CN110564005A - 一种负离子添加剂 - Google Patents

一种负离子添加剂 Download PDF

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CN110564005A
CN110564005A CN201910804170.8A CN201910804170A CN110564005A CN 110564005 A CN110564005 A CN 110564005A CN 201910804170 A CN201910804170 A CN 201910804170A CN 110564005 A CN110564005 A CN 110564005A
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anion
powder
polyurethane
molecular sieve
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丛穆
张宇璇
张斌
郑虹
任晓珊
张明远
滕腾
周宇飞
刘宏宇
任书伯
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FAW Group Corp
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Abstract

本发明公开了一种负离子添加剂，属于汽车内饰材料技术领域，用于添加入合成革材料中，由于负离子粉体的分散及分散稳定性直接影响着负离子产品的最终质量和各种性能，分散均匀程度越高，其质量性能也越好，同时负离子添加剂不能对生产工艺带来负面影响。本发明的设计并制备了一种负离子添加剂，适用于聚氨酯涂料、聚氨酯合成革的生产体系。所发明的负离子添加剂为核壳结构的电气石@13X分子筛，原料中的电气石为粒径6‑20微米粉体，最终产品的粒径为8‑20微米，其在在聚氨酯中的分散基本均匀，制得的负离子聚氨酯革，表面质量无缺陷，断裂强力、断裂伸长率等机械性能保持不变，同时负离子散发量≥3000个/cm3。

Description

一种负离子添加剂
技术领域
本发明属于汽车内饰材料技术领域。
背景技术
负离子粉体即电气石粉具有永久电极的特性，可以在温度和压力的微小变化的情况下引起电势差，使空气电离，其中游离电子会附着于气态水和氧气分子转化成空气负离子。
由于负离子具有净化空气、消除空气中的异味和有害气体,以及缓解疲劳,促进人体的新陈代谢等优点,如开发可以释放负氧离子的合成革,主要用于飞机等狭小密闭空间，此类产生负离子,有利于改善狭小空间的环境,提高驾乘人员感官体验。
一般具有负离子功能的产品采用直接将负离子粉体通过机械力制成超细粉体后，加入生产原料之中。这会导致电气石粉末在高分子聚合物基体中的分散性和稳定性均不能满足实际应用的要求。原因是电气石粉体的表面能大，超细负离子粉末颗粒的表面活性非常高，单个颗粒不能稳定存在，往往会通过相互吸引而团聚，从而降低其表面能来形成稳定状态。而且团聚之后，会导致超细粉体性能的劣化，不利于负离子粉末性能的体现。在应用中电气石粉与高分子聚合物表面性能差异较大，使得它更不易在非极性聚合物中均匀分散和稳定存在，若直接填充于有机物中，易导致材料的某些性能下降，从而影响复合材料的整体综合性能。
目前针对负离子功能产品尤其是负离子合成革等复合材料的开发，基本全部采用电气石、奇冰石粉等材料，加工成超细粉体后直接加入聚氨酯合成体系，以期获得负离子发生效果。但是这种工艺目前存在问题：电气石粉体的表面能大，超细负离子粉末颗粒的表面活性非常高，单个颗粒不能稳定存在，往往会通过相互吸引而团聚，从而降低其表面能来形成稳定状态。而且团聚之后，会导致超细粉体性能的劣化，不利于负离子粉末性能的体现,更容易出现产品质量问题。在应用中电气石粉与高分子聚合物表面性能差异较大，使得它更不易在非极性聚合物中均匀分散和稳定存在，若直接填充于有机物中，易导致材料的某些性能下降，从而影响复合材料的整体综合性能。
发明内容
由于负离子粉体的分散及分散稳定性直接影响着负离子产品的最终质量和各种性能，分散均匀程度越高，其质量性能也越好，同时负离子添加剂不能对生产工艺带来负面影响。据此本发明的设计并制备了一种负离子添加剂，适用于聚氨酯涂料、聚氨酯合成革的生产体系。所发明的负离子添加剂为核壳结构的电气石@13X分子筛，其制备方法如下：
a)通过机械剪切，将电气石制成粒径6-20微米粉体A；
b)将偏铝酸钠、氢氧化钠、硅酸钠、水按照以下摩尔比混合，SiO2:Al2O3＝3～5:1、Na2O:SiO2＝1～1.5:1和H2O:Na2O＝35～65:1，混合均匀后得到溶胶B；
c)粉末A加入溶胶B中，质量比为A:B＝3～5％，继续搅拌均匀后，室温静置3～8h；
d)放入聚四氟乙烯内衬的不锈钢反应釜中，98±2℃下静置5～14h；
e)产物用去离子水洗涤、过滤、烘干，得到电气石@13X分子筛复合材料。
本发明的有益效果：
电气石@13X分子筛复合材料作为负离子添加剂的优异特性来源于其材料特征：外壳为13X分子筛骨架带有负电荷、微孔可以吸附水分子、二氧化碳，有助于电气石产生的游离电子传递到空气分子中，更容易形成负离子；同时表面含有硅羟基、铝羟基，可以和聚氨酯合成原料TDI反应，聚氨酯中加入分子筛粒子后，聚氨酯为连续相，而分子筛粒子被分散在其中，形成“海－岛”结构，在材料受到外力产生裂纹时，分子筛粒子会阻止裂纹向某一方向发展，而将裂纹细化，消耗了能量，延缓了断裂，因而提高了材料的机械强度。同时由于分子筛粒子表面电荷分布不均，使聚氨酯的硬链段结晶形态发生改变，形成小而多的硬段结晶片层，分散在软段中，这类细晶的表面积大，与软段以化学键相联，也可以认为增加了物理交联并改变了应力分布。另外分子筛的微孔可以吸附二氧化碳气体和水分，使聚氨酯/分子筛复合材料中的微气泡孔减少，提高聚氨酯/电气石@13X分子筛复合材料的性能。
由此可见本发明解决了电气石粉体和聚氨酯体系的兼容性问题，可以作为聚氨酯涂料、聚氨酯合成革的负离子添加剂。
附图说明
图1为电气石@13X分子筛复合材料的XRD谱图；
图2为电气石粉体的SEM照片；
图3为电气石@13X分子筛复合材料的SEM照片
图4为电气石@13X分子筛复合材料在PU体系中的分散照片，
具体实施方式
实施例1
a)通过机械剪切，将电气石制成粒径6～20微米粉体A(如图2所示)；
b)将偏铝酸钠、氢氧化钠、硅酸钠、水按照以下摩尔比混合，SiO2:Al2O3＝3～5:1、Na2O:SiO2＝1～1.5:1和H2O:Na2O＝35～65:1，混合均匀后得到溶胶B；
c)粉末A加入溶胶B中，质量比为A:B＝3～5％，继续搅拌均匀后，室温静置3～8h；
d)放入聚四氟乙烯内衬的不锈钢反应釜中，98±2℃下静置5～14h；
e)产物用去离子水洗涤、过滤、烘干，得到电气石@13X分子筛复合材料。
如图1所示，电气石@13X分子筛复合材料的衍射峰分别与电气石和13X分子筛相对应。
如图3所示为电气石@13X分子筛复合材料的SEM照片，所述的电气石@13X分子筛复合材料粒径为8～20微米。对比图2和图3可看出颗粒外表面附着一层新的颗粒状物质致使粒径增大，由此可知该图3中产品为核壳结构。
实施例2
将聚酯多元醇(PEA)或聚醚多元醇(PTMG)或两者按一定的比例计量的混合物加入到备有搅拌器、温度计的三口瓶中，加入150℃，真空干燥9小时后的实施例1所制备的电气石@13X分子筛复合材料，开动真空泵和搅拌器，在真空度为0.09MPa、温度为120℃左右的条件下脱水2～3h。降温至40℃时，加入计量的TDI，搅拌，缓慢升温至80℃，在80-85℃保温反应2h，再于室温下放置4～5h，使其和TDI充分反应后，真空脱泡0.5h左右，制得预聚体，然后加入计量的扩链交联剂3,3′-二氯-4,4′-二氨基二苯甲烷(MOCA)，搅拌均匀，倒入到预热好的模具中，在平板硫化机上于120℃硫化10min，脱模后，在100℃下熟化24h。室温放置7天。
其组成计量比如下：
按照NCO/OH的比值在1.3-1.4之间来计算多元醇和TDI的计量比；MOCA按照-NH2/-NCO为0.9比例加入，电气石@13X分子筛按照聚氨酯质量的3％加入。
如图4可知，电气石@13X分子筛复合材料在聚氨酯中的分散基本均匀,虽然也有个别粒子团聚，但在其中所占比例较少。说明电气石@13X分子筛复合材料在聚氨酯体系下具有良好的分散性。
实施例3
一种革用负离子聚氨酯树脂的面层浆料，按照以下组分按质量份数组成：
水性聚氨酯树脂(科思创：Bayhydrol A 2601)：100份
水：20～40份
水性油墨(BASF：Joncryl 678)：10～30份
负离子添加剂(即电气石@13X分子筛复合材料)：3～5份。
将采用本发明的负离子聚氨酯树脂面层浆料，以干法贴面工艺复合到基布上，速度：8m/min，面层厚度100μm，烘箱温度102℃；制得的负离子聚氨酯革，表面质量无缺陷，断裂强力、断裂伸长率等机械性能保持不变(如下表所示)，同时负离子散发量≥3000个/cm3。

Claims (2)

1.一种负离子添加剂，其特征在于，该负离子添加剂为核壳结构的电气石@13X分子筛，所述的电气石为6-20微米粉体，电气石@13X分子筛为8～20微米颗粒状粉体。
2.如权利要求1所述的负离子添加剂的制备方法，其特征在于，该方法具体步骤如下：
a)通过机械剪切，将电气石制成粒径6-20微米粉体A；
b)将偏铝酸钠、氢氧化钠、硅酸钠、水按照以下摩尔比混合，SiO2:Al2O3＝3～5:1、Na2O:SiO2＝1～1.5:1和H2O:Na2O＝35～65:1，混合均匀后得到溶胶B；
c)粉末A加入溶胶B中，质量比为A:B＝3～5％，继续搅拌均匀后，室温静置3～8h；
d)放入聚四氟乙烯内衬的不锈钢反应釜中，98±2℃下静置5～14h；
e)产物用去离子水洗涤、过滤、烘干，得到电气石@13X分子筛复合材料。
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CN114716732A (zh) * 2022-03-31 2022-07-08 浙江氧倍加新材料科技有限公司 一种石墨烯表面修饰微米级电气石负离子释放功能粉体的制备方法

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