CN115612120A - 一种基于Pickering乳液法制备新型水性聚氨酯的方法 - Google Patents
一种基于Pickering乳液法制备新型水性聚氨酯的方法 Download PDFInfo
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- CN115612120A CN115612120A CN202211232259.XA CN202211232259A CN115612120A CN 115612120 A CN115612120 A CN 115612120A CN 202211232259 A CN202211232259 A CN 202211232259A CN 115612120 A CN115612120 A CN 115612120A
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Abstract
本发明提供了一种基于Pickering乳液法制备新型水性聚氨酯的方法,主要内容是首先将聚氨酯在溶剂中合成,然后利用Pickering固体粒子将聚氨酯的溶剂溶液乳化分散在水中,最后将溶剂减压蒸馏除去便到得到一种新型水性聚氨酯树脂。本发明解决了传统外乳化法制备的水性聚氨酯因小分子乳化剂的使用带来的环境危害及其在聚氨酯材料中迁移造成的成膜性、耐水性、和粘接性差等问题,以及内乳化法制备的水性聚氨酯因分子结构中引入亲水基团而带来的耐水性差的问题,并且制备的水性聚氨酯兼具聚合物和Pickering固体粒子二者的性能优势,可赋予聚氨酯材料新特性。
Description
技术领域
本发明涉及水性聚氨酯树脂开发领域,具体涉及一种基于Pickering乳液法制备新型水性聚氨酯的方法。
背景技术
聚氨酯(polyurethane,简称PU)是聚氨基甲酸酯的简称,是由多异氰酸酯和多元醇/胺反应制备得到。其具有优异的机械强度,良好的耐磨性、韧性,低温柔韧性好,耐腐蚀,以及良好的加工性能等优点,已被广泛应用于商业和工业领域。
1937年德国的拜耳(Bayer)及其同事首次利用异氰酸酯与多元醇化合物进行逐步加成反应制得了各种聚氨酯树脂和聚脲化合物。但由于原料不溶于水,所用的溶剂多为N,N-二甲基甲酰胺等有机溶剂。出于成本、环境等多方面的压力,后来才发展起来了以水为分散介质的水性聚氨酯(WPU)。由于水性聚氨酯分散液滴的高界面面积,不含表面活性剂或者无表面活性的聚氨酯乳液是热力学不稳定的体系。因此,通常需要在聚氨酯配方中加入表面活性剂或者制备具有表面活性的聚氨酯。鉴于此,水性聚氨酯的制备方法大体上可以对应分为两种,一种是外乳化法,另一种是内乳化法。外乳化法需要在聚氨酯体系中加入一定的有机乳化剂对其进行强制乳化,而这些传统的乳化剂大多具有毒性、制得的乳液稳定性差,由于外加乳化剂用量大,亦使产品的成膜性不良,并影响涂膜的耐水性、强韧性和粘接性。内乳化法是目前制备水性聚氨酯常用的方法。该方法在聚氨酯结构中引入一些亲水基团,借助于这些亲水基团的作用使聚氨酯乳化,从而制成水性聚氨酯。但该法制备得到水性聚氨酯由于结构中均存在亲水结构,如羧基、磺酸基、季铵盐等,会使得水性聚氨酯的耐磨性、耐水性、粘结性、耐湿擦和手感等与溶剂型相比具有一定的差距。因此,用一种能够替代表面活性剂及亲水基团的物质用于稳定聚氨酯分散在水体系中,但又尽量降低该物质给聚氨酯带来性能上的不足具有重要意义。
Ramsden和Pickering进行的研究揭示了另一种稳定液滴的方法,即用固体颗粒稳定乳液。这种以固体颗粒制备的Pickering乳液具有许多独特的特点,如优越的稳定性和低毒性,有望于用于水性聚氨酯的制备。另外,用固体颗粒稳定的聚氨酯乳液不仅避免了传统外乳化法制备的水性聚氨酯因小分子乳化剂的使用带来的环境危害及其在聚氨酯材料中迁移造成的成膜性、耐水性、和粘接性差等问题,以及内乳化法制备的水性聚氨酯因分子结构中引入亲水基团而带来的耐水性差的问题,并且制备的材料兼具有机聚合物和无机粒子的性能优势,可赋予聚氨酯材料新特性。
基于此,本发明的目的是首先将聚氨酯在溶剂中合成,然后用Pickering固体粒子代替表面活性剂或亲水扩链剂将聚氨酯的溶剂溶液分散在水中,最后将溶剂减压除去便到得到一种新型水性聚氨酯分散体。
发明内容
本发明提供了一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于首先将聚氨酯在溶剂中合成,然后利用Pickering固体粒子将聚氨酯的溶剂溶液分散在水中,最后将溶剂减压除去便到得到一种新型水性聚氨酯,具体步骤如下:
(1) 制备聚氨酯的溶剂溶液:将二异氰酸酯与大分子二元醇按照摩尔配比为 (4~10): 1加入反应器中,在温度为60~90°C,搅拌速度为500~3000 rpm以及惰性气体保护下搅拌反应0.5-2 h,反应结束后向反应器中加入小分子扩链剂,其与大分子二元醇的摩尔比为(3~9): 1,并加入溶剂,使得固含量20%~50%,温度为10~90oC,搅拌速度为200~2000 rpm,在催化剂二月桂酸二丁基锡的条件下反应0.5~4 h,得到聚氨酯的溶剂溶液。
(2) 制备Pickering固体粒子分散液:向另一个反应器中加入一定量的Pickering固体粒子和去离子水,使得Pickering固体粒子的浓度为0.1~5 wt%,常温下搅拌分散0.5-2h,搅拌速度为600~1500 rpm,得到Pickering固体粒子分散液。
(3) 将步骤 (1) 得到的聚氨酯的溶剂溶液和步骤 (2) 得到Pickering固体粒子分散液按照质量比为 (0.5~2.5): 1混合,高速乳化分散1~10 min,搅拌速度为4000~10000rpm,乳化结束后用50~400目筛子过滤,所得的滤液即为Pickering固体粒子稳定的Pickering乳液。
(4) 将制备的Pickering固体粒子稳定的Pickering乳液进行减压蒸馏以除去溶剂,得到Pickering固体粒子稳定的聚氨酯乳液。
所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的Pickering固体粒子为二氧化硅纳米颗粒、二氧化钛纳米颗粒、氧化锌纳米颗粒、碳酸钙粒纳米颗粒、锂皂土、淀粉纳米颗粒、纤维素纳米颗粒、壳聚糖纳米颗粒、姜黄素纳米颗粒、明胶纳米颗粒、大豆分离蛋白纳米颗粒以及它们的改性产物中的一种或几种的混合物。
所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的Pickering固体粒子的接触角为15~80°,粒径为15~800 nm。
所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、赖氨酸二异氰酸酯、1,4-苯二异氰酸酯、1,4-环己烷二异氰酸酯、2,6-甲苯二异氰酸酯和三甲基1,6-六亚甲基二异氰酸酯中的一种或几种的混合物。
所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的大分子二元醇为聚丙二醇、聚硅氧烷二醇、聚四氢呋喃醚二醇、聚ε-己内酯二元醇、聚碳酸酯二醇和聚乙二醇中的一种或几种的混合物。
所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的小分子扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、一缩二乙二醇、1,6-己二醇、对苯二酚二羟乙基醚、间苯二酚二羟乙基醚、乙二胺以及丁二胺中的一种或几种的混合物。
所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的溶剂为乙酸甲酯、乙酸乙酯、乙酸异丙酯、二氯甲烷、三氯甲烷、二氯乙烷、1-氯代正丙烷、1-氯代正丁烷、乙丙醚、丙醚以及异丙醚中的一种或几种的混合物。
附图说明
附图1:实施例1中基于Pickering乳液法制备新型水性聚氨酯乳液以及未加入Pickering固体粒子直接将聚氨酯的乙酸乙酯溶液分散在去离子水中然后去溶剂制备得的液体外观图对比,其中A为基于Pickering乳液法制备新型水性聚氨酯乳液,B为及未加入Pickering固体粒子直接将聚氨酯的乙酸乙酯溶液分散在去离子水中然后去溶剂制备得的液体。
附图2:实施例1中基于Pickering乳液法制备新型水性聚氨酯乳液粒径分析图。
附图3:实施例1中基于Pickering乳液法制备新型水性聚氨酯乳液以及聚氨酯的乙酸乙酯溶液的成膜材料的应力应变对比曲线图,其中A为基于Pickering乳液法制备新型水性聚氨酯乳液的成膜材料,B为聚氨酯的乙酸乙酯溶液的成膜材料。
具体实施方式
下面给出本发明的四个实施例,以具体说明基于Pickering乳液法制备新型水性聚氨酯的制备方法。
实施例1
称取20.00 g聚四氢呋喃二醇(Mn=2000)加入到三口烧瓶中,在110℃下真空干燥脱水2 h;干燥后,降温到70°C并通氮气保护,再往其中加入13.32 g异佛尔酮二异氰酸酯,在磁石搅拌下反应1.5 h;反应完成后,升温到80℃,加入4.50 g溶解于56.73 g乙酸乙酯的1,4-丁二醇和两滴催化剂二月桂酸二丁基锡回流反应2 h,得到聚氨酯的乙酸乙酯溶液;同时,称取2.00 g纳米SiO2(接触角为20°)加入100.00 g去离子水中搅拌分散30 min,得到纳米SiO2分散液。
称取90.00 g聚氨酯的乙酸乙酯溶液和90.00 g纳米SiO2分散液混合并用乳化器在搅拌速度为5000 rpm的条件下高速乳化5 min,并用200目筛子过滤,所得滤液为纳米SiO2稳定的Pickering乳液。最后将制备的纳米SiO2稳定的Pickering乳液进行减压蒸馏以除去乙酸乙酯,得到纳米SiO2稳定的聚氨酯乳液。
实施例2
称取20.00 g聚丙二醇(Mn=2000)加入到三口烧瓶中,在110℃下真空干燥脱水2h;干燥后,降温到75°C并通氮气保护,再往其中加入11.20 g 1,4-苯二异氰酸酯,在磁石搅拌下反应1 h;反应完成后,升温到80℃,加入7.08 g溶解于46.79 g乙酸异丙酯的1,6-己二醇和两滴催化剂二月桂酸二丁基锡回流反应3 h,得到聚氨酯的乙酸异丙酯溶液;同时,称取1.50 g纤维素纳米晶体加入75.00 g去离子水中搅拌分散1 h,得到纤维素纳米晶体分散液。
称取80.00 g聚氨酯的乙酸异丙酯溶液和50.00 g纤维素纳米晶体分散液混合并用乳化器在搅拌速度为4000 rpm的条件下高速乳化7 min,并用250目筛子过滤,所得滤液为纤维素纳米晶体稳定的Pickering乳液。最后将制备的纤维素纳米晶体稳定的Pickering乳液进行减压蒸馏以除去乙酸异丙酯,得到纤维素纳米晶体稳定的聚氨酯乳液。
实施例3
称取20.00 g聚ε-己内酯二元醇(Mn=2000)加入到三口烧瓶中,在110℃下真空干燥脱水2 h;干燥后,降温到70°C并通氮气保护,再往其中加入20.02 g二苯基甲烷二异氰酸酯,在磁石搅拌下反应1 h;反应完成后,升温到80℃,加入13.88 g溶解于100.09 g二氯甲烷的对苯二酚二羟乙基醚和两滴催化剂二月桂酸二丁基锡回流反应2 h,得到聚氨酯的二氯甲烷溶液;同时,称取1.00 g明胶纳米颗粒加入100.00 g去离子水中搅拌分散45 min,得到明胶纳米颗粒分散液。
称取100.00 g聚氨酯的二氯甲烷溶液和100.00 g明胶纳米颗粒分散液混合并用乳化器在搅拌速度为7500 rpm的条件下高速乳化3 min,并用200目筛子过滤,所得滤液为明胶纳米颗粒稳定的Pickering乳液。最后将制备的明胶纳米颗粒稳定的Pickering乳液进行减压蒸馏以除去二氯甲烷,得到明胶纳米颗粒稳定的聚氨酯乳液。
实施例4
称取20.00 g聚硅氧烷二醇(Mn=2000)加入到三口烧瓶中,在110℃下真空干燥脱水2 h;干燥后,降温到70°C并通氮气保护,再往其中加入13.57 g赖氨酸二异氰酸酯,在磁石搅拌下反应1.5 h;反应完成后,降温到15℃,加入3.00 g溶解于54.86 g乙丙醚的乙二胺和两滴催化剂二月桂酸二丁基锡回流反应4 h,得到聚氨酯的乙丙醚溶液;同时,称取0.50g聚苯乙烯纳米球加入66.67 g去离子水中搅拌分散30 min,得到聚苯乙烯纳米球分散液。
称取90.00 g聚氨酯的乙丙醚溶液和60.00 g聚苯乙烯纳米球分散液混合并用乳化器在搅拌速度为5000 rpm的条件下高速乳化5 min,并用200目筛子过滤,所得滤液为聚苯乙烯纳米球稳定的Pickering乳液。最后将制备的聚苯乙烯纳米球稳定的Pickering乳液进行减压蒸馏以除去乙丙醚,得到聚苯乙烯纳米球稳定的聚氨酯乳液。
Claims (7)
1.本发明提供了一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于首先将聚氨酯在溶剂中合成,然后利用Pickering固体粒子将聚氨酯的溶剂溶液分散在水中,最后将溶剂减压蒸馏除去便到得到一种新型水性聚氨酯,具体制备方法如下:
(1) 制备聚氨酯的溶剂溶液:将二异氰酸酯与大分子二元醇按照摩尔配比为 (4~10):1加入反应器中,在温度为60~90°C,搅拌速度为500~3000 rpm以及惰性气体保护下搅拌反应0.5-2 h,反应结束后向反应器中加入小分子扩链剂,其与大分子二元醇的摩尔比为 (3~9): 1,并加入溶剂,使得固含量20%~50%,温度为10~90oC,搅拌速度为200~2000 rpm,在催化剂二月桂酸二丁基锡的条件下反应0.5~4 h,得到聚氨酯的溶剂溶液;
(2) 制备Pickering固体粒子分散液:向另一个反应器中加入一定量的Pickering固体粒子和去离子水,使得Pickering固体粒子的浓度为0.1~5 wt%,常温下搅拌分散0.5-2 h,搅拌速度为600~1500 rpm,得到Pickering固体粒子分散液;
(3) 将步骤 (1) 得到的聚氨酯的溶剂溶液和步骤 (2) 得到Pickering固体粒子分散液按照质量比为 (0.5~2.5): 1混合,高速乳化分散1~10 min,搅拌速度为4000~10000rpm,乳化结束后用50~400目筛子过滤,所得的滤液即为Pickering固体粒子稳定的Pickering乳液;
(4) 将制备的Pickering固体粒子稳定的Pickering乳液进行减压蒸馏以除去溶剂,得到Pickering固体粒子稳定的聚氨酯乳液。
2.根据权利要求1所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的Pickering固体粒子为二氧化硅纳米颗粒、二氧化钛纳米颗粒、氧化锌纳米颗粒、碳酸钙粒纳米颗粒、锂皂土、淀粉纳米颗粒、纤维素纳米颗粒、壳聚糖纳米颗粒、姜黄素纳米颗粒、明胶纳米颗粒、大豆分离蛋白纳米颗粒以及它们的改性产物中的一种或几种的混合物。
3.根据权利要求1所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的Pickering固体粒子的接触角为15~80,粒径为15~800 nm。
4.根据权利要求1所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、赖氨酸二异氰酸酯、1,4-苯二异氰酸酯、1,4-环己烷二异氰酸酯、2,6-甲苯二异氰酸酯和三甲基1,6-六亚甲基二异氰酸酯中的一种或几种的混合物。
5.根据权利要求1所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的大分子二元醇为聚丙二醇、聚硅氧烷二醇、聚四氢呋喃醚二醇、聚ε-己内酯二元醇、聚碳酸酯二醇和聚乙二醇中的一种或几种的混合物。
6.根据权利要求1所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的小分子扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、一缩二乙二醇、1,6-己二醇、对苯二酚二羟乙基醚、间苯二酚二羟乙基醚、乙二胺以及丁二胺中的一种或几种的混合物。
7.根据权利要求1所述的一种基于Pickering乳液法制备新型水性聚氨酯的方法,其特征在于所述的溶剂为乙酸甲酯、乙酸乙酯、乙酸异丙酯、二氯甲烷、三氯甲烷、二氯乙烷、1-氯代正丙烷、1-氯代正丁烷、乙丙醚、丙醚以及异丙醚中的一种或几种的混合物。
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