CN109535375B - 一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法 - Google Patents

一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法 Download PDF

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CN109535375B
CN109535375B CN201811441442.4A CN201811441442A CN109535375B CN 109535375 B CN109535375 B CN 109535375B CN 201811441442 A CN201811441442 A CN 201811441442A CN 109535375 B CN109535375 B CN 109535375B
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diisocyanate
isocyanate
polyurethane
composite material
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徐井水
张玲
李春海
杨海英
伍海芳
张婷
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Guangdong University of Petrochemical Technology
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Abstract

本发明公开了一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法。通过将纳米级、亚微米级或微米级的层状无机颗粒搅拌分散于无水溶剂中，然后加入异氰酸酯直接进行充分的接枝改性，至反应体系不产生气体，静置一段时间后、过滤除去上层溶剂，即获得改性层状无机颗粒；然后与脱水多元醇和熔融异氰酸酯，在75‑80℃下继续搅拌反应得到预聚体；真空脱泡后加入计量的脱水扩链剂，快速搅拌一段时间，迅速倒入预热的模具，放入120℃的平板硫化机中加压固化，然后将样品置于鼓风烘箱中100℃熟化24小时，室温放置一段后，即获得聚氨酯纳米复合材料。本发明利用高度剥离的二维纳米片不仅可有效增强聚氨酯材料的机械性能，且对聚氨酯材料有良好的增韧效果，制备出综合性能优异聚氨酯纳米复合材料。

Description

一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法
技术领域
本发明涉及聚氨酯纳米复合材料领域，具体涉及一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法。
背景技术
热塑性聚氨酯弹性体（TPU）是由多异氰酸酯和带有羟基的聚酯或聚醚二元醇和低分子二元醇扩链剂，通过逐步加成聚合反应制成的线状或稍有支化或交联的高分子材料。TPU分子中既含有柔性软链段又含有刚性硬链段，软链段决定了TPU的一些最终性能，如弹性、低温屈绕性；硬链段则显示的是硬度、弹性模量、脱模性和热稳定性等，硬链段通过分子间氢键获得强的物理交联结构，形成微相分离结构，即使无化学交联结构也表现出了橡胶弹性，其弹性模量介于塑料和橡胶之间，在较宽的硬度范围内仍能保持较好的弹性；TPU还兼有塑料加工工艺性能，这使得TPU具有强度高、韧性好、耐磨、耐油等优异性能，在交通工具、建筑、食品包装和家电用密封垫等领域有着广泛的应用前景。然而，TPU存在耐热性较差、模量低缺点，这些不足已经成为聚氨酯弹性体材料在实际应用过程中亟待克服的困恼。
基于此，大量研究者采用各种物理和化学方法对聚氨酯弹性体改性，如利用TPU为基体与具有刚性及各向异性的无机纳米颗粒制备的复合材料成为热点之一。文献Synthesis and characterization of polyurethane/organo-montmorillonitenanocomposites. Appl. Clay Sci., 2010, 47: 242-248 中公开了一种聚氨酯/蒙脱土纳米复合材料，发现利用丙酮为溶剂、季铵盐离子交换法改性原料蒙脱土原位合成出热稳定性和硬度均有改进的聚氨酯纳米复合材料。
文献Laponite/聚氨酯纳米复合材料制备及性能研究，高分子学报，2013,7,943-949中公开了通过溶剂交换法将无机Laponite从水相转移到N, N-二甲基乙酰胺中，在超声波作用下应用溶液共混方法制备了热塑性聚氨酯/Laponite纳米复合材料，发现由于所制备材料体系中网络结构的存在，使得其强度、硬度合韧性得到同步提高。
文献Preparation and properties of PU/MCMMT nanocomposites. Polym.Adv. Technol. 2010, 21, 296-299公开一种利用预先季铵盐和异氰酸酯共同作用对蒙脱土有机化改性，然后利用原位法制备出聚氨酯纳米复合材料，当无机填料加入量为4%（质量分数）时，纳米材料的强度提高大约24%相对于纯聚氨酯样品。
然而，基于现有文献报道中常选用片层结构颗粒蒙脱土作为增强聚氨酯填充料，由于无机颗粒与聚氨酯基体之间的差的相容性，常采用季铵盐或与之复配的改性剂对其预先处理获得有机蒙脱土颗粒。由此获得的有机蒙脱土表面的烷基链是非极性的，与聚氨酯体系相容性差，且接枝上的功能团被这些非极性的烷基链包埋而不能参与聚氨酯的聚合反应，从而难以完全实现纳米片均匀分布在聚氨酯基体中，导致制备的复合材料性能提升不显著。
鉴于此，本发明提供一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，通过采用聚氨酯合成原料之一，即异氰酸酯的分子结构中活性基团（-NCO）与填充料表面的活性基团（如-OH、-C=O等）反应对其接枝改性，利用异氰酸酯修饰的原料层状颗粒如蒙脱土、水滑石、石墨烯等，解决了无机填料与聚氨酯基体间相容性差的问题，从而保证了它们能有效参与到后续的聚氨酯的原位聚合反应系统中去，实现对二维层状颗粒的高效剥离，并且高剥离的二维纳米片与聚氨酯体系之间存在的共价键或氢键作用，使得二维纳米片均匀分散在聚氨酯基体中，由此制备的聚氨酯纳米材料具有良好的综合性能，是一种高效的增强增韧手段。
发明内容
本发明的目的是提供一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，由此制备出的聚氨酯纳米复合材料具有良好的机械性能同时，成本也可较好降低。
本发明提供的一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，该制备方法包括以下步骤：
（1）片层结构颗粒接枝改性：将纳米级、亚微米级或微米级的层状无机颗粒搅拌分散于无水溶剂中，配比为3-8g:100mL，加入过量的异氰酸酯，充分混合，升温至80℃，直至体系不产生二氧化碳气体为止，得到异氰酸酯改性层状颗粒混合液，静置0.5-1小时，过滤除去上层溶剂，即获得改性层状颗粒絮状混合物；
（2）聚氨酯纳米复合材料的制备：将步骤（1）所获得的改性层状颗粒絮状混合物分散在计量的多元醇中，再加入计量的异氰酸酯于80℃下继续搅拌反应1.5-3小时，获得预聚体；将预聚体真空脱泡后加入计量的扩链剂，搅拌30-90秒，倒入预热至60℃的模具，放入120℃的平板硫化机中加压固化30分钟，然后将样片放在鼓风烘箱中100℃熟化24 小时，室温放置一周后，制得热塑性聚氨酯弹性体纳米复合材料；其中，多元醇、扩链剂和异氰酸酯在使用前分别进行预处理，预处理的方法是：多元醇和扩链剂分别在100-110℃下真空脱水1.5-2.5小时，异氰酸酯放置真空烘箱于45-60℃下缓慢熔化，多元醇:异氰酸酯:扩链剂三者经预处理后的投料质量比为100:25-60:10-35，改性层状颗粒絮状混合物与多元醇、异氰酸酯和扩链剂三者经预处理后的总质量的质量比为0.5-5:100。
在步骤（1）中，所述片层无机颗粒为水滑石、蒙脱土、石墨烯或云母。
在步骤（1）或步骤（2）中，所述异氰酸酯为脂肪族异氰酸酯中的六亚甲基二异氰酸酯（HDI）、赖氨酸二异氰酸酯（LDI）、多亚甲基多苯基二异氰酸酯（PAPI）、三甲基-1, 6-六亚甲基二异氰酸酯（TMHDI）、四甲基二亚甲基二异氰酸酯(TMDI)、二环己基甲烷二异氰酸酯(HMDI)、1,4-环己烷二异氰酸酯、异氟尔酮二异氰酸酯（IPDI）和香族异氰酸酯中的苯二亚甲基二异氰酸酯(XDI)、4,4`-二苯基甲烷二异氰酸酯（MDI）、甲苯二异氰酸酯 (TDI)、1,5-奈二异氰酸酯（NDI）中的一种或复配。
在步骤（1）中，所述无水溶剂为经脱水后的二甲基甲酰胺（DMF）、经脱水后的二甲基乙酰胺（DMAC）中的一种或复配。
在步骤（2）中，所述多元醇为聚己内酯二醇、聚己二酸乙二酯、聚醚聚氧化丙烯醚、聚四氢呋喃、端羟基聚丁二烯、端羟基聚丁二烯-丙烯腈和端羟基聚异戊二烯聚酯中的一种或多种复配，其中，聚四氢呋喃为聚四氢呋喃二醇PTMG-1000或聚四氢呋喃二醇PTMG-2000。
在步骤（2）中，所述扩链剂为1,4-丁二醇、氢醌双（2-羟乙基）醚、氢化双酚A、间苯二酚二羟乙基醚、3,3’-二氯-4,4’-二苯甲烷二胺，3,5-二甲硫基甲苯二胺（DMTDA）或3,5-二氨基对氯苯甲酸异丁酯。
采用上述方法制备的聚氨酯纳米复合材料，利用高剥离二维纳米片被较好均匀分散在聚氨酯基质中的应用也在本发明的保护范围之内。
本发明的有益之处在于：
利用二维纳米片可有效提高材料的耐热性、强度、模量和气体阻隔性能，聚氨酯纳米复合材料采用在逐步聚合过程中调节其分子链结构和添加的二维纳米片层填充料。然而，层状无机填充料与聚氨酯基体间存在相容性差的缺陷。为此，本发明专利预先采用异氰酸酯活性基团与层状颗粒表面的活性基团发生接枝反应，这样既避免了其它改性剂引入到聚氨酯逐步缩聚反应系统因改性剂与聚氨酯体系相容性差而影响最后制品的综合性能，又可利用接枝改性后的二维层状颗粒中的活性基团能有效参与到聚氨酯反应合成体系中，从而实现二维纳米片层均匀分散在聚氨酯基体中，由此所制得的复合材料具有良好的机械性能，降低成本，这是一种高效的增强增韧手段。
附图说明
图1是本发明实施例1中聚氨酯/蒙脱土纳米复合材料的电镜图；
图2是本发明实施例1中聚氨酯/蒙脱土纳米复合材料的XRD状态图。
具体实施方式
下面结合说明书附图和具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
下述各个实施例及对比例最终产品的性能测试中，对比例1为实验室相同条件下自制的热塑性聚氨酯弹性体，与实施例1-4中聚氨酯弹性体/蒙脱土纳米复合材料，一同参照JIS K7311-1995《热塑性聚氨酯弹性体的试验》方法进行测定。以下各个实施例与对比例的性能测试均进行五次平行试验取平均值。
实施例1
将纳米级的蒙脱土粉体3g分散在脱水二甲基乙酰胺 (DMAC) 100mL中，加入过量的二甲基甲烷-4,4′-二异氰酸酯（MDI），充分混合，升温至80℃，使得MDI与蒙脱土层间少量的水和蒙脱土表面的羟基充分反应，直至体系不产生二氧化碳气体为止，得到MDI改性层状颗粒混合液，静置1小时，上层为乙酰胺，下层为改性层状颗粒絮状混合物。过滤除去上层溶剂乙酰胺，得到改性层状颗粒絮状混合物。
将聚四氢呋喃二醇（PTMG-1000）和1,4-丁二醇（BDO）分别在105℃下真空脱水2小时，二甲基甲烷-4,4′-二异氰酸酯（MDI）放置真空烘箱于55℃下缓慢熔化，然后将100g聚四氢呋喃二醇加入三口烧瓶中，再加入计量的改性层状颗粒絮状混合物0.83g，在80℃下搅拌分散1.5小时，加入计量的53.6g MDI，于80℃下继续搅拌反应2小时得到预聚体；将预聚体真空脱泡后加入计量的12 g 1,4-丁二醇，搅拌30秒后倒入预热至60℃的模具，放入120℃的平板硫化机中加压固化30分钟，然后放在鼓风烘箱中100℃熟化24小时，室温放置一周后，制得热塑性聚氨酯弹性体纳米复合材料。裁样测其性能，测试结果如表1。
实施例2
将纳米级的蒙脱土粉体4g分散在脱水二甲基甲酰胺（DMF）100mL中，加入过量的1,5-奈二异氰酸酯，充分混合，升温至80℃，使得1,5-奈二异氰酸酯与石墨烯分子结构中羟基充分反应，直至体系不产生二氧化碳气体为止，得到1,5-奈二异氰酸酯改性层状颗粒混合液，静置1小时，上层为乙酰胺，下层为改性层状颗粒絮状混合物。过滤除去上层溶剂乙酰胺，得到改性层状颗粒絮状混合物。
将聚己内酯二醇和3,5-二甲硫基甲苯二胺（DMTDA）分别在105℃下真空脱水2小时，1,5-奈二异氰酸酯放置真空烘箱于50℃下缓慢熔化，然后将100g聚己内酯二醇加入三口烧瓶中，再加入计量的改性层状颗粒絮状混合物1g，在80℃下搅拌分散1.5小时，加入计量的45g 1,5-奈二异氰酸酯，于80℃下继续搅拌反应2小时得到预聚体；将预聚体真空脱泡后加入计量的29g DMTDA，搅拌30秒后倒入预热至60℃的模具，放入120℃的平板硫化机中加压固化30分钟，然后放在鼓风烘箱中100℃熟化24小时，室温放置一周后，制得热塑性聚氨酯弹性体纳米复合材料。裁样测其性能，测试结果如表1。
实施例3
将纳米级的蒙脱土粉体7g分散在脱水二甲基乙酰胺 (DMAC) 100mL中，加入过量的异氟尔酮二异氰酸酯（IPDI），充分混合，升温至80℃，使得IPDI与水滑石层间少量的水和水滑石表面的羟基充分反应，直至体系不产生二氧化碳气体为止，得到IPDI改性层状颗粒混合液，静置1小时，上层为乙酰胺，下层为改性层状颗粒絮状混合物。过滤除去上层溶剂乙酰胺，得到改性层状颗粒絮状混合物。
将聚己二酸乙二酯和间苯二酚二羟乙基醚分别在105℃下真空脱水2小时，异氟尔酮二异氰酸酯（IPDI）放置真空烘箱于55℃下缓慢熔化，然后将100g聚己二酸乙二酯加入三口烧瓶中，再加入计量的改性层状颗粒絮状混合物1.4g，在80℃下搅拌分散1.5小时，加入计量的24g IPDI，于80℃下继续搅拌反应2小时得到预聚体；将预聚体真空脱泡后加入计量的13g 间苯二酚二羟乙基醚，搅拌30秒后倒入预热至60℃的模具，放入120℃的平板硫化机中加压固化30分钟，然后将样片放在鼓风烘箱中100℃熟化24小时，室温放置一周后，制得热塑性聚氨酯弹性体纳米复合材料。裁样测其性能，测试结果如表1。
实施例4
将纳米级的蒙脱土粉体8g分散在脱水二甲基乙酰胺 (DMAC) 100mL中，加入过量的三甲基-1,6-六亚甲基二异氰酸酯（TMHDI），充分混合，升温至80℃，使得TMHDI与云母层间少量的水和云母表面的羟基充分反应，直至体系不产生二氧化碳气体为止，得到TMHDI改性层状颗粒混合液，静置1小时，上层为乙酰胺，下层为改性层状颗粒絮状混合物。过滤除去上层溶剂乙酰胺，得到改性层状颗粒絮状混合物。
将聚醚聚氧化丙烯醚和3,3’-二氯-4,4’-二苯甲烷二胺分别在105℃下真空脱水2小时，三甲基-1,6-六亚甲基二异氰酸酯放置真空烘箱于55℃下缓慢熔化，然后将100g聚醚聚氧化丙烯醚加入三口烧瓶中，再加入计量的改性层状颗粒絮状混合物2.7g，在80℃下搅拌分散1.5小时，加入计量的45g 三甲基-1,6-六亚甲基二异氰酸酯，于80℃下继续搅拌反应2小时得到预聚体；将预聚体真空脱泡后加入计量的35g 3,3’-二氯-4,4’-二苯甲烷二胺，搅拌30秒后倒入预热至60℃的模具，放入120℃的平板硫化机中加压固化30分钟，然后放在鼓风烘箱中100℃熟化24小时，室温放置一周后，制得热塑性聚氨酯弹性体纳米复合材料。裁样测其性能，测试结果如表1。
对比例1和实施例1-4的样品性能测试结果如表1。
表1
Figure 780192DEST_PATH_IMAGE001
以上所述，仅是本发明的较佳实施例而已，并不用以限制本发明，故凡是依据本发明的技术实际对以上实施例所作的任何修改、等同替换、改进等，均仍属于本发明技术方案的范围内。

Claims (6)

1.一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，其特征在于，该制备方法包括以下步骤：
（1）层状结构颗粒接枝改性：将纳米级、亚微米级或微米级的层状无机颗粒搅拌分散于无水溶剂中，配比为3-8g:100mL，加入过量的异氰酸酯，充分混合，升温至80℃，直至体系不产生二氧化碳气体为止，得到异氰酸酯改性层状颗粒混合液，静置0.5-1小时，过滤除去上层溶剂，即获得改性层状颗粒絮状混合物；
（2）聚氨酯纳米复合材料的制备：将步骤（1）所获得的改性层状颗粒絮状混合物分散在计量的多元醇中，再加入计量的异氰酸酯于80℃下继续搅拌反应1.5-3小时，获得预聚体；将预聚体真空脱泡后加入计量的扩链剂，搅拌30-90秒，倒入预热至60℃的模具，放入120℃的平板硫化机中加压固化30分钟，然后将样片放在鼓风烘箱中100℃熟化24小时，室温放置一周后，制得热塑性聚氨酯弹性体纳米复合材料；其中，多元醇、扩链剂和异氰酸酯在使用前分别进行预处理，预处理的方法是：多元醇和扩链剂分别在100-110℃下真空脱水1.5-2.5小时，异氰酸酯放置真空烘箱于45-60℃下缓慢熔化，多元醇:异氰酸酯:扩链剂三者经预处理后的投料质量比为100:25-60:10-35，改性层状颗粒絮状混合物与多元醇、异氰酸酯和扩链剂三者经预处理后的总质量的质量比为0.5-5:100。
2.如权利要求1所述的一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，其特征在于，在步骤（1）中，所述片层无机颗粒为水滑石、蒙脱土、石墨烯、氧化石墨烯或云母。
3.如权利要求1所述的一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，其特征在于，在步骤（1）或步骤（2）中，所述异氰酸酯为脂肪族异氰酸酯中的六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、多亚甲基多苯基二异氰酸酯、三甲基-1,6-六亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异氟尔酮二异氰酸酯、1,4-环己烷二异氰酸酯和芳香族异氰酸酯中的苯二亚甲基二异氰酸酯、4，4`-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、1,5-奈二异氰酸酯中的一种或复配。
4.如权利要求1所述的一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，其特征在于，在步骤（1）中，所述无水溶剂为经脱水后的二甲基甲酰胺、经脱水后的二甲基乙酰胺中的一种或复配。
5.如权利要求1所述的一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，其特征在于，在步骤（2）中，所述多元醇为聚己内酯二醇、聚己二酸乙二酯、聚醚聚氧化丙烯醚、聚四氢呋喃、端羟基聚丁二烯、端羟基聚丁二烯-丙烯腈和端羟基聚异戊二烯聚酯中的一种或多种复配，其中，聚四氢呋喃为聚四氢呋喃二醇PTMG-1000或聚四氢呋喃二醇PTMG-2000。
6.如权利要求1所述的一种高度剥离的二维纳米片增强聚氨酯复合材料的制备方法，其特征在于，在步骤（2）中，所述扩链剂为1,4-丁二醇、氢醌双（2-羟乙基）醚、氢化双酚A、间苯二酚二羟乙基醚、3,3’-二氯-4,4’-二苯甲烷二胺，3,5-二甲硫基甲苯二胺或3,5-二氨基对氯苯甲酸异丁酯。
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