CN108727554B - 一种高耐水性水性聚氨酯改性蒙脱土纳米复合乳液 - Google Patents
一种高耐水性水性聚氨酯改性蒙脱土纳米复合乳液 Download PDFInfo
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Abstract
本发明公开了一种高耐水性水性聚氨酯改性蒙脱土纳米复合乳液,属于有机‑无机纳米复合乳液领域。本发明采用酸离解的聚醚胺,对蒙脱土进行插层改性。通过铵离子替换蒙脱土层间钠离子,使蒙脱土层间距增加,同时引入与异氰酸酯基有反应活性的基团。然后将形成的插层改性的有机蒙脱土溶液与聚氨酯反应,制备水性聚氨酯蒙脱土纳米复合乳液。采用以上方法制备的纳米复合乳液具有较好的分散稳定性,同时无机纳米颗粒的引入使水性聚氨酯涂层的热、力学性能明显提高,蒙脱土片层结构又使得阻隔性能增强。该分散体可广泛应用于阻隔性能优异、耐高温的食品、医药包装等领域。
Description
技术领域
本发明涉及一种高耐水性水性聚氨酯改性蒙脱土纳米复合乳液,属于有机-无机纳米复合乳液领域。
背景技术
水性聚氨酯以水为分散介质,具有高分子量、低粘度、易施工、环保、安全、卫生等优点,在涂料、胶粘剂、油墨、密封剂等领域得到很好的应用。但是水性聚氨酯乳胶膜的力学性能(强度、模量)、粘附力、耐水性等性能还不能与传统的溶剂型聚氨酯相媲美,因此限制了该涂膜的进一步广泛应用。将无机纳米材料如二氧化硅、粘土、碳纳米管等引入水性聚氨酯体系可以有效提高体系的力学性能,但是体系耐水性提高不明显甚至下降。蒙脱土(MMT)是由硅酸盐氧化物四面体和铝氧化物四面体共享一个八面体,厚度约1nm层状结构。MMT可通过静电作用、分子间作用、表面改性、离子交换等方法对其进行剥离,形成分离片层,剥离后的MMT在聚合物基质中以片层形式分散开,大量片层结构所形成的“曲折路径”会阻碍水分或气体通过,因而达到很好阻隔效果。目前相对于通过熔融、溶液法制备聚合物粘土纳米复合材料,如何在水性聚合物体系中控制粘土的分散及定向排列,是制备高耐水性、阻隔性水性聚合物粘土纳米复合涂层面临的主要挑战。
Mohammad Mizanur Rahman等人将烷基季铵盐改性的蒙脱土(Cloisite 15A)加入水性聚氨酯中,改性后的蒙脱土与水性聚氨酯基质之间只是通过分子间氢键作用达到相容的效果,因而水性聚氨酯的力学性能和耐水性提升的并不明显。
发明内容
为了解决上述问题,本发明采用的阳离子改性剂-含有氨基的醚基改性剂,存在可反应的氨基,与水性聚氨酯之间通过共价键作用,显著提升了水性聚氨酯的耐水性及力学性能等。
本发明提供了一种高强度,高阻隔,高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液的制备方法。本发明通过含氨基的醚基化合物插层改性蒙脱土,在水性聚氨酯乳化过程中原位引入改性粘土,制得高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液的制备方法。改性蒙脱土的引入可有效提高水性聚氨酯乳胶膜的力学性能、耐水性,该分散体可应用于高性能涂料、粘合剂、密封剂、油墨等功能材料领域。
本发明的第一个目的是提供一种高耐水性水性聚氨酯改性蒙脱土纳米复合乳液,其制备方法包括:利用含氨基的醚基化合物改性剂改性蒙脱土,将改性蒙脱土加入水性聚氨酯中混合,得到纳米复合乳液;其中,所述含氨基的醚基化合物改性剂为聚醚胺。
在一种实施方式中,所述聚醚胺使用时,还包括对聚醚胺进行酸解离;具体是:将聚醚胺与盐酸重量比1:(1-5)加入烧杯中,搅拌5-30min,搅拌速度100-500rmp/min,然后在频率为40-100Hz的超声波下超声分散30-120min,备用。
在一种实施方式中,阳离子型改性剂改性蒙脱土,包括蒙脱土与水重量比(0.005-1):1加入到容器中充分溶胀,然后加入酸化聚醚胺,在40-100℃下搅拌3-8h,搅拌速度为100-2000rmp,将得到的有机蒙脱土干燥,分散到溶剂中备用。
在一种实施方式中,所述的聚醚胺其分子链末端为伯胺或仲胺基,数均分子量范围为200-3000。
在一种实施方式中,所述的纳米复合乳液中蒙脱土的含量为水性聚氨酯用量的0.01wt%-40wt%。
在一种实施方式中,所述纳米复合乳液中的水性聚氨酯与改性蒙脱土的重量比按干重计为100:(0.1-20)。
在一种实施方式中,所述纳米复合乳液的固含为5%-20%。
在一种实施方式中,所述的蒙脱土为纳基蒙脱土、钾基蒙脱土、钙基蒙脱土或锂基蒙脱土,其比表面积为30-1000m2/g,孔径3-30nm,阳离子交换容量30-300meq/100g;
在一种实施方式中,所述纳米复合乳液的制备方法,包括:
(1)聚醚胺与盐酸重量比1:(1-5)加入烧杯中,搅拌5-30min,搅拌速度100-500rmp/min,然后在频率为40-100Hz的超声波下超声分散30-120min,备用;
(2)蒙脱土与水重量比(0.005-1):1加入到容器中充分溶胀,然后加入酸解离的聚醚胺(含氨基的醚基改性剂),在40-100℃下搅拌3-8h,搅拌速度为100-2000rmp/min,将得到的改性蒙脱土干燥,分散到溶剂中备用;
(3)将聚氨酯树脂加入反应容器中,加入改性蒙脱土分散液,在40-100℃下搅拌3-8h,搅拌速度100-2000rmp/min。
(4)纳米复合乳液的制备:聚氨酯预聚体的温度降低到25℃,加入中和剂,反应1-2h,然后升温至60℃,向其中加入改性蒙脱土分散液,反应2-4h,最后在室温下高速搅拌乳化1h,制得高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液。
在一种实施方式中,所述(4)中聚氨酯预聚体的制备:按配比在二异氰酸酯化合物中,滴加低聚物多元醇和催化剂,滴加完毕后在50℃反应1-2h,然后逐渐升温至60℃,加入亲水单体,在此温度下进行反应6-8h,用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量,当接近NCO理论值时,得到聚氨酯预聚体。
在一种实施方式中,所述的二异氰酸酯化合物选用2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷4,4’-二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯、间苯二甲基异氰酸酯中的一种。
在一种实施方式中,所述的低聚物多元醇选用聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇、α,ω-二羟基聚二甲基硅氧烷、二羟基聚二苯基硅氧烷、二羟基聚三氟丙基甲基硅氧烷中一种或几种,其分子量范围为400-10000。
在一种实施方式中,所述的亲水单体选用二羟甲基丙酸,二羟甲基丁酸,1,2-二羟基-3-丙磺酸钠中的一种。
在一种实施方式中,所述的水性聚氨酯/改性蒙脱土纳米复合乳液的固含为5-20%,pH范围为7.5-9.0,固含量为10-50%,粒径范围为100-3000nm。
本发明的第二个目的是提供所述纳米复合乳液制备得到的膜。
本发明的第三个目的是提供所述纳米复合乳液在制备包装材料方面的应用,包括食品、医药领域的包装材料。
本发明的原理在于:由于未改性的蒙脱土在聚合物基质中很难达到良好的分散性;本发明先采用盐酸对聚醚胺进行酸解改性,将其制备成阳离子改性剂,接着将其加入蒙脱土分散液中,通过改性剂中的阳离子与蒙脱土层间Na+进行离子交换,将亲有机的聚醚胺改性剂引入蒙脱土中,从而进一步有效打开蒙脱土层间距;阳离子改性剂,即酸化后的聚醚胺分子结构中存在可反应的氨基,利用氨基与异氰酸酯反应,可进一步增强与水性聚氨酯基质的相互作用。将形成的改性蒙脱土分散液与聚氨酯作用,制备高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液。
本发明的有益效果:
本发明采用酸化后的聚醚胺作为阳离子改性剂,使其进入蒙脱土层间,有效打开蒙脱土层间距,改善了蒙脱土与有机物的相容性;同时聚醚胺结构中的氨基与异氰酸酯反应,进一步提升蒙脱土与水性聚氨酯基质的相互作用,制备强度更高,耐吸湿性更佳的水性聚氨酯/改性蒙脱土纳米复合材料。同时,无机纳米颗粒的引入使水性聚氨酯涂层的热、力学性能明显提高。本发明的纳米复合乳液可广泛应用于耐湿热的食品、医药包装等领域。
附图说明
图1实施例1的水性聚氨酯膜的SEM图;
图2实施例2的高耐水性水性聚氨酯/改性蒙脱土纳米复合膜的SEM图;
图3实施例1和实施例2的膜的拉伸性能;
图4实施例1和实施例2的膜的吸水率曲线。
具体实施方式
为了更好的解释本发明,下面结合具体实施例对本发明进行进一步详细解释。
实施例1:水性聚氨酯乳液及膜的制备
在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入24.08g异佛尔酮二异氰酸酯(IPDI)和四滴二月桂酸二丁基锡(DBTDL)催化剂,室温下一边搅拌一边用滴液漏斗滴加70.92g聚碳酸酯二醇(PCD2000),滴加速度控制在1.5h内,滴加完毕后在50±5℃反应1-2h,温度控制在40-50℃;然后升温至60±5℃,加入5g二羟甲基丙酸(DMPA),反应3-5h;通过甲苯-二正丁胺反滴定法测定反应程度,直到测定NCO基团含量达到理论值;得到聚氨酯预聚体。
向聚氨酯预聚体的体系中滴加去离子水进行乳化;制膜,干燥即制得水性聚氨酯膜。
如图1所示,为得到的水性聚氨酯膜的SEM图,从图中可以看出水性聚氨酯膜的断裂面光滑无纹路,无刚性断裂。
实施例2:高耐水性水性聚氨酯/改性蒙脱土纳米复合及膜
水性聚氨酯/聚醚胺改性蒙脱土纳米复合乳液的制备如下:
(1)有机胺-聚醚胺2000对蒙脱土进行改性,具体改性实例如下:
称取蒙脱土1.0g,加100ml蒸馏水配成1%的蒙脱土分散液,溶胀1h。常温磁力搅拌60min,超声波分散30min。称取1.6g聚醚胺,在常温下加入适量盐酸,配置聚醚胺的盐酸水溶液,在80℃强力搅拌下逐滴滴加如蒙脱土分散液中,滴加时间控制在30rnin,反应5h,待反应完成后,自然冷却至常温,过滤;然后分别用去离子水及50%的乙醇水溶液洗涤,冷冻干燥,即得聚醚胺改性蒙脱土(OMMT)。
(2))水性聚氨酯与改性蒙脱土混合制备,具体操作如下:
取一定质量的OMMT,用20mL二甲基甲酰胺(DMF)在常温下溶胀1h,超声波分散30min,使其充分分散在DMF中;将分散后的OMMT滴加到三乙胺中和后的聚氨酯预聚体中,升温到60℃,反应2h;待反应完成后,自然冷却至常温,加水乳化,得到高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液。
水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜的制备:
将得到的水性聚氨酯/改性蒙脱土纳米复合乳液,成膜干燥,最后制得高耐水性水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜。
如图2所示,从图中可以看出水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜的断裂面呈现刚性断裂,蒙脱土的加入提高了复合材料的刚性。
对比实施例1:水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合及膜
水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合乳液的制备如下:
(1)十二烷基季铵盐对蒙脱土进行改性,具体改性实例如下:
称取蒙脱土1.0g,加100ml蒸馏水配成1%的蒙脱土分散液,溶胀1h。将十二烷基季铵盐在80℃强力搅拌下逐滴滴加入蒙脱土分散液中,滴加时间控制在30rnin,反应5h,待反应完成后,自然冷却至常温,过滤;然后分别用去离子水及50%的乙醇水溶液洗涤,冷冻干燥,即得十二烷基季铵盐改性蒙脱土(OMMT)。
(2)水性聚氨酯与改性蒙脱土混合制备,具体操作如下:
取一定质量的OMMT,用20mL二甲基甲酰胺(DMF)在常温下溶胀1h,超声波分散30min,使其充分分散在DMF中;将分散后的OMMT滴加到三乙胺中和后的聚氨酯预聚体中,升温到60℃,反应2h;待反应完成后,自然冷却至常温,加水乳化,得到高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液。
水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合膜的制备:
将得到的水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合乳液,成膜干燥,最后制得高耐水性水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合膜。
对实施例1、实施例2、对比实施例1得到的膜进行拉伸性能和吸水率测试,结果如图3和图4所示。
从图3中可以看出水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜显示出比纯水性聚氨酯略低的断裂伸长率,但水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜显示出高得多的始模量及应力,同时水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合膜的模量和强度相较纯水性聚氨酯膜高,但比水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜低。
从图4中可以看出相较于纯水性聚氨酯膜和水性聚氨酯/十二烷基季铵盐改性蒙脱土纳米复合膜,水性聚氨酯/聚醚胺改性蒙脱土纳米复合膜显示出更低的吸水率。
其中,拉伸测试的样品用哑铃模具(ASTM D638V型)进行切割处理,使用美国Instron公司5960型微机控制电子万能试验机根据GB 1040-92对聚合物纳米复合材料进行拉伸试验;吸水率(WA)测试将干燥后样品(m1)置于蒸馏水中,室温下浸泡,一定时间取出后用吸水纸吸去表面去离子水并称重(m2),吸水率(WA)按公式(1)进行计算:
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (4)
1.一种纳米复合乳液,其特征在于,所述纳米复合乳液的制备方法如下:
(1)聚醚胺与盐酸重量比1:(1-5)加入烧杯中,搅拌5-30min,搅拌速度100-500rpm/min,然后在频率为40-100Hz的超声波下超声分散30-120min,备用;
(2) 蒙脱土与水重量比(0.005-1):1加入到容器中充分溶胀,然后加入酸解离的聚醚胺,在40-100℃下搅拌3-8h,搅拌速度为100-2000rmp/min,将得到的改性蒙脱土干燥,分散到溶剂中备用;
(3) 纳米复合乳液的制备:聚氨酯预聚体的温度降低到25℃,加入中和剂,反应1-2h,然后升温至60℃,向其中加入改性蒙脱土分散液,反应2-4h,最后在室温下高速搅拌乳化1h,制得高耐水性水性聚氨酯/改性蒙脱土纳米复合乳液;
所述纳米复合乳液的固含为5%-20%;
所述的聚醚胺其分子链末端为伯胺或仲胺基,数均分子量范围为200-3000。
2.根据权利要求1所述纳米复合乳液制备得到的膜。
3.一种包装材料,其特征在于,所述包装材料的制备包括利用权利要求1所述纳米复合乳液。
4.根据权利要求3所述的包装材料,其特征在于,所述包装材料为食品或者医药领域的包装材料。
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