CN113292764B - 一种耐压缩聚氨酯泡棉及其制备方法 - Google Patents

一种耐压缩聚氨酯泡棉及其制备方法 Download PDF

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CN113292764B
CN113292764B CN202110496030.6A CN202110496030A CN113292764B CN 113292764 B CN113292764 B CN 113292764B CN 202110496030 A CN202110496030 A CN 202110496030A CN 113292764 B CN113292764 B CN 113292764B
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高虎亮
魏琼
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Hubei Xiangyuan New Material Technology Inc
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Abstract

本发明公开了一种耐压缩聚氨酯泡棉，包括组分A和组分B；其中，所述组分A包括分子链中不含F、O、N元素的聚二元醇以及膨胀微球、低沸点发泡剂、催化剂、表面活性剂；所述组分B包括二异氰酸酯、扩链剂、交联剂、聚二元醇；其中二异氰酸酯过量；所述组分A和所述组分B混合后涂覆于高分子材料或金属材料薄膜表面，固化成型后即得到所述聚氨酯泡棉。本发明还公开了一种耐压缩聚氨酯泡棉的制备方法。本发明最终聚氨酯分子嵌段有序化排列，且具备微观层次的三级压缩‑减震结构，共同赋予本发明的聚氨酯泡棉良好的耐压缩性，同时在压缩条件下具有较长的使用时间，能够较好的适应使用环境，保护器件。

Description

一种耐压缩聚氨酯泡棉及其制备方法
技术领域
本发明属于发泡材料技术领域，具体涉及一种超耐压缩的聚氨酯泡棉及其制备方法。
背景技术
作为新兴的高分子材料，聚氨酯由于其独特的物理性能而受到了广泛的关注，应用领域众多。而作为发泡材料使用的聚氨酯，软硬可调、加工范围宽泛、易于成型，在家具、建材、体育器械、交通运输等领域年消耗量巨大。
目前在电子产品行业应用的聚氨酯发泡材料主要是聚氨酯发泡片材，在边框密封、模组保护、硬件支撑等功能性领域发挥作用，且鉴于电子产品的灵巧性大多数情况会进行压缩使用，使用厚度往往集中在原厚度的50％-80％，更有甚者将原厚度压缩75％使用。这就对聚氨酯发泡材料的压缩性能提出了较高的要求，既要保证材料压缩幅度较大，又要使其具备良好的回弹性及较合理的压缩反弹力，同时在较大幅度的压缩条件下使用，材料要保证稳定性，不因压缩而出现使用周期变短、泡孔壁塌陷、分子链断裂等异常现象。
常规的聚氨酯发泡材料，采用异氰酸酯与聚酯、聚醚型多元醇、扩链剂、交联剂等聚合得到，泡孔采用外加发泡剂或异氰酸酯与水反应放出二氧化碳得到；其中聚多元醇作为分子结构的软段，异氰酸酯及扩链剂、交联剂等作为分子结构的硬段。聚氨酯材料的软段主要影响材料的弹性及低温性能，硬段之间的链段吸引力远大于软段之间的链段吸引力，硬相不溶于软相中，而是分布其中，形成一种不连续的微相结构，常温下在软段中起物理交联点的作用，并起增强作用。软硬段共同作用，使得聚氨酯体现出了独特的优异性能。
但是同时原材料种类、分子量、软硬段含量、开孔率、孔径分布等因素均会制约发泡材料的后期压缩性能。另外还有一个不可忽略的因素，即氢键的作用，聚氨酯分子中有大量的高电负性的N、O原子和氢原子，氢键的作用广泛存在，显著的影响聚氨酯的分子形态和力学行为，一方面氢键的存在影响了发泡材料的微观聚集态结构，另一方面又制约了软段分子链的嵌段运动及应力消耗。因此若要提升聚氨酯泡沫材料的压缩性能，除恰当控制开孔率、降低孔径分布差异外，还应恰当选择基础原材料，借以消除软段分子链运动的束缚，提升硬段分子链的增强效果，达到合理的匹配而发挥最大的功效。
发明内容
针对现有技术的以上缺陷或改进需求中的一种或者多种，本发明提供了一种耐压缩聚氨酯泡棉及其制备方法，聚氨酯泡棉中聚氨酯分子嵌段有序化排列，且具备微观层次的三级压缩-减震结构，包括发泡剂气化形成的适度开孔减震结构，膨胀后的闭孔膨胀微球在压缩过程对外界应力散点耗散形成的减震结构以及以大分子特殊硬段为“支撑体”，无任何氢键作用的软段为“弹簧簧体”，形成的具备类似于“减震弹簧”的减震结构，共同赋予聚氨酯泡棉良好的耐压缩性。
为实现上述目的，按照本发明的一个方面，提供一种耐压缩聚氨酯泡棉，所述聚氨酯泡棉包括组分A和组分B；其中，
所述组分A包括分子链中不含F、O、N元素的聚二元醇以及膨胀微球、低沸点发泡剂、催化剂、表面活性剂；
所述组分B包括二异氰酸酯、扩链剂、交联剂、聚二元醇；其中二异氰酸酯过量；各组分反应后形成预聚体。
所述组分A和所述组分B混合后涂覆于高分子材料或金属材料薄膜表面，固化成型后即得到所述聚氨酯泡棉。
优选地，所述高分子材料或金属材料薄膜为PET薄膜、PBT薄膜、PC薄膜、PP薄膜、铝膜或铜膜等。
本发明软段选择不含有F、O、N等高电负性原子的聚二元醇，规避了软段分子链中或与相隔基团形成氢键的可能，最大限度的保证分子链的嵌段运动不受影响。而同时B组分采用含苯环的异氰酸酯、含苯环的聚碳酸酯二醇及聚对苯二甲酸乙二醇酯二醇、交联剂合成预聚体，预聚体中异氰酸酯及交联剂形成硬段并同时与分子链中大部分为刚性基团的聚二元醇链接，构成“硬段+半硬段”、“分子链中氢键、分子链间氢键”的双重刚性加强。进一步地，不含F、O、N等高电负性原子的聚二元醇与预聚体交联固化，最终形成的聚氨酯分子中嵌段有序化排列，形成了类似于“减震弹簧”的结构。
作为本发明的进一步改进，组分A中所述分子链中不含F、O、N元素的聚二元醇为聚丁二烯二醇(PBDG)、氢化聚丁二烯二醇(HPBDG)、聚异戊二烯二醇(PSPG)、氢化聚异戊二烯二醇(HPSPG)、聚乙烯二醇(PEG)等直链型聚烯烃二醇中的一种；并且分子量优选为5000-10000。
作为本发明的进一步改进，组分A中所述膨胀微球为核-壳结构，其中核芯为低沸点碳氢化合物，壳体为聚苯乙烯类或聚丙烯酸酯类高分子聚合物，膨胀温度为90-100℃；所述低沸点发泡剂为正戊烷、异戊烷、环戊烷、己烷、异己烷、环己烷中的一种；所述催化剂为有机金属类催化剂，具体为新葵酸铋、异辛酸铋、新葵酸锌、异辛酸锌中的一种；所述表面活性剂为聚硅氧烷，分子量优选为1000。
作为本发明的进一步改进，组分B中所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、苯二亚甲基二异氰酸酯(XDI)等小分子芳香族二异氰酸酯中的一种，官能度优选为2。
作为本发明的进一步改进，组分B中所述交联剂为二乙醇胺、三乙醇胺、三羟甲基丙烷中的一种；所述聚二元醇为含苯环结构的聚碳酸酯二醇(PCG)、聚对苯二甲酸乙二醇酯二醇(PETG)中的一种，分子量在300-800间。
作为本发明的进一步改进，所述组分A中的聚烯烃二醇按100份计，膨胀微球添加量为3-5份；低沸点发泡剂添加量为5-10份；催化剂的添加量为0.2-0.3份；表面活性剂的添加量为0.5-1.0份；
作为本发明的进一步改进，所述组分B中的交联剂添加量占组分B中聚酯二元醇质量的3-5wt％，所述异氰酸酯的添加量通过最终体系中异氰酸酯基团的过量质量份数来确定，本发明优选实施例中其整体过量比例控制在15wt％，即最终的异氰酸酯基团的含量为15wt％；
对于组分A和组分B之间的混合比例，根据前文，组分A中的聚烯烃二醇按100份计时，组分A的添加量为108.7～116.3份，此时相对应的，B组分的添加量为5.6-11.2份。
按照本发明的另一个方面，提供一种耐压缩聚氨酯泡棉的制备方法，用于制备权利要求1-9任一项所述的耐压缩聚氨酯泡棉，包括如下步骤：
将组分A和所述组分B混合后按照涂覆厚度0.1mm-0.5mm涂覆于高分子材料或金属材料薄膜表面，在115℃～120℃温度下加热固化15min～20min，得到所述聚氨酯泡棉；
所述组分A包括分子链中不含F、O、N元素的聚二元醇以及膨胀微球、低沸点发泡剂、催化剂、表面活性剂；
所述组分B包括二异氰酸酯、扩链剂、交联剂、聚二元醇；其中二异氰酸酯过量。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，具有以下有益效果：
与常规的聚多元醇、异氰酸酯、发泡剂直接进行混合发泡不同，本发明的聚氨酯泡棉材料，进行了分子级别的设计，有序化了聚氨酯的分子结构及微观结构，形成了利于实现压缩减震及回弹恢复的三级缓冲结构：选用液态发泡剂气化的发气方式，结合表面活性剂的使用，赋予材料一定的开孔率，具备一级压缩缓冲减震结构；外加的膨胀微球，膨胀后作为散点压缩应力耗散单元，形成二级压缩减震结构；前文提到的软硬段的合理布局，特别是软段不含氢键、硬段多氢键化布局的“减震弹簧”结构，为三级减震结构单元。
通过三级减震结构单元共同作用，其中以及结构中合理的开孔率保证在初始压缩的过程中，仅仅是材料中的空气被排出，基本不改变材料本身的宏观结构；二级减震结构又使得材料在受到进一步压缩的过程中，可以耗散外界的压缩应力，不至于造成应力集中而产生破损点；三级减震结构则可以再进一步通过分子层次的微观调节，抵消外界应力，同时保证材料在高温情况下及长时间压缩的情况下具备蠕变性与形变恢复性且不发生泡孔壁的破裂，最终使得材料具备良好的压缩性，可以保证在压缩70％以上幅度的情况下，在70℃甚至以上的温度条件下，存放120小时甚至以上的时间，压缩损失在10％以下。因此本发明的泡棉具有较高的耐压缩性，同时在压缩条件下具有较长的使用时间，能够较好的适应使用环境，保护器件。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
本实施例为A1和B1的组合，其中组分A包括：分子量为5000的聚丁二烯二醇100份、膨胀微球3份、正戊烷5份、异辛酸铋0.2份、聚硅氧烷0.5份；组分B包括分子量为300的聚碳酸酯二醇100份、二乙醇胺3份、甲苯二异氰酸酯142.13份，异氰酸酯基团含量为15wt％。将组分A和组分B分别混合，并取组分B中11.2份与上述组分A混合；再按照涂覆厚度0.1mm涂覆于PET薄膜表面，在温度115℃下加热固化20min，得到聚氨酯泡棉。
实施例2
本实施例为A2和B2的组合，其中组分A包括：分子量为6000的氢化聚丁二烯二醇100份、膨胀微球3.5份、异戊烷6份、新葵酸铋0.25份、聚硅氧烷0.6份；组分B包括分子量为500的聚碳酸酯二醇100份、三乙醇胺3.5份、二苯基甲烷二异氰酸酯187.08份，异氰酸酯基团含量为15wt％。将组分A和组分B分别混合，并取组分B中9.3份与上述组分A混合；再按照涂覆厚度0.2mm涂覆于PBT薄膜表面，在温度116℃下加热固化19min，得到聚氨酯泡棉。
实施例3
本实施例为A3和B3的组合，其中组分A包括：分子量为7000的聚异戊二烯二醇100份、膨胀微球4份、环戊烷7份、异辛酸锌0.25份、聚硅氧烷0.7份；组分B包括分子量为800的聚碳酸酯二醇100份、三羟甲基丙烷4份、苯二亚甲基二异氰酸酯99.93份，异氰酸酯基团含量为15wt％。将组分A和组分B分别混合，并取组分B中8份与上述组分A混合；再按照涂覆厚度0.3mm涂覆于PC薄膜表面，在温度117℃下加热固化18min，得到聚氨酯泡棉。
实施例4
本实施例为A4和B4的组合，其中组分A包括：分子量为8000的氢化聚异戊二烯二醇100份、膨胀微球4.5份、己烷8份、新葵酸锌0.3份、聚硅氧烷0.8份；组分B包括分子量为300的聚对苯二甲酸乙二醇酯二醇100份、二乙醇胺4.5份、甲苯二异氰酸酯148.23份，异氰酸酯基团含量为15wt％。将组分A和组分B分别混合，并取组分B中8份与上述组分A混合；再按照涂覆厚度0.3mm涂覆于PC薄膜表面，在温度118℃下加热固化17min，得到聚氨酯泡棉。
实施例5
本实施例为A5和B5的组合，其中组分A包括：分子量为10000的聚乙烯二醇100份、膨胀微球5份、环己烷10份、异辛酸铋0.3份、聚硅氧烷1.0份；组分B包括分子量为800的聚对苯二甲酸乙二醇酯二醇100份、三乙醇胺5份、苯二亚甲基二异氰酸酯101.99份，异氰酸酯基团含量为15wt％。将组分A和组分B分别混合，并取组分B中5.6份与上述组分A混合；再按照涂覆厚度0.5mm涂覆于铝膜表面，在温度120℃下加热固化15min，得到聚氨酯泡棉。
实施例1至实施例5中组分A和组分B中各成分具体如下表：
Figure BDA0003054313750000071
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Figure BDA0003054313750000081
实施例6
本实施例为A1和B5的组合，其中组分成分参考上文，其他条件和实施例1相同，在此不作一一赘述。
实施例7
本实施例为A2和B4的组合，其中组分成分参考上文，其他条件和实施例1相同，在此不作一一赘述。
实施例8
本实施例为A4和B1的组合，其中组分成分参考上文，其他条件和实施例1相同，在此不作一一赘述。
实施例9
本实施例为A5和B2的组合，其中组分成分参考上文，其他条件和实施例1相同，在此不作一一赘述。
对比例1
本对比例中组分A和组分B的成分与实施例1相同，不同之处在于：本对比例将将组分A和组分B中所有原材料一起搅拌混合。
对比例2
本对比例中组分A和组分B的成分与实施例5相同，不同之处在于：本对比例将将组分A和组分B中所有原材料一起搅拌混合。
对上述实施例和对比例进行压缩测试，压缩测试的方法为：将样品裁切成25mm*50mm，叠加到20mm厚度，压缩75％，于70℃放置120h后，各样品单独放置30min后，再叠加测试厚度变化百分率。结果如下：
Figure BDA0003054313750000091
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本发明制备得到的聚氨酯泡棉，最终聚氨酯分子嵌段有序化排列，且具备微观层次的三级压缩-减震结构，包括发泡剂气化形成的适度开孔减震结构，膨胀后的闭孔膨胀微球在压缩过程对外界应力散点耗散形成的减震结构以及以大分子特殊硬段为“支撑体”，无任何氢键作用的软段为“弹簧簧体”，形成的具备类似于“减震弹簧”的减震结构，共同赋予本发明的聚氨酯泡棉良好的耐压缩性，由压缩测试结果可知：将组分A和组分B分开制备再进行混合，相比组分A和组分B各成分直接混合，聚氨酯泡棉的耐压缩性能大大提高。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，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，均应包含在本发明的保护范围之内。

Claims (8)

1.一种耐压缩聚氨酯泡棉，其特征在于，其原料包括组分A和组分B；其中，
所述组分A包括分子链中不含F、O、N元素的聚二元醇以及膨胀微球、低沸点发泡剂、催化剂、表面活性剂；所述分子链中不含F、O、N元素的聚二元醇为聚丁二烯二醇、氢化聚丁二烯二醇、聚异戊二烯二醇、氢化聚异戊二烯二醇或聚乙烯二醇中的一种；
所述组分B包括二异氰酸酯、扩链剂、交联剂、聚二元醇，其中二异氰酸酯过量，各组分反应后形成预聚体；
组分B中，所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或苯二亚甲基二异氰酸酯中的一种，所述聚二元醇为含苯环结构的聚碳酸酯二醇、聚对苯二甲酸乙二醇酯二醇中的一种；
所述组分A和所述组分B混合后涂覆于高分子材料或金属材料薄膜表面，固化成型后即得到所述聚氨酯泡棉。
2.根据权利要求1所述的耐压缩聚氨酯泡棉，其特征在于，组分A中所述膨胀微球为核-壳结构，其中核芯为低沸点碳氢化合物，壳体为聚苯乙烯类或聚丙烯酸酯类高分子聚合物。
3.根据权利要求1所述的耐压缩聚氨酯泡棉，其特征在于，组分A所述低沸点发泡剂为正戊烷、异戊烷、环戊烷、己烷、异己烷、环己烷中的一种。
4.根据权利要求1或3所述的耐压缩聚氨酯泡棉，其特征在于，组分A所述催化剂为有机金属类催化剂，具体为新葵酸铋、异辛酸铋、新葵酸锌、异辛酸锌中的一种；所述表面活性剂为聚硅氧烷。
5.根据权利要求1所述的耐压缩聚氨酯泡棉，其特征在于，组分B中所述交联剂为二乙醇胺、三乙醇胺、三羟甲基丙烷中的一种。
6.根据权利要求1所述的耐压缩聚氨酯泡棉，其特征在于，所述组分A中的聚二元醇按100份计，膨胀微球添加量为3-5份；低沸点发泡剂添加量为5-10份；催化剂的添加量为0.2-0.3份；表面活性剂的添加量为0.5-1.0份；对应的组分B的添加量为5.6-11.2份。
7.根据权利要求1或6所述的耐压缩聚氨酯泡棉，其特征在于，所述组分B中的交联剂添加量占组分B中聚二元醇质量的3-5wt%，且最终的异氰酸酯基团的含量为15wt%。
8.一种耐压缩聚氨酯泡棉的制备方法，用于制备权利要求1-7任一项所述的耐压缩聚氨酯泡棉，其特征在于，包括如下步骤：
将组分A和所述组分B混合后按照涂覆厚度0.1mm-0.5mm涂覆于高分子材料或金属材料薄膜表面，在115℃~120℃温度下加热固化15min~20min，得到所述聚氨酯泡棉；
所述组分A包括分子链中不含F、O、N元素的聚二元醇以及膨胀微球、低沸点发泡剂、催化剂、表面活性剂；所述分子链中不含F、O、N元素的聚二元醇为聚丁二烯二醇、氢化聚丁二烯二醇、聚异戊二烯二醇、氢化聚异戊二烯二醇或聚乙烯二醇中的一种；
所述组分B包括二异氰酸酯、扩链剂、交联剂、聚二元醇，其中二异氰酸酯过量。
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