CN109438670A - 高透明的软质热塑性聚氨酯弹性体及其制备方法和应用 - Google Patents

高透明的软质热塑性聚氨酯弹性体及其制备方法和应用 Download PDF

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CN109438670A
CN109438670A CN201811593220.4A CN201811593220A CN109438670A CN 109438670 A CN109438670 A CN 109438670A CN 201811593220 A CN201811593220 A CN 201811593220A CN 109438670 A CN109438670 A CN 109438670A
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high transparency
polyurethane elastomers
quaternary ammonium
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王小妹
梁智昊
梁植辉
陈华伟
伍雪芬
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Foshan Huabolun Material Technology Co Ltd
Sun Yat Sen University
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Sun Yat Sen University
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Abstract

本发明公开了一种高透明的软质热塑性聚氨酯弹性体及其制备方法和应用。所述聚氨酯弹性体由以下按重量百分比计算的原料制成：二异氰酸酯单体15~29%，二元醇单体52~70%，扩链剂1~10%，二羟基磺酸季铵盐3~8%，链终止剂2~6%；所述链终止剂为结晶型烷基醇；所述二羟基磺酸季铵盐的季铵阳离子中，甲基数量不多于3个。所述热塑性聚氨酯弹性体具有透明度高，柔软性好，同时又不含增塑剂和防粘剂，是一种优秀的可用作软质鞋材、手机壳材料、医疗和包装材料的聚氨酯弹性体材料。

Description

高透明的软质热塑性聚氨酯弹性体及其制备方法和应用
技术领域
本发明涉及聚氨酯弹性体领域，具体涉及一种高透明的软质热塑性聚氨酯弹性体及其制备方法和应用。
背景技术
热塑性聚氨酯弹性体(TPU)是一种介于橡胶和塑料之间的材料，具有高强度、高韧性、耐磨、耐油等优异性能。随着TPU在软质鞋材、手机壳、医疗和包装领域的应用越来越广，其加工性和柔软性都需要进一步改善。早期可使用的最柔软的TPU的邵尔A硬度也只在80～85之间，加工相当困难。经过几年发展，慢慢探索出提高TPU柔软性的途径。例如，通过添加增塑剂或者与其他较软的材料共混可降低TPU的硬度，但通常会使制品的机械性能和物理性能下降，甚至可能引发环境问题。另外，通过增大TPU软段中多元醇的分子量，使软段微区增加，硬段比例减小，可也获得软质TPU。但是，随着多元醇分子量增大，TPU的熔融黏度升高，所需的加工温度增高；且分子结晶速率加快，容易导致产品发雾，透明度低。
软质TPU材料较粘稠，形成的粒料容易粘在一起或注塑成型时不易脱模，通常需要添加芥酸酰胺等防粘剂来降低粘性。但是防粘剂一般呈细粉末状，不易分散混合，且防粘剂在使用过程中容易迁移、析出，导致产品表面形成一层很薄的粉状物或蜡状物质，影响产品性能，并存在一定的健康和安全危害。另外，制造不含防粘剂等小分子助剂的TPU粒料可允许处理器增加干燥温度，从而缩短材料的处理时间。
因此，开发一种透明度高，柔软性好，同时又不含增塑剂和防粘剂的TPU十分有意义。
发明内容
本发明的目的是克服上述现有技术中的不足，提供一种高透明的软质热塑性聚氨酯弹性体。该热塑性聚氨酯弹性体为离子聚合物，具有透明度高，柔软性好，邵尔A硬度低于80，且不含增塑剂和防粘剂等特点。
本发明的另一目的是提供所述高透明的软质热塑性聚氨酯弹性体的制备方法。
本发明的另一目的是提供所述高透明的软质热塑性聚氨酯弹性体的应用。
本发明上述目的通过以下技术方案实现：
一种高透明的软质热塑性聚氨酯弹性体，所述聚氨酯弹性体由以下按重量百分比计算的原料制成：二异氰酸酯单体15～29％，二元醇单体52～70％，扩链剂1～10％，二羟基磺酸季铵盐3～8％，链终止剂2～6％；所述链终止剂为结晶型烷基醇；所述二羟基磺酸季铵盐的季铵阳离子中，甲基数量不多于3个。
通过二羟基磺酸季铵盐与异氰酸酯反应，在TPU中引入离子基团，大体积季铵阳离子基团的介入破坏了分子链，特别是硬段链节的规整排列，降低了硬段的结晶，提高了产品透明度，并产生自由体积软化聚合物和降低熔融粘度；而离子基团的静电力可提高分子间相互作用，避免因硬段结晶下降导致拉伸强度不足，因此引入了二羟基磺酸季铵盐TPU变得更柔软和透明。
优选地，所述二羟基磺酸季铵盐为式(Ⅰ)或式(Ⅱ)中任意一种或几种的混合物：
其中，季铵阳离子上不同烷基链的n值独立选自1～18，n不同时为1。
优选地，所述季铵阳离子为四己基铵离子、四辛基铵离子、四癸基铵离子、二癸基二甲基铵离子、双十二烷基二甲基铵离子、双十六烷基二甲基铵离子、十二烷基三甲基铵离子、十六烷基三甲基铵离子、十八烷基三甲基铵离子中任意一种。
结晶型烷基醇通常是因为具有长的碳链，容易结晶成蜡状，也有称作醇蜡。例如十六烷醇是白色固体，而十五烷醇是液体，所以十六烷醇属于结晶型烷基醇，而十五烷醇不属于结晶型烷基醇。结晶型烷基醇的羟基与异氰酸酯基反应封端，形成具有可结晶端基的聚氨酯弹性体。可结晶端基可降低TPU的粘性，起到防粘连作用，可减少或不用防粘连剂。由于TPU粘性降低，加工过程中可增加颗粒的干燥温度，节省时间和成本。
优选地，所述结晶型烷基醇为碳原子数在16个以上的脂肪伯醇。当烷基醇的碳原子数小于16时，烷基的结晶性不足，影响TPU的抗粘连性。
优选地，所述结晶型烷基醇为饱和醇。
优选地，所述二异氰酸酯单体的-NCO摩尔数与二元醇单体、扩链剂、二羟基磺酸铵盐和链终止剂的总-OH摩尔数的比值R为0.9～1.0。
优选地，所述二异氰酸酯单体为异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)、间苯二甲撑二异氰酸酯(XDI)、1,5-萘二异氰酸酯(NDI)、二环己基甲烷二异氰酸酯(HMDI)中的一种或几种的混合物。
现有技术中如果不添加增塑剂，单纯通过增大二元醇单体的分子量来获得软质TPU的方法，一般需要二元醇单体的分子量在3000以上。本发明主要通过引入季铵阳离子基团来增大自由体积，实现TPU的软化，因此二元醇单体的分子量选择范围更宽。另外，随着二元醇单体的分子量增大，物料熔融黏度升高，所需的加工温度增高，本发明可选用较低分子量的二元醇单体，使加工温度不至于特别高。
优选地，所述二元醇单体的分子量为1000～5000。
所述二元醇为聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚碳酸酯二醇、聚己内酯二醇、聚醚二元醇、聚四氢呋喃二醇中的一种或几种的混合物。优选地，所述扩链剂为乙二醇，二甘醇，丙二醇，二丙二醇，丁二醇，戊二醇，己二醇，1,4-环己烷二甲醇中的一种或几种的混合物。
所述高透明的软质热塑性聚氨酯弹性体的制备方法，包括如下步骤：将干燥的各组分按配方比例称量并混合均匀，经双螺杆挤出机熔融反应，温度为150～230℃，冷却、造粒、干燥得到TPU粒料。
所述高透明的软质热塑性聚氨酯弹性体在作为软质鞋材、手机壳材料、医疗和包装材料中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明通过在TPU中引入大体积的季铵阳离子基团，破坏了聚合物分子链，尤其是硬段链节的规整排列，增大了链段间的自由体积，使TPU透明度和柔软性提高，熔融粘度降低；而离子基团间的静电相互作用，可避免因硬段结晶下降导致力学性能变差。同时使用可结晶的烷基醇作为链终止剂来封端TPU，起到防粘连作用，可减少或不用防粘连剂，避免因防粘连剂迁移、析出影响产品的外观和使用性能。综上，本发明获得的热塑性聚氨酯弹性体具有高透明、软质的特点并且不含增塑剂和防粘剂。
具体实施方式
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。
实施例
本发明实施例中所用结晶型长链醇链终止剂可选用贝克休斯公司的Unilin-350醇，Unilin-550醇。其中，Unilin-350醇平均链长约为26个碳；Unilin-550醇平均链长为40个碳。
参照HG/T 2368-2011测定TPU的邵尔A硬度；按GB/T 1040.3-2006测定TPU的拉伸强度和断裂伸长率，采用Ⅳ型试样，拉伸速度为500mm/min；按HG/T2914-1997测定TPU的粘连面积，用以表征防粘连特性。
透明度：将TPU粒料在挤出机或压延机中制备成厚度分别为2mm、4mm、6mm、8mm……(以此类推)的片材，目测透明、无发雾的最厚片材的厚度作为TPU透明度的表征数据。
实施例1～4的原料用量如表1所示，对比例1～5的原料用量如表2所示。实施例和对比例的制备方法如下步骤：将干燥的各组分按配方比例称量并混合均匀，经双螺杆挤出机熔融反应，温度为150～230℃，冷却、造粒、干燥得到TPU粒料。
表1实施例1～4的原料用量
表2对比例1～5的原料用量
表3实施例和对比例所制备TPU的性能测试结果
实施例1～4所制备热塑性聚氨酯弹性体邵尔A硬度均低于80，符合手机壳、皮革等软质产品的使用要求，TPU粒料压延成8mm厚的片材时依然保持透明，透明度高，且抗粘连性好。
由实施例1和对比例1可见，当二羟基磺酸季铵盐的质量百分比少于3％时，所制备的TPU柔软性不足，邵尔A硬度大于80，且透明度降低；由实施例1和对比例2、3可见，当链终止剂的质量百分比少于2％，或者链终止剂的烷烃链长小于16个碳时，所制备的TPU抗粘连性不够。这是因为链终止剂用量太少时，降粘效果有限，而链终止剂的烷烃链长小于16个时，烷烃不易结晶，导致防粘效果差；由实施例1和对比例4可见，当二羟基磺酸季铵盐为2-(二乙醇胺基)乙磺酸四甲基铵盐，即季铵阳离子含多于三个甲基时，由于季铵阳离子的体积较小，起不到破坏硬段结晶和增大自由体积的作用，故TPU的透明度和柔软性较差；由实施例4和对比例5可见，当二羟基磺酸季铵盐的质量百分比大于8％时，由于大体积季铵阳离子过度破坏硬段微相的形成，离子基团间的静电作用力不足以弥补力学性能的损失，导致TPU的拉伸强度明显降低。
显然，本发明的上述实施例仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。本领域技术人员应当理解，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

1.一种高透明的软质热塑性聚氨酯弹性体，其特征在于，所述聚氨酯弹性体由以下按重量百分比计算的原料制成：二异氰酸酯单体15~29%，二元醇单体52~70%，扩链剂1~10%，二羟基磺酸季铵盐3~8%，链终止剂2~6%；所述链终止剂为结晶型烷基醇；所述二羟基磺酸季铵盐的季铵阳离子中，甲基数量不多于3个。
2.根据权利要求1所述高透明的软质热塑性聚氨酯弹性体，其特征在于，所述二羟基磺酸季铵盐为式（Ⅰ）或式（Ⅱ）中任意一种或几种的混合物：
其中，季铵阳离子上不同烷基链的n值独立选自1~18，n不同时为1。
3.根据权利要求2所述高透明的软质热塑性聚氨酯弹性体，其特征在于，所述季铵阳离子为四己基铵离子、四辛基铵离子、四癸基铵离子、二癸基二甲基铵离子、双十二烷基二甲基铵离子、双十六烷基二甲基铵离子、十二烷基三甲基铵离子、十六烷基三甲基铵离子、十八烷基三甲基铵离子中任意一种。
4.根据权利要求1所述高透明的软质热塑性聚氨酯弹性体，其特征在于，所述结晶型烷基醇为碳原子数在16个以上的脂肪伯醇。
5.根据权利要求4所述高透明的软质热塑性聚氨酯弹性体，其特征在于，所述结晶型烷基醇为饱和醇。
6.根据权利要求1所述高透明的软质热塑性聚氨酯弹性体，其特征在于，
所述二异氰酸酯单体的-NCO摩尔数与二元醇单体、扩链剂、二羟基磺酸季铵盐和链终止剂的总-OH摩尔数的比值R为0.9~1.0。
7.根据权利要求1所述高透明的软质热塑性聚氨酯弹性体，其特征在于，所述二元醇单体的分子量为1000~5000。
8.根据权利要求1所述高透明的软质热塑性聚氨酯弹性体，其特征在于，所述扩链剂为乙二醇，二甘醇，丙二醇，二丙二醇，丁二醇，戊二醇，己二醇，1,4-环己烷二甲醇中的一种或几种的混合物。
9.权利要求1~8任一项所述高透明的软质热塑性聚氨酯弹性体的制备方法，其特征在于，包括如下步骤：将干燥的各组分按配方比例称量并混合均匀，经双螺杆挤出机熔融反应，温度为150~230℃，冷却、造粒、干燥得到TPU粒料。
10.权利要求1~8所述高透明的软质热塑性聚氨酯弹性体在作为软质鞋材、手机壳材料、医疗和包装材料中的应用。
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