CN110003644A - 一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备方法 - Google Patents

一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备方法 Download PDF

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CN110003644A
CN110003644A CN201910203019.9A CN201910203019A CN110003644A CN 110003644 A CN110003644 A CN 110003644A CN 201910203019 A CN201910203019 A CN 201910203019A CN 110003644 A CN110003644 A CN 110003644A
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polyamide
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冯新星
王修行
潘凯
张长琦
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Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
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Abstract

本发明公开了一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备方法。所述制备方法包括如下步骤：(1)聚酰胺弹性体、熔体粘度调节剂、泡孔成核剂和发泡助剂的混合物经挤出机挤出得到发泡颗粒；(2)发泡颗粒、表面活性剂和化学发泡剂于反应釜中混合，于惰性气氛中升温后开始搅拌并保温；继续升温，冲入物理发泡剂使所述反应釜增压，经保温保压后进行泄压，再经冷却定型即得。本发明发泡材料具有回弹性好、泡孔尺寸大小均匀、发泡材料密度低、发泡效果好等优点，同时针对聚酰胺弹性体熔体粘度和熔体强度较低、发泡困难的特点，引入熔体粘度调节剂来改善熔体粘度与强度利于发泡，适合推广使用；同时利用化学与物理发泡的方法，其发气量大，可控性高。

Description

一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备 方法
技术领域
本发明涉及一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备方法，属于高分子发泡材料技术领域。
背景技术
泡状材料是通过在聚合物基体中引入大量的气泡而形成的一种复合材料，这种材料由于具备质轻、比表面积大、比强度高、导热率低、隔热隔音性能好、可吸收冲击载荷等特点，可应用在缓冲材料、包装运输、减震阻尼、鞋底、汽车装饰件等领域，在现实生活中占据着重要的地位。随着科技的发展，研究的深入，目前常用的发泡材料种类越来越多，其中基于聚苯乙烯、聚乙烯、聚丙烯、聚氨酯等的发泡材料应用较广，主要集中在汽车轻量化、建筑、包装、交通运输、工业与农业等领域。现如今随着各行业逐渐追求轻质化，发泡材料在市场上的应用前景越来越广，消费量逐渐加大，发泡材料的制备显得越来越重要。
目前常用发泡材料虽然具备很大的优势，但在实际应用与制备中或多或少存在一定的缺陷，如：聚苯乙烯发泡材料虽具有高的刚性，但是其回弹性低、不易降解；聚氨酯发泡材料虽可具备一定的回弹性与柔性，但在制备过程中会释放异氰酸酯等对人体有害的残留物；聚丙烯与聚乙烯发泡材料韧性较差、耐高温性较差等；这些因素限制了其应用范围。
聚酰胺弹性体由聚酰胺硬段与聚醚或聚酯软段组成，具备塑料与弹性体的双重优势，具有很多材料无法媲美的优势，柔韧性好、比重轻、耐磨耐疲劳、低温特性好等，目前已经成为汽车、航空航天、体育用品、电子机械、渗透分离等领域不可或缺的高附加值材料。但聚酰胺弹性体熔融后粘度与强度相对较差，材料粘度太低不能包裹生长的气泡，易造成气泡合并或破裂，导致发泡成型困难，故需要制备聚酰胺弹性体发泡材料必须解决这一问题。
发明内容
本发明的目的是提供一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备方法，所述热塑性聚酰胺弹性体发泡材料具备质轻、回弹性好、泡孔尺寸大小均匀、发泡材料密度低、发泡效果好等优点，且制备方法简单。
本发明所提供的热塑性聚酰胺弹性体物理化学联合发泡材料的制备方法，包括如下步骤：
(1)聚酰胺弹性体、熔体粘度调节剂、泡孔成核剂和发泡助剂的混合物经挤出机挤出得到发泡颗粒；
(2)所述发泡颗粒、表面活性剂和化学发泡剂于反应釜中混合，于惰性气氛中升温后开始搅拌并保温；继续升温，冲入物理发泡剂使所述反应釜增压，经保温保压后进行泄压，再经冷却定型即得所述热塑性聚酰胺弹性体物理化学联合发泡材料；
升温以使所述化学发泡剂充分发泡，增压以使所述物理发泡剂达到超临界状态。
上述的制备方法中，所述聚酰胺弹性体为由聚酰胺与聚醚或聚酯形成的嵌段共聚物；
所述聚酰胺可为聚酰胺66、聚酰胺6、聚酰胺11、聚酰胺12、聚酰胺1010、聚酰胺1212、聚酰胺1012、聚酰胺1111、聚酰胺1011、聚酰胺1313、聚酰胺1211、聚酰胺1311和聚酰胺1312中的至少一种；
所述聚醚为聚乙二醇、聚丙二醇和聚四氢呋喃醚二醇中至少一种；
所述聚酯为聚己内酯二醇和/或聚碳酸酯型二醇。
所述的制备方法中，所述熔体粘度调节剂可为聚酰胺6、聚酰胺66、聚丙烯、聚乙烯、乙烯-醋酸乙烯共聚物和丙烯腈-丁二烯-苯乙烯共聚物中至少一种，其相对分子量为20000～25000；
所述的制备方法中，所述泡孔成核剂可为滑石粉、纳米二氧化硅、纳米二氧化钛、纳米蒙脱土和纳米碳酸钙中至少一种；
所述发泡助剂可为抗氧剂和/或润滑剂；
所述抗氧剂可为抗氧剂1010、抗氧剂1098和抗氧剂1076中至少一种；
所述润滑剂可为硬脂酸和不饱和脂肪酸锌中至少一种。
所述的制备方法中，所述表面活性剂可为十二烷基硫酸钠、十二烷基苯磺酸钠、月桂醇硫酸钠、平平加O、脂肪醇聚氧乙烯醚硫酸铵(AESA)中至少一种
所述化学发泡剂可为偶氮二甲酰胺、2,2'-偶氮二异丁腈、偶氮二碳酸铵、碳酸氢铵、偶氮胺基苯、二亚硝基五次甲基四胺、苯磺酰肼、对甲基苯磺酰肼和4,4-氧代双苯磺酰肼等中至少一种。
优先偶氮二甲酰胺、2,2'-偶氮二异丁腈和/或4,4-氧代双苯磺酰肼；
所述物理发泡剂可为氮气、氩气、二氧化碳气体、低沸点的卤代烃或脂肪烃等；优选二氧化碳气体；
所述卤代烃可为氯(代)甲烷、二氯甲烷、氯(代)乙烷、氯(代)丙烷、氯(代)丁烷等；
所述脂肪烃可为丙烷、丁烷等。
上述的制备方法中，步骤(1)中，采用双螺杆挤出机进行挤出，所述挤出的条件如下：
转速为50～150转/分钟，工作温度为160～220℃；
所述发泡颗粒为表面光滑的颗粒状，颗粒直径为1～5mm。
上述的制备方法中，步骤(2)中，所述保温的条件如下：
温度为120～150℃，搅拌转速为200～400转/分钟，时间为20～30分钟；
所述保温保压的条件如下：
继续升温到180～200℃，压力为5～25MPa，继续搅拌，时间为0.5～5小时。
上述的制备方法中，所述聚酰胺弹性体、所述熔体粘度调节剂、所述泡孔成核剂、所述发泡助剂、所述表面活性剂与所述化学发泡剂的质量比为：100：5～50：0.5～5：0.2～4：0.5～3：5～20，具体可为100：5～10：0.5～2：2～4：0.5～1.5：10～20、100：10～50：2～5：0.2～2：1.5～3：5～10、100：5～50：0.5～5：0.2～4：0.5～3：5～20、100：5：0.5：4：0.5：20、100：10：2：2：1.5：10或100：50：5：0.2：3：5。
本发明方法制备的热塑性聚酰胺弹性体发泡材料，密度为0.05～0.5g/cm3，泡孔直径为10～200μm。
本发明提供的聚酰胺弹性体物理化学联合发泡材料具有回弹性好、泡孔尺寸大小均匀、发泡材料密度低、发泡效果好等优点，同时针对聚酰胺弹性体熔体粘度和熔体强度较低、发泡困难的特点，引入熔体粘度调节剂来改善熔体粘度与强度利于发泡，适合推广使用；同时利用化学与物理发泡的方法，其发气量大，可控性高。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、
将1000g聚酰胺弹性体(聚酰胺1212和聚四氢呋喃醚二醇共聚弹性体，两者质量比例20：80)、50g聚酰胺6、5g纳米碳酸钙、20g抗氧剂1010、20g硬脂酸混合均匀，然后加入双螺杆挤出机中，控制挤出机螺杆转速为100转/分钟，挤出机工作温度控制在160℃，挤出并造粒，制备符合要求的发泡小颗粒，直径为1mm。
将上述制备得到的发泡小颗粒与5g十二烷基硫酸钠、200g偶氮二甲酰胺加入到高压反应釜中，充氮气置换釜内空气，升温至150℃开始搅拌，控制搅拌速率为200转/分钟，保温20分钟；再升温至200℃，同时通入二氧化碳使釜内压力达到5MPa，继续搅拌，并在此温度与压力下保持5小时后，通过泄压装置快速泄压，并经过冷却定型，最后出料得到热塑性聚酰胺弹性体物理化学联合发泡材料，性能见表1。
实施例2、
将1000g聚酰胺弹性体(聚酰胺66、聚酰胺1010和聚丙二醇共聚弹性体，三者者质量比例7：15：78)、100g聚丙烯、20g纳米蒙脱土、10g抗氧剂1010、10g不饱和脂肪酸锌混合均匀，然后加入双螺杆挤出机中，控制挤出机螺杆转速为50转/分钟，挤出机工作温度控制在220℃，挤出并造粒，制备符合要求的发泡小颗粒，直径为3mm。
将上述制备得到的发泡小颗粒与15g月桂醇硫酸钠、60g偶氮二甲酰胺和40g的4,4-氧代双苯磺酰肼加入到高压反应釜中，充氮气置换釜内空气，升温至120℃开始搅拌，控制搅拌速率为400转/分钟，保温30分钟；再升温至180℃，同时通入氯(代)丙烷使釜内压力达到25MPa，继续搅拌，并在此温度与压力下保持0.5小时后，通过泄压装置快速泄压，并经过冷却定型，最后出料得到热塑性聚酰胺弹性体物理化学联合发泡材料，性能见表1。
实施例3、
将1000g聚酰胺弹性体(聚酰胺1012和聚碳酸酯型二醇共聚弹性体，两者质量比例20：80)、300g聚酰胺66、200g丙烯腈-丁二烯-苯乙烯共聚物、50g纳米二氧化硅、2g抗氧剂1098混合均匀，然后加入双螺杆挤出机中，控制挤出机螺杆转速为150转/分钟，挤出机工作温度控制在200℃，挤出并造粒，制备符合要求的发泡小颗粒，直径为5mm。
将上述制备得到的发泡小颗粒与30g平平加O、25g偶氮二甲酰胺与25g的2,2'-偶氮二异丁腈加入到高压反应釜中，充氮气置换釜内空气，升温至130℃开始搅拌，控制搅拌速率为300转/分钟，保温25分钟；再升温至190℃，同时通入二氧化碳使釜内压力达到15MPa，继续搅拌，并在此温度与压力下保持2小时后，通过泄压装置快速泄压，并经过冷却定型，最后出料得到热塑性聚酰胺弹性体物理化学联合发泡材料，性能见表1。
表1发泡材料性能
由表1中的数据可以看出，本发明制备的材料不仅孔径小、均匀，而且冲击回弹高、强度高，断裂伸长大(断裂伸长率低)。
以上所述实例仅为本发明的举例说明而已，并非用以限定本发明的实质技术内容范围，任何他人在不脱离本发明的内容研究范围情况下，相关技术人员对此所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种热塑性聚酰胺弹性体发泡材料的制备方法，包括如下步骤：
(1)聚酰胺弹性体、熔体粘度调节剂、泡孔成核剂和发泡助剂的混合物经挤出机挤出得到发泡颗粒；
(2)所述发泡颗粒、表面活性剂和化学发泡剂于反应釜中混合，于惰性气氛中升温后开始搅拌并保温；继续升温，冲入物理发泡剂使所述反应釜增压，经保温保压后进行泄压，再经冷却定型即得所述热塑性聚酰胺弹性体发泡材料。
2.根据权利要求1所述的制备方法，其特征在于：所述聚酰胺弹性体为由聚酰胺与聚醚或聚酯形成的嵌段共聚物；
所述聚酰胺为聚酰胺66、聚酰胺6、聚酰胺11、聚酰胺12、聚酰胺1010、聚酰胺1212、聚酰胺1012、聚酰胺1111、聚酰胺1011、聚酰胺1313、聚酰胺1211、聚酰胺1311和聚酰胺1312中的至少一种；
所述聚醚为聚乙二醇、聚丙二醇和聚四氢呋喃醚二醇中至少一种；
所述聚酯为聚己内酯二醇和/或聚碳酸酯型二醇。
3.根据权利要求1或2所述的制备方法，其特征在于：所述熔体粘度调节剂为聚酰胺6、聚酰胺66、聚丙烯、聚乙烯、乙烯-醋酸乙烯共聚物和丙烯腈-丁二烯-苯乙烯共聚物中至少一种。
4.根据权利要求1-3中任一项所述的制备方法，其特征在于：
所述泡孔成核剂为滑石粉、纳米二氧化硅、纳米二氧化钛、纳米蒙脱土和纳米碳酸钙中至少一种；
所述发泡助剂为抗氧剂和/或润滑剂；
所述抗氧剂为抗氧剂1010、抗氧剂1098和抗氧剂1076中至少一种；
所述润滑剂为硬脂酸和/或不饱和脂肪酸锌。
5.根据权利要求1-4中任一项所述的制备方法，其特征在于：所述表面活性剂为十二烷基硫酸钠、十二烷基苯磺酸钠、月桂醇硫酸钠、平平加O、脂肪醇聚氧乙烯醚硫酸铵中至少一种；
所述化学发泡剂为偶氮二甲酰胺、2,2'-偶氮二异丁腈、偶氮二碳酸铵、碳酸氢铵、偶氮胺基苯、二亚硝基五次甲基四胺、苯磺酰肼、对甲基苯磺酰肼和4,4-氧代双苯磺酰肼中至少一种；
所述物理发泡剂为氮气、氩气、二氧化碳气体、低沸点的卤代烃或脂肪烃。
6.根据权利要求1-5中任一项所述的制备方法，其特征在于：步骤(1)中，采用双螺杆挤出机进行挤出，所述挤出的条件如下：
转速为50～150转/分钟，工作温度为160～220℃。
7.根据权利要求1-6中任一项所述的制备方法，其特征在于：步骤(2)中，所述保温的条件如下：
温度为120～150℃，搅拌转速为200～400转/分钟，时间为20～30分钟；
所述保温保压的条件如下：
继续升温到180～200℃，压力为5～25MPa，继续搅拌，时间为0.5～5小时。
8.根据权利要求1-7中任一项所述的制备方法，其特征在于：所述聚酰胺弹性体、所述熔体粘度调节剂、所述泡孔成核剂、所述发泡助剂、所述表面活性剂与所述化学发泡剂的质量比为：100：5～50：0.5～5：0.2～4：0.5～3：5～20。
9.权利要求1-8中任一项所述方法制备的热塑性聚酰胺弹性体发泡材料。
10.根据权利要求9所述的热塑性聚酰胺弹性体发泡材料，其特征在于：所述热塑性聚酰胺弹性体发泡材料的密度为0.05～0.5g/cm3，泡孔直径为10～200μm。
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