CN115403727A - 聚氨酯软硬段调节与力致变色功能一体复合加工助剂及其制备方法 - Google Patents
聚氨酯软硬段调节与力致变色功能一体复合加工助剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚氨酯软硬段调节与力致变色功能一体复合加工助剂及其制备方法,属于高分子加工助剂合成与应用技术领域。该制备方法基于螺吡喃有机小分子,通过改造该小分子结构形成双羟基螺吡喃;并以丙烯酸甲酯为配体,与稀土元素铕形成有机化稀土即丙烯酸稀土配合物,将该丙烯酸稀土配合物与双羟基螺吡喃按照比例混合后,得到聚氨酯软硬段调节剂,并赋予其力致变色功能。采用该助剂,能够在TPU成型过程中调控软硬段相态结构,同时实现力学性能保持与力致变色性能赋予,获得力致可变色透明TPU薄膜。
Description
技术领域
本发明涉及一种聚氨酯加工助剂及其制备方法,尤其涉及一种聚氨酯软硬段调节与力致变色功能一体复合加工助剂及其制备方法,属于高分子加工助剂合成与应用技术领域。
背景技术
力致变色材料是一类常见的智能材料,主要是指在外加机械力的作用下其光学性质能够可逆变化的材料,其在具有力致变色响应特性的同时,又具有聚合物合成简单、易于加工且成本低等诸多优点,从而受到广泛关注。力致变色材料特有的功能性使其在信息存储、显示技术、应力传感等领域有着重要的应用前景。
目前现有技术中的力致变色材料大多是直接将具有光感应的小分子染料与热塑性树脂基体进行共混形成,当材料受到外力刺激发生时,由于其中的染料分子在聚集和分散状态下呈现出完全不同的可见光吸收或荧光发射特性,因此可用来感知基体树脂的的应变量和受力程度。但上述小分子染料掺杂的情况情况,在力影响灵敏度、对比度和可逆性等方面效果均较一般,同时由于其不能很好的与树脂基体融合在一起,因此对树脂的力学性能是有一定影响的,尤其当树脂基体为聚氨酯树脂时,其影响较大。因此需要一种能够复合加工助剂,其能够同时具有力致变色功能和调节聚氨酯软硬段的功能。
发明内容
为解决上述技术问题,本发明提供了一种聚氨酯软硬段调节与力致变色功能一体复合加工助剂及其制备方法,其以丙烯酸甲酯为配体与稀土元素形成有机化稀土,然后该有机化稀土与双羟基螺吡喃按照比例混合,得到聚氨酯软硬段调节剂,并赋予其力致变色功能。
本发明的技术方案是:
本发明公开了一种聚氨酯软硬段调节与力致变色功能一体复合加工助剂的制备方法,包括下述步骤:
S1,双羟基螺吡喃的制备:
使用2,3,3-三甲基-3H-吲哚和2-溴乙醇在氮气保护气氛下进行吲哚羟基化反应,生成羟基吲哚;然后将羟基吲哚和氢氧化钠在室温反应下进行吲哚环化反应,生成环化吲哚;
使用3-氯甲基-5-硝基水杨醛和氢氧化钠在丙酮溶剂中进行水杨醛羟基化反应,生成羟基化水杨醛;
将上述制备所得的环化吲哚和羟基化水杨醛在乙醇和水等体积比形成的溶液中加热反应后,生成双羟基螺吡喃;
S2,丙烯酸稀土配合物的制备:
使用氧化铕和甲基丙烯酸在二甲基甲酰胺溶剂中进行反应生成配合物中间体Eu(MAA)3;然后使用甲基丙烯酸羟乙酯与Eu(MAA)3进行碳碳双键聚合反应,生成丙烯酸稀土配合物,记为Eu配合物;
S3,以上述制备所得的双羟基螺吡喃和丙烯酸稀土配合物复配形成所述复合加工助剂。
其进一步的技术方案是:
步骤S1吲哚羟基化反应中,2,3,3-三甲基-3H-吲哚和2-溴乙醇的摩尔比为1:(4-5),且该吲哚羟基化反应在120-125℃下搅拌反应4-5h。
其进一步的技术方案是:
步骤S1吲哚环化反应中,羟基吲哚和氢氧化钠的摩尔比为1:(2-2.5),且该反应所用溶剂为水,于室温下搅拌反应30-40min。
其进一步的技术方案是:
步骤S1水杨醛羟基化反应中,3-氯甲基-5-硝基水杨醛和氢氧化钠的摩尔比为1:(0.9-1.0),且该反应进行时先将3-氯甲基-5-硝基水杨醛溶解在丙酮中,80-85℃回流搅拌30-40min后,将NaOH溶液逐滴加入烧瓶,反应3-3.5h。
其进一步的技术方案是:
步骤S1双羟基化螺吡喃合成反应中,环化吲哚和羟基化水杨醛的摩尔比为1:(1-1.2),且该反应进行时,先将羟基化水杨醛在氮气气氛下溶解于无水乙醇和水的混合物中形成第一反应物,再将环化吲哚溶解于无水乙醇和水的混合物中后用蠕动泵将其加入第一反应物中,80-85℃油浴下搅拌回流反应5-6h。
其进一步的技术方案是:
步骤S2中氧化铕与甲基丙烯酸按照摩尔比为1:(5-6)反应生成配合物中间体Eu(MAA)3,且该配合物中间体Eu(MAA)3与甲基丙烯酸羟乙酯按照摩尔比为1:(8-10)进行反应生成Eu配合物。
其进一步的技术方案是:
步骤S2中配合物中间体Eu(MAA)3的反应生成过程中,先将氧化铕用二甲基甲酰胺溶解后,再用恒压滴液漏斗向其中加入甲基丙烯酸,反应中打开冷凝水并不断搅拌,且反应初期温度控制60℃下反应1-1.5h后,将反应温度提高至90℃后继续反应9-10h,得到所述配合物中间体Eu(MAA)3。
其进一步的技术方案是:
步骤S3中所述双羟基螺吡喃和丙烯酸稀土配合物的复配摩尔比为1:(1-1.2)。
本发明还公开了一种上述制备方法制备所得的聚氨酯软硬段调节与力致变色功能一体复合加工助剂,该复合加工助剂包括按摩尔比1:(1-1.2)复配的双羟基螺吡喃和丙烯酸稀土配合物。
本发明还公开了一种上述复合加工助剂在聚氨酯材料中的应用,将所述复合加工助剂加入异氰酸酯反应物中,于氮气气氛下搅拌溶解并混合均匀后得到功能化异氰酸酯溶液,然后加入羟基化合物、封端剂和催化剂后搅拌反应至反应结束,得到具有软硬段调节功能与力致变色功能的聚氨酯材料。
本发明的有益技术效果是:本发明基于螺吡喃有机小分子,通过改造该小分子结构形成双羟基螺吡喃;并以丙烯酸甲酯为配体,与稀土元素铕形成有机化稀土即丙烯酸稀土配合物,将该丙烯酸稀土配合物与双羟基螺吡喃按照比例混合后,得到聚氨酯软硬段调节剂,并赋予其力致变色功能。采用该助剂,能够在TPU成型过程中调控软硬段相态结构,同时实现力学性能保持与力致变色性能赋予,获得力致可变色透明TPU薄膜。
附图说明
图1为本申请所述聚氨酯材料经紫外光照射后的结果图,其中1a、1b和1c分别为纯聚氨酯材料在紫外光照射前、中和后的情况;2a、2b和2c分别为使用本申请所述加工助剂的聚氨酯材料在紫外光照射前、中和后的情况;
图2为本申请所述聚氨酯材料的力学性能测试图,其中1为纯聚氨酯材料,2为使用了本申请所述加工助剂的聚氨酯材料。
具体实施方式
为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,下面结合具体实施例,对本发明的具体实施方式作进一步详细描述,以下实施例用于说明本发明,但不用来限制本发明的范围。
具体实施例
S1,双羟基螺吡喃的制备:
S11,吲哚羟基化:称取2,3,3-三甲基-3H-吲哚52mmol溶解在2-溴乙醇260mmol中,置于100mL三口烧瓶中,通氮气保护,安装冷凝回流装置,在120℃油浴下搅拌反应4.5h;将溶液加入快速搅拌的乙酸乙酯中,随即产生沉淀,用布氏漏斗过滤,再用少量乙酸乙酯清洗,60℃烘箱干燥,得浅棕色粉末,为羟基吲哚,产率83%;
S12,吲哚环化:称取羟基吲哚20mmol和NaOH 40mmol于250mL烧杯中,加入100.0mL水后室温搅拌30min;用石油醚萃取溶液三次;旋蒸除去石油醚得到黄色油状物,为环化吲哚,产率80%;
S13,水杨醛羟基化:称取3-氯甲基-5-硝基水杨醛10mmol溶解在40.0mL的丙酮中,80℃回流搅拌30min;称取3M NaOH溶液3.0mL逐滴加入烧瓶,反应3h;溶液冷却到室温,旋蒸出溶剂;产物在水中重新结晶,干燥,最终得浅黄色粉末,为羟基化水杨醛,产率76%;
S14,双羟基化螺吡喃:称取羟基化水杨醛5mmol加入250mL三口烧瓶,加入30.0mL无水乙醇和30.0mL水,装好冷凝回流装置,充氮气保护,搅拌至溶解;称取环化吲哚6mmol溶于30.0mL无水乙醇和30.0mL水,用蠕动泵将其加入烧瓶;80℃油浴中搅拌回流反应5h;反应后液体在旋转蒸发仪中除去溶剂后,在乙腈:水=7:3中重结晶,烘干,得紫黑色粉末,为双羟基螺吡喃,产率70%。
其中步骤S1中双羟基螺吡喃的化学反应原理为:
S2,丙烯酸稀土配合物的制备:
在带有球形冷凝管的三颈瓶(100mL)中,加入氧化铕(Eu2O3)10mmol,再加入20.0mLDMF,搅拌;用恒压滴液漏斗(30min滴完)加入甲基丙烯酸(MMA)60mmol,打开冷凝水并不断的搅拌。在反应初期,控制体系内温度60℃,反应1h,溶液为乳白色非均相体系,随后将体系温度升高到90℃,继续反应9h,得到澄黄色透明溶液,为配合物中间体Eu(MAA)3的DMF溶液;称取Eu(MAA)3的DMF溶液8mL置于100mL三口烧瓶中,通N2,冷凝水,60℃;称取甲基丙烯酸羟乙酯(HEMA)1.9500g置于体系中,搅拌均匀;称取AIBN 0.0195g溶于5.0mL DMF中,用注射器打入体系中;反应10h,得黄色透明溶液,为丙烯酸稀土配合物,记为Eu配合物。
其中Eu配合的化学反应原理为:
S3,聚氨酯膜材的准备:PBA-1000在真空烘箱除水24h。称取MDI 5.5mmol,双羟基螺吡喃0.15mmol和Eu配合物0.15mmol加入250mL三口烧瓶中,全程N2保护,油浴升温到60℃搅拌反应30min得功能化异氰酸酯溶液,之后加入PBA-1000 8mmol,HDI 5mmol,DBTDL 3滴,再加入适量DMF搅拌均匀,随后升温至80℃反应2h,再加入BDO 2mmol,搅拌均匀后继续反应3h,将溶液倒入聚四氟乙烯盘中置于60℃烘箱成型24h,得聚氨酯膜材。
采用万能试验机对上述制备所得的聚氨酯膜材进行力学性能及拉伸变色性能的测试。测试条件为:拉伸速率250mm/min。测试结果参见说明书附图1和说明书附图2。从附图中可见,本申请制备所得的聚氨酯材料的力学性能优异,同时具有力致变色功能。
以上所述仅是本发明的优选实施方式,并不用于限制本发明,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (10)
1.一种聚氨酯软硬段调节与力致变色功能一体复合加工助剂的制备方法,其特征在于,包括下述步骤:
S1,双羟基螺吡喃的制备:
使用2,3,3-三甲基-3H-吲哚和2-溴乙醇在氮气保护气氛下进行吲哚羟基化反应,生成羟基吲哚;然后将羟基吲哚和氢氧化钠在室温反应下进行吲哚环化反应,生成环化吲哚;
使用3-氯甲基-5-硝基水杨醛和氢氧化钠在丙酮溶剂中进行水杨醛羟基化反应,生成羟基化水杨醛;
将上述制备所得的环化吲哚和羟基化水杨醛在乙醇和水等体积比形成的溶液中加热反应后,生成双羟基螺吡喃;
S2,丙烯酸稀土配合物的制备:
使用氧化铕和甲基丙烯酸在二甲基甲酰胺溶剂中进行反应生成配合物中间体Eu(MAA)3;然后使用甲基丙烯酸羟乙酯与Eu(MAA)3进行碳碳双键聚合反应,生成丙烯酸稀土配合物,记为Eu配合物;
S3,以上述制备所得的双羟基螺吡喃和丙烯酸稀土配合物复配形成所述复合加工助剂。
2.根据权利要求1所述的制备方法,其特征在于:步骤S1吲哚羟基化反应中,2,3,3-三甲基-3H-吲哚和2-溴乙醇的摩尔比为1:(4-5),且该吲哚羟基化反应在120-125℃下搅拌反应4-5h。
3.根据权利要求1所述的制备方法,其特征在于:步骤S1吲哚环化反应中,羟基吲哚和氢氧化钠的摩尔比为1:(2-2.5),且该反应所用溶剂为水,于室温下搅拌反应30-40min。
4.根据权利要求1所述的制备方法,其特征在于:步骤S1水杨醛羟基化反应中,3-氯甲基-5-硝基水杨醛和氢氧化钠的摩尔比为1:(0.9-1.0),且该反应进行时先将3-氯甲基-5-硝基水杨醛溶解在丙酮中,80-85℃回流搅拌30-40min后,将NaOH溶液逐滴加入烧瓶,反应3-3.5h。
5.根据权利要求1所述的制备方法,其特征在于:步骤S1双羟基化螺吡喃合成反应中,环化吲哚和羟基化水杨醛的摩尔比为1:(1-1.2),且该反应进行时,先将羟基化水杨醛在氮气气氛下溶解于无水乙醇和水的混合物中形成第一反应物,再将环化吲哚溶解于无水乙醇和水的混合物中后用蠕动泵将其加入第一反应物中,80-85℃油浴下搅拌回流反应5-6h。
6.根据权利要求1所述的制备方法,其特征在于:步骤S2中氧化铕与甲基丙烯酸按照摩尔比为1:(5-6)反应生成配合物中间体Eu(MAA)3,且该配合物中间体Eu(MAA)3与甲基丙烯酸羟乙酯按照摩尔比为1:(8-10)进行反应生成Eu配合物。
7.根据权利要求6所述的制备方法,其特征在于:步骤S2中配合物中间体Eu(MAA)3的反应生成过程中,先将氧化铕用二甲基甲酰胺溶解后,再用恒压滴液漏斗向其中加入甲基丙烯酸,反应中打开冷凝水并不断搅拌,且反应初期温度控制60℃下反应1-1.5h后,将反应温度提高至90℃后继续反应9-10h,得到所述配合物中间体Eu(MAA)3。
8.根据权利要求1所述的制备方法,其特征在于:步骤S3中所述双羟基螺吡喃和丙烯酸稀土配合物的复配摩尔比为1:(1-1.2)。
9.一种权利要求1至8中任一项制备方法制备所得的聚氨酯软硬段调节与力致变色功能一体复合加工助剂,其特征在于:包括按摩尔比1:(1-1.2)复配的双羟基螺吡喃和丙烯酸稀土配合物。
10.一种权利要求9所述复合加工助剂在聚氨酯材料中的应用,其特征在于:将所述复合加工助剂加入异氰酸酯反应物中,于氮气气氛下搅拌溶解并混合均匀后得到功能化异氰酸酯溶液,然后加入羟基化合物、封端剂和催化剂后搅拌反应至反应结束,得到具有软硬段调节功能与力致变色功能的聚氨酯材料。
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