乙二醇溶于惰性溶剂中,得到溶液B;将环氧植物油溶于惰性溶剂中,得到溶液C;
(2)将溶液A和溶液B分别同时泵入微通道反应装置中的第一微混合器,混合后通入第一微反应器,反应,得到含有羟基化合物的反应液;
(3)在步骤(2)进行的同时,将溶液C和第一微反应器流出液分别同时泵入微通道反应装置中的第二微混合器,混合后,通入第二微反应器,反应,得到含有植物多元醇的反应液,分离,得到植物油多元醇;
(4)将步骤(3)得到的植物油多元醇溶于惰性溶剂中,得到溶液D;将环氧丙烷和碱性催化剂溶于惰性溶剂中,得到溶液E;将溶液D与溶液E分别同时泵入釜式反应器中反应,得到聚氨酯多元醇;
步骤(1)中,溶液A中,2,3-环氧丁烷和酸性催化剂的摩尔比为(1.0~1.25):(0.1~0.2),2,3-环氧丁烷的浓度为2.20~4.50 mmol/mL;
步骤(1)中,溶液B中,二缩三乙二醇的浓度为1.20~3.0 mmol/mL;
步骤(1)中,溶液C中,环氧植物油的浓度为0.15~0.40 mmol/mL;
步骤(2)中,溶液A和溶液B的泵入速率比为1:0.6~3.5;反应的温度为70~100℃;
步骤(3)中,控制第一微反应器流出液和溶液C的泵入速率比为1:0.5~2.0;反应的温度为80~140℃;
步骤(4)中,溶液D中,植物多元醇的浓度为0.10~0.25 mmol/mL;溶液E中,环氧丙烷的浓度为3.0~6.50 mmol/mL,环氧丙烷与步骤(1)中所述环氧植物油中环氧基团的摩尔比为5~15:1;碱性催化剂与步骤(1)中所述环氧植物油的质量百分比为0.02%~0.1%;
步骤(4)中,溶液D和溶液E的泵入速率比为1.5~6.5:1;所述反应的温度为80~150℃。
2.根据权利要求1所述的聚氨酯多元醇的制备方法,其特征在于,步骤(2)中,反应的停留时间为5~10 min。
3.根据权利要求1所述的聚氨酯多元醇的制备方法,其特征在于,步骤(3)中,反应的停留时间为5~15 min。
4.根据权利要求1所述的聚氨酯多元醇的制备方法,其特征在于,步骤(4)中,所述的反应的时间2.5~3 h。
5.权利要求1~4中任意一项所述方法制备得到的聚氨酯多元醇。
6.权利要求5所述的聚氨酯多元醇在制备聚氨酯弹性体中的应用。
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GB202012618D0 (en) | 2020-09-30 |
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