CN107250231A - 用于生产基于热塑性聚氨酯的泡沫的方法 - Google Patents

用于生产基于热塑性聚氨酯的泡沫的方法 Download PDF

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CN107250231A
CN107250231A CN201680009282.9A CN201680009282A CN107250231A CN 107250231 A CN107250231 A CN 107250231A CN 201680009282 A CN201680009282 A CN 201680009282A CN 107250231 A CN107250231 A CN 107250231A
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H·鲁道夫
山本悦弘
E·根岸
野村晃
T·苫多
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Abstract

本发明涉及一种用于生产发泡热塑性聚氨酯颗粒的方法，其包括以下步骤：a)在第一挤出机(E1)中使热塑性聚氨酯熔融，b)在第二挤出机(E2)中注入气体发泡剂，c)在第三挤出机(E3)中将气体发泡剂均匀地浸注到热塑性聚氨酯熔体中，d)将浸注的热塑性聚氨酯熔体通过模板挤出，并且在水下造粒设备中，在温度和压力条件下，对熔体进行造粒，以形成发泡热塑性聚氨酯颗粒。

Description

用于生产基于热塑性聚氨酯的泡沫的方法
本发明涉及由包含发泡剂的聚合物熔体来生产膨胀粒料的方法。热塑性聚合物，特别是热塑性聚氨酯(TPU)的膨胀粒料具有弹性和摩擦特性，因此被广泛地用于各种应用中。热塑性聚氨酯的膨胀粒料的用途的实例包括可重复使用的体操垫、身体保护器、汽车构件(building)中的装饰元件、消音器和减震器、包装或鞋底。对于所有的这些领域，粒料部分的高弹性和良好的均匀性都具有决定性的重要意义。
WO 2007/082838公开了一种生产包含发泡剂的膨胀热塑性聚氨酯的方法。该方法的第一步包括将热塑性聚氨酯挤出成粒料。在第二步骤中，在压力下，将粒料于水性悬浮液中用发泡剂浸渍，并且在第三步骤中使其膨胀。在所述方法的另一个实施方案中，将热塑性聚氨酯与发泡剂一起在挤出机中熔融，并且不使用防止发泡的设备，将熔体进行造粒。在通过挤出生产中，挥发性有机化合物用作发泡剂。
WO 2013/153190涉及一种由含有推进剂的聚合物熔体来生产膨胀颗粒的方法，其包括以下步骤：a)将含有推进剂的聚合物熔体压过温度控制在150℃至280℃的多孔板而进入造粒室；b)采用切割设备，使压过所述温度受控的多孔板的聚合物熔体粉碎成单独的膨胀颗粒；c)利用流体流将颗粒从造粒室排出，其中推进剂含有CO2或N2或CO2和N2的结合，以及使温度控制在10℃至60℃并且具有压力高于环境压力0.7巴至20巴的流体流过造粒室，其中对于造粒室中的流体的压力和温度以及多孔板的温度进行选择，使得流体中的颗粒在压力下通过其所含有的推进剂以产生具有封闭表皮的膨胀颗粒的方式来膨胀。
如果仅使用一个挤出机来生产发泡热塑性聚氨酯颗粒(E-TPU)，则有时难以控制所有的工艺参数(例如温度、压力和转速)，以达到所需的产品特性，例如泡孔尺寸、密度、表皮厚度和独立的泡孔比例。生产过程中的保留时间和转速的变化是受限的。
本发明的目的是解决上述问题，并且提供用于生产发泡热塑性聚氨酯颗粒的精确且灵活的方法。
所述问题通过用于生产发泡热塑性聚氨酯颗粒的方法被解决，所述方法包括以下步骤：
a)在第一挤出机E1中使热塑性聚氨酯熔融，
b)在第二挤出机E2中注入气体发泡剂，
c)在第三挤出机E3中将气体发泡剂均匀地浸注(impregnating)到热塑性聚氨酯熔体中，
d)将浸注的热塑性聚氨酯熔体穿过模板挤出，并且在水下造粒设备中，在温度和压力条件下，对熔体进行造粒，以形成发泡热塑性聚氨酯颗粒。
在步骤a)中，将热塑性聚氨酯在第一挤出机E1中熔融，挤出机E1优选为单螺杆挤出机。通过调节参数(例如温度、压力和转速)，将热塑性聚氨酯(TPU)的熔体粘度控制在一定范围内，以获得适合于气体定量给料的粘度并且稳定地进料到第二挤出机E2中。将挤出机E1仅用于使TPU熔融，这使得可以选择与硬度和分子量无关的多种TPU。
热塑性聚氨酯可为本领域技术人员已知的任何所需的热塑性聚氨酯(TPU)。热塑性聚氨酯及其制造方法已被广泛地记载于例如Gerhard W.Becker和Dietrich Braun，Kunst-stoffhandbuch，第7卷，“Polyurethane”，Carl Hanser Verlag，Munich，Vienna，Vienna，1993中。
在步骤b)中，在第二挤出机E2中，将气体发泡剂注入到热塑性聚氨酯熔体中，挤出机E2优选为双螺杆挤出机。优选使用CO2和/或N2，更优选CO2和N2的结合作为气体发泡剂。另外，可将共发泡剂加入到聚合物熔体中。有用的共发泡剂包括烷烃(例如乙烷、丙烷、丁烷、戊烷)、醇(例如乙醇、异丙醇)、卤代烃或CFC或它们的混合物。单独使用CO2和/或N2及其结合作为发泡剂是特别有利的，因为它们都是不可燃烧的惰性气体，因此在制造中不会产生潜在的爆炸性气氛。将单独的挤出机E2用于注入气体发泡剂，这能够延长气体发泡剂注入时间。
如果不使用步骤c)，则必须通过控制第二挤出机的参数来适当地分散气体发泡剂，并且必须通过调节螺杆形状和控制温度，在第二挤出机E2的后半部分进行冷却。
将三个挤出机E1、E2和E3串联连接，优选挤出机E1直接连接到挤出机E2，并且挤出机E2直接连接到挤出机E3。最优选使用单螺杆挤出机作为挤出机E1和挤出机E3，使用双螺杆挤出机作为挤出机E2。
将气体发泡剂均匀地浸注到热塑性聚氨酯熔体中在第三挤出机E3中进行。通过控制第三挤出机E3的参数，TPU的稳定和冷却通过低旋转和低剪切速率来进行，以获得期望的泡孔尺寸、比重、表皮厚度和独立的泡孔比例，所述第三挤出机E3在特定形状的螺杆中具有冷却单元。将单独的挤出机E3用于将气体发泡剂浸注到热塑性聚氨酯熔体中，这能够使气体在熔融的TPU中更好地扩散。
在步骤d)中，将浸注的热塑性聚氨酯熔体通过模板挤出，并且在水下造粒设备中，在温度和压力条件下，将熔体进行造粒，以形成发泡热塑性聚氨酯颗粒(E-TPU)。
优选地，在步骤d)中所形成的发泡热塑性聚氨酯颗粒的堆积密度范围为30至250kg/m3，优选范围为100至200kg/m3。
优选地，水下造粒设备中，水的压力范围为1至20巴，温度范围为10至50℃，以达到发泡热塑性聚氨酯颗粒所需的堆积密度。
实施例
原料：
Elastollan 1180A(BASF SE的市售TPU)
Elastollan 1196A(BASF Japa的市售TPU)
Elastollan ET880(BASF Japan的市售TPU)
Elastollan SP9324(BASF SE的市售TPU)
交联剂聚醚多元醇-MDI基预聚物
用于TPU成形的粘合剂
C8008C-B：15％/MCP
将下列装配的设备用于实施例1-12：
连接3种不同类型的挤出机且分别连接以下装置；
1.将干燥器连接到第一挤出机。
2.将气体定量给料系统(Gas dosing system)连接到第二挤出机。
3.将水下造粒系统连接到第三挤出机。
在第一挤出机中使TPU熔融，温度条件根据使用的TPU等级进行调整。
使用注射泵将氮气和/或二氧化碳注入第二挤出机(双螺杆挤出机)。
加热器区域C1-C12和AD(接合器)的设定温度
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 AD
200 200 190 190 190 190 190 190 190 190 190 190 190 180 180
控制条件
转速：47rpm
出口压力：7.5MPa
发泡剂：
N2：压力8MPa(0.4至0.5％，相对于TPU)
CO2：压力4MPa(1.1至1.4％，相对于TPU)
将第三挤出机(具有可起冷却作用的四螺纹螺杆的单螺杆挤出机)用于气体在熔融的TPU中的扩散。
加热器区域C1-C4和AD(接合器)的设定温度
螺杆 C1 C2 C3 C4 AD
160 170 190 190 190 180
控制条件
转速：24rpm
入口压力：8MPa
模压：9MPa
水下造粒：
接合器(过滤器和模具之间)和模具的设定温度
接合器 模具
188 200
将下列装配的设备用于比较实施例13-15：
对比实施例例仅使用1个挤出机来实现使TPU熔融、气体定量供给和气体扩散。
加热器区域C1-C12和AD(接合器)的设定温度
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 AD
160 180 190 190 190 190 190 190 190 190 190 190 190 180 180
水下造粒：
接合器(过滤器和模具之间)和模具的设定温度
接合器 模具
188 200
模塑条件：
使用PU粘合剂Elastan C8008使实施例1-15的TPU泡沫颗粒成型，然后在80℃下压制30分钟。将模制品的物理特性总结于表1中。
测试：
根据JIS K 6767测定模制品密度和抗压强度。
根据JIS K 6400测定拉伸强度和断裂伸长率。
根据JIS K 7311测定撕裂强度和回弹性。
测定压缩变形

Claims (5)

1.一种用于生产发泡热塑性聚氨酯颗粒的方法，其包括以下步骤：
a)在第一挤出机E1中使热塑性聚氨酯熔融，
b)在第二挤出机E2中注入气体发泡剂，
c)在第三挤出机E3中将气体发泡剂均匀地浸注到热塑性聚氨酯熔体中，
d)将浸注的热塑性聚氨酯熔体通过模板挤出，并且在水下造粒设备中，在温度和压力条件下，对熔体进行造粒以形成发泡热塑性聚氨酯颗粒。
2.根据权利要求1的所述方法，其中步骤d)中形成的发泡热塑性聚氨酯颗粒的堆积密度范围为30至250kg/m3。
3.根据权利要求1或2的所述方法，其中将CO2、N2或CO2和N2的结合用作气体发泡剂。
4.根据权利要求1至3中任一项所述的方法，其中将单螺杆挤出机用作挤出机E1和挤出机E3，而将双螺杆挤出机用作挤出机E2。
5.根据权利要求1至3中任一项所述的方法，其中水下造粒设备中，水的压力范围为1至20巴并且温度范围为10至50℃。
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