CN105637021B - 膨胀热塑性弹性体的制备方法 - Google Patents
膨胀热塑性弹性体的制备方法 Download PDFInfo
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- CN105637021B CN105637021B CN201480057303.5A CN201480057303A CN105637021B CN 105637021 B CN105637021 B CN 105637021B CN 201480057303 A CN201480057303 A CN 201480057303A CN 105637021 B CN105637021 B CN 105637021B
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Classifications
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- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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Abstract
本发明涉及一种制备膨胀热塑性弹性体的方法,所述方法包括以下步骤:(a)在存在或不存在另一种原料的情况下,将用于制备热塑性弹性体的单体和/或低聚物添加至聚合物加工机的第一阶段中,(b)在聚合物加工机的第一阶段中,将单体和/或低聚物以及任选添加的另一种原料混合并使该单体和/或低聚物反应以产生聚合物熔体,(c)将该聚合物熔体传送至聚合物加工机的第二阶段中,并在存在或不存在另一种原料的情况下添加物理发泡剂以获得包含发泡剂的聚合物熔体,(d)将包含发泡剂的聚合物熔体模塑成膨胀热塑性弹性体。
Description
本发明涉及一种制备膨胀热塑性弹性体、特别是呈粒料形式的膨胀热塑性弹性体的方法。热塑性聚氨酯为用于该方法中的热塑性弹性体的实例。
膨胀热塑性弹性体的用途包括例如制备所有类型的固体发泡材料制品,例如用于体操垫、身体保护装置、汽车构造中的饰板元件、声音及振动吸收器、封装或鞋底。优选步骤为用膨胀弹性体粒料填充模具并施加热量以使各个粒料最初在其表面熔融并从而将其熔合在一起。除简单制品外,可以此方式制备复杂成形的中间体或具有底切的成品模制品。
发泡材料(包括尤其是珠粒泡沫)为人所熟知且已广泛记载于例如Ullmann的Enzyklopadie der technischen Chemie,第4版,第20卷,第416页及以后的文献中。
WO-A 2007/082838公开了一种制备含有发泡剂的膨胀热塑性聚氨酯的方法。该方法的第一步骤包括将热塑性聚氨酯挤出成粒料。在第二步骤中,在压力下在含水悬浮液中用发泡剂浸渍该粒料,并且在第三步骤中进行膨胀。在该方法的另一个实施方案中,将热塑性聚氨酯连同发泡剂一起在挤出机中熔融,并在不使用防止发泡的装置的情况下对熔体进行造粒。未记载热塑性聚氨酯的制备及在相同机器中进一步加工成膨胀热塑性聚氨酯。
可热塑性加工的聚氨酯弹性体的制备已知于例如EP-A 1 213 307。通过其中所记载的方法获得的聚氨酯为致密的且不用于制备膨胀弹性体。
WO-A 2011/005705记载了一种在挤出机中制备发泡聚氨酯的方法。将用于制备聚氨酯的单体引入挤出机的第一部分中并在第二位置处混入发泡剂,之后在真空压力下干预脱挥发。聚合物熔体随后在挤出机中或其下游端发泡且发泡材料被挤出。此处在制备方法中即使微小的变化也可导致不同的泡沫构造,因此若想获得均匀的泡沫,则过程控制必须非常严格。所获得的中间体及成品制品由交联聚氨酯构成,其随后不可能通过热成型或其他热处理来进一步加工。因此,所需中间体或成品制品必须被模塑成最后的最终形状。无法实现具有底切的复杂成形的几何体。
制备可膨胀热塑性聚氨酯粒料材料已知于DE-A 1 300 282。然而,进一步加工需要例如在挤出机中再次熔融,在此情况下发泡通常已在挤出机中发生。特别是,不可能以此方式制备膨胀粒料材料。
WO-A 96/20966记载了一种方法,其中将聚氨酯制备组分在挤出机中混合、施用至带上并在该带上发泡且固化。DE-A 100 56 251记载了另一种制备聚氨酯泡沫的方法,其中在自挤出机出现单体时立即进行固化单体以形成聚氨酯的步骤。WO-A 96/20966和DE-A100 56 251均记载了由热固性聚氨酯组成的泡沫。这些泡沫原则上不可能如同热塑性弹性体一样在模具中进一步加工。值得注意的是,在WO-A 96/20966中获得的聚氨酯泡沫就形状而言是非常有限的,因为带加工仅能够制备块状泡沫(slabstock foam),其不具有所限定的轮廓。这些材料不能被直接模塑成成形制品,而需要例如通过机械加工或切割被进一步加工成中间体或最终制品,在此情况下可能产生大量的废品。记载于该两篇文献中的材料也并非随后可热成型的,因为材料交联并因此不可再被软化。因此,直接模塑复杂成形的成品制品是不可能的,并且由材料后续制备复杂成形的成品制品仅在巨大花费且不便并产生切割废品的情况下是可能的。特别是,在任一情况下均无法获得珠粒。
本发明的目的为提供一种制备膨胀热塑性弹性体的方法,特别是一种制备具有所限定的孔隙率的膨胀粒料材料的方法。
该目的通过一种制备膨胀热塑性弹性体的方法来实现,所述方法包括以下步骤:
(a)在存在或不存在另一种原料的情况下,将用于制备热塑性弹性体的单体和/或低聚物添加至聚合物加工机的第一阶段中,
(b)在聚合物加工机的第一阶段中,将单体和/或低聚物以及任选添加的另一种原料混合,并使单体和/或低聚物反应以产生聚合物熔体,
(c)将聚合物熔体传送至聚合物加工机的第二阶段中,并在存在或不存在另一种原料的情况下添加物理发泡剂以获得包含发泡剂的聚合物熔体,
(d)将包含发泡剂的聚合物熔体模塑成膨胀热塑性弹性体。
本发明的方法提供一种在无其他干预步骤的情况下,由待使用的单体和任选的另一种反应物或原料直接获得包含膨胀热塑性弹性体的发泡中间体制品(例如膨胀粒料材料)的方法。该方法还为改变泡沫结构提供了巨大空间。根据本发明获得的膨胀热塑性弹性体珠粒通过模塑被进一步加工成复杂成形的成品制品,即在无巨大花费或不便且不产生切割废品的情况下。
在步骤(d)中的模塑期间可改变工艺条件以产生不同孔隙率的泡沫和具有不间断表皮的膨胀热塑性弹性体。例如,可因触感原因而需要不间断表皮。不间断表皮还可用于减缓或甚至完全防止湿气进入发泡热塑性弹性体中。
根据本发明,除术语“弹性体”以外,还使用术语“聚合物”,遵循一般语言用法。就通过本发明方法制备的热塑性弹性体的主要组分而言,术语“聚合物”表示热塑性弹性体。
有用的聚合物加工机可包括尤其是螺杆活塞机或熔体泵。还可使用能够制备聚合物及随后的聚合物珠粒的任何其他机器。然而,尤其优选螺杆活塞机。
优选挤出机用作螺杆活塞机以进行本发明的方法。通常,随着单体和/或低聚物的转化率提高,无论使用哪种设备其中的粘度也会提高。
在本发明的一个实施方案中,步骤(b)和(c)在一个设备中进行。在此情况下,第一阶段为螺杆活塞机的第一区段,在该区段中在存在或不存在另一种原料的情况下进行单体和/或低聚物至聚合物的转化,且第二阶段为螺杆活塞机的第二区段,该区段紧邻第一区段的下游并向该区段中注入物理发泡剂。此设备尤其适合于采用挤出机以制备粒料。
或者,还可在步骤(b)中采用第一螺杆活塞机以制备聚合物,并在步骤(c)中采用第二螺杆活塞机以注入物理发泡剂,在此情况下在第一和第二螺杆活塞机之间存在耦合,以使在第一螺杆活塞机中获得的聚合物熔体直接转移至第二螺杆活塞机中。因此,将聚合物熔体供给至第二螺杆活塞机以进行步骤(c),从而避免了熔融聚合物的其他必要步骤。在本文中使用的适当设备的实例为串行式挤出机,其中螺杆活塞机的第一阶段为串行式挤出机的第一挤出机,且螺杆活塞机的第二阶段为串行式挤出机的第二挤出机。
在一个特别优选的实施方案中,双螺杆挤出机用作螺杆活塞机的第一阶段。向此双螺杆挤出机中注入用于制备热塑性弹性体的单体和/或低聚物以及任选的另一种原料。在双螺杆挤出机中,使单体和/或低聚物反应以产生热塑性弹性体。在此情况下,将螺杆活塞机的第一阶段配置为使得滞留时间足以将使用的单体和/或低聚物转化成热塑性弹性体。这可例如通过改变第一阶段的长度、螺杆活塞机中至少一个螺杆的旋转速度以及螺杆的螺纹深度来实现。第一阶段的几何数据及至少一个螺杆的旋转速度决定滞留时间。
在螺杆活塞机的第二阶段中随后添加物理发泡剂。为确保物理发泡剂在聚合物熔体中的均匀分布,螺杆活塞机的第二阶段将包括例如合适的螺杆上的混合单元。此外,本文中还可使用静态混合器。
还可使用熔体泵作为挤出机的替代物。为实现物理发泡剂在聚合物中的均匀分布,优选在进入造粒系统的上游处使熔体泵后接静态混合器。
通常,粒料材料通过将聚合物熔体挤出成线料,随后切割成粒料材料来制备。由于其掺混有物理发泡剂,则自挤出机涌出的聚合物熔体因压力下降而经受膨胀以制备发泡产物,同时造粒,由此制备膨胀粒料材料。
在一个优选的实施方案中,粒料材料通过下列方法获得:在步骤(d)中迫使聚合物熔体通过经温度调节的造粒冲模(pelletizing die);使用切割设备将迫使通过经温度调节的造粒冲模的聚合物熔体切割成各个膨胀的粒料;并使用液体料流将该粒料从造粒室中输出。在此实施方案中,经温度调节的造粒冲模的温度优选在150℃至280℃之间。
为防止聚合物熔体在造粒室中不可控的发泡,并且为获得均匀发泡的粒料材料,有利地向造粒室施加高于环境的压力。进一步尤其优选,使造粒室充满液体,因而将含有发泡剂的热塑性聚合物熔体直接压入液体中。水优选为在造粒室中使用的液体。
为制备具有不间断表皮的膨胀粒料,一个优选的实施方案提供了以料流形式流过造粒室的经温度调节的液体具有10℃至60℃范围内的温度和比环境压力高0.7巴至20巴范围内的压力,同时选择造粒室中的液体的压力和温度以及造粒冲模的温度,使得粒料在加压液体中通过其包含的物理发泡剂膨胀以制备具有不间断表皮的膨胀粒料。
在聚合物加工机中,造粒设备处的所需造粒压力以及熔体的所需温度取决于待加工的弹性体以及所使用的辅助材料和所使用的物理发泡剂。所需压力和所需温度进一步取决于弹性体中组分之间的混合比率。
在造粒室中,将迫使通过经温度调节的造粒冲模的聚合物模塑成线料,切割装置将该线料粉碎成各个膨胀粒料。切割装置可以例如实施为快速旋转刀片。所得粒料的形状取决于造粒冲模中的孔洞的形状和尺寸,以及迫使熔体通过造粒冲模中的孔洞的压力和切割设备的速度。优选选择迫使压力、切割设备的速度和造粒冲模中的孔洞的尺寸,使得粒料的形状基本上为球形。刀片的数目、孔洞的数目与旋转刀片速度之间的关系为本领域技术人员所已知。
使用例如流过造粒室的经温度调节的液体而将粒料从造粒室中输出。选择经温度调节的液体的压力和温度,使得聚合物线料/粒料通过其包含的物理发泡剂以可控的方式膨胀,从而在粒料的表面上形成不间断表皮。
使粒料连同经温度调节的液体一起流入例如干燥器中,在该干燥器中粒料与液体分离。已制备的膨胀粒料可被收集在容器中,同时将液体过滤并通过泵送回到造粒室中。
在液体温度处于控制下的加压液体中进行造粒可防止含有发泡剂的聚合物熔体产生不可控的膨胀,其中可使不间断表皮无法形成。此类珠粒起初会具有低的堆积密度,但会快速地各自再次塌陷。结果为具有高堆积密度和低弹性的不均匀珠粒。本发明的方法以可控方式减缓粒料的膨胀来制备具有不间断表皮和内部多孔状结构的均匀结构化颗粒,其中在表面处泡孔尺寸较小并朝向中心增大。在中心处的泡孔尺寸小于250μm,优选小于100μm。膨胀粒料的堆积密度通常在30g/l至250g/l范围内且优选在80g/l至140g/l范围内。
通过控制造粒室中经温度调节的液体的压力和温度以及通过控制造粒冲模的温度来管理粒料膨胀。当粒料膨胀过快和/或以不可控方式膨胀时,意味着未形成不间断表皮,造粒室中的液体的压力升高和/或造粒室中经温度调节的液体的温度下降。粒料周围的经温度调节的液体的压力升高抵消物理发泡剂的膨胀效果并抑制粒料的膨胀。降低造粒室中经温度调节的液体的温度导致珠粒上更厚的表皮并因此提供更多的膨胀阻力。当经温度调节的液体相对于所使用的物理发泡剂处于过高压力或过低温度时,粒料的膨胀可被过度阻碍或甚至完全停止,从而制备堆积密度过高的粒料。在此情况下,使造粒室中经温度调节的液体的压力下降和/或经温度调节的液体的温度升高。
优选在流过造粒室的经温度调节的液体中的压力介于0.7巴至20巴之间时,由含有发泡剂的聚合物熔体制备膨胀粒料。液体中的压力更优选在5巴至15巴之间,甚至更优选在10巴至15巴之间。
作为调节造粒室中经温度调节的液体的压力和/或温度的附加方案或替代方案,还可通过经温度调节的造粒冲模的温度来影响粒料的膨胀。降低经温度调节的造粒冲模的温度具有将来自聚合物熔体的热量更快速地释放至环境中的效果。此有助于形成不间断表皮,该不间断表皮为稳定发泡粒料的前提条件。如果经温度调节的造粒冲模和/或造粒室中的液体的温度过低,则聚合物熔体将冷却过快,并可在充分膨胀之前开始固化。粒料通过其包含的物理发泡剂的膨胀受到如此严重的阻碍以致于形成具有过高堆积密度的粒料。因此,在此情况下,将造粒室中经温度调节的液体的温度和/或经温度调节的造粒冲模的温度升高。
造粒室中液体的温度优选在10℃至60℃之间,以使粒料可进行受控的膨胀,其中形成不间断的发泡表皮。液体的温度优选在25℃至45℃之间。经温度调节的造粒冲模的温度优选在150℃至280℃之间,更优选在220℃至260℃之间,甚至更优选在245℃至255℃范围内。
造粒冲模部分上的过度温度导致珠粒表面上的较薄表皮及随后的表面塌陷。造粒冲模部分上的过低温度降低膨胀程度并导致珠粒上形成较厚的未发泡表面。
使用本发明的方法获得的粒料材料的珠粒重量优选在1mg至40mg范围内。膨胀热塑性弹性体的密度优选在30g/l至350g/l范围内。
根据本发明,术语物理发泡剂描述发泡剂,其化学结构在膨胀过程期间保持不变、其聚集状态在膨胀过程期间可改变,并且其在膨胀过程中为气态。发泡剂例如记载于由Richard Gendron编辑的Thermoplastic Foam Processing Principles andDevelopment,CRC Press,2005中。
在一个优选的实施方案中,物理发泡剂包括二氧化碳、氮气或二氧化碳与氮气的混合物。在本文中,可使用氮气与二氧化碳的任何所需混合物。然而,优选将含有50重量%至100重量%的二氧化碳和0重量%至50重量%的氮气的二氧化碳与氮气的混合物用作发泡剂。替代性地或另外地,发泡剂还可包括有机发泡剂,例如烷烃、卤代烃或其混合物。就此而言,有用的烷烃包括例如乙烷、丙烷、丁烷和戊烷。单独使用CO2和/或N2以及其组合作为发泡剂而不添加另一种发泡剂是尤其有利的,因为其为不可燃的惰性气体,所以在制造中不可能产生潜在爆炸性环境。这使得成本密集型安全防护措施变得不必要并极大地降低了制造中的潜在风险。同样有利的是无需在将产品运送出去之前储存产品以使可燃性挥发物呈气体放出。
向包含发泡剂的聚合物熔体中另外添加一种以上的成核剂产生另一个优点。有用的成核剂尤其包括各自单独地或呈任何混合物形式的滑石、氟化钙、苯基次膦酸钠、氧化铝、碳黑、石墨、颜料和细分散的聚四氟乙烯。尤其优选滑石用作成核剂。成核剂占热塑性模塑组合物或聚合物熔体的总质量的比例优选在0重量%至4重量%范围内且尤其在0.1重量%至2重量%范围内。成核剂可在第一阶段中或在第二阶段中添加。
可例如使用气体或液体进料单元(取决于物理发泡剂的物理状态)将物理发泡剂经由喷射阀添加至聚合物加工机中。
用于制备膨胀粒料材料的热塑性弹性体选自例如热塑性聚酯弹性体(例如聚醚酯或聚酯酯)、热塑性共聚酰胺(例如聚醚共聚酰胺)或苯乙烯嵌段共聚物(例如苯乙烯丁二烯嵌段共聚物)。热塑性弹性体尤其优选为热塑性聚氨酯。
除反应产生热塑性弹性体的单体和/或低聚物之外,还可添加其他原料。其他原料的混合物可用于调节弹性体的物理和/或化学特性。此外,催化剂也可任选地作为另一种原料添加以催化单体和/或低聚物的反应从而产生聚合物。
其他添加剂可选自例如成核剂、表面活性物质、填料、阻燃剂(例如含磷系统)、成核剂、氧化稳定剂、另外的其他稳定剂(例如抗水解、光、热或变色),增强剂和增塑剂、增滑剂和脱模助剂、染料和颜料以及其任何所需混合物。当使用填料时,这些填料可为有机和/或无机粉末或纤维材料以及其混合物。填料的平均粒径或(在纤维填料的情况下)长度应为泡孔尺寸以下。优先0.1μm至100μm范围内,优选1μm至50μm范围内的平均粒径或平均纤维长度。
当使用热塑性聚氨酯时,热塑性聚氨酯可为本领域技术人员已知的任何所需热塑性聚氨酯。热塑性聚氨酯及其制备方法广泛记载于例如Gerhard W.Becker和DietrichBraun,Kunststoffhandbuch,第7卷,Polyurethane,Carl Hanser Verlag,Munich,Vienna,1993中。
在一个优选的实施方案中,通过使异氰酸酯与作为单体或低聚物的分子量优选为0.5kg/mol至10kg/mol的异氰酸酯反应性化合物及任选地分子量优选为0.05kg/mol至0.5kg/mol的增链剂的混合物反应来制备热塑性聚氨酯。在另一个优选的实施方案中,通过另外向混合物中添加至少一种链转移剂、催化剂和任选地至少一种填料、助剂和/或掺合剂来制备热塑性聚氨酯。
热塑性聚氨酯的制备需要呈任何比率的异氰酸酯和异氰酸酯反应性化合物的混合物。任选地另外添加增链剂、链转移剂、催化剂及填料、助剂和/或掺合剂且可单独或以所有可能的变化形式进行。
优选的实施方案使用脂族、脂环族和/或芳族异氰酸酯作为有机异氰酸酯。特别优先使用芳族、脂族和/或脂环族二异氰酸酯。优选的二异氰酸酯的实例为三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、七亚甲基二异氰酸酯、八亚甲基二异氰酸酯、2-甲基-1,5-五亚甲基二异氰酸酯、2-乙基-1,4-亚丁基二异氰酸酯、1,5-五亚甲基二异氰酸酯、1,4-亚丁基二异氰酸酯、1-异氰酸基-3,3,5-三甲基-5-异氰酸基甲基环己烷、1,4-双(异氰酸基甲基)环己烷、1,3-双(异氰酸基甲基)环己烷、1,4-环己烷二异氰酸酯、1-甲基-2,4-环己烷二异氰酸酯、1-甲基-2,6-环己烷二异氰酸酯、2,2'-二环己基甲烷二异氰酸酯、2,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、1,5-亚萘基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、3,3'-二甲基联苯二异氰酸酯、1,2-二苯基乙烷二异氰酸酯和亚苯基二异氰酸酯。
除异氰酸酯之外,热塑性模塑组合物还由具有至少两个异氰酸酯反应性的含氢基团的化合物构成。异氰酸酯反应性的含氢基团优选为羟基。特别优选具有至少两个异氰酸酯反应性的含氢基团的化合物选自聚醚醇、聚酯醇和聚碳酸酯二醇。在本上下文中,聚酯醇、聚醚醇和/或聚碳酸酯二醇通常也包含在术语“多元醇(polyol)”内。
优选由聚醚醇制备热塑性聚氨酯。在本文中尤其优选使用聚醚二醇。聚四氢呋喃为特别优选的聚醚二醇。优选使用聚醚醇,例如分子量在0.6kg/mol至2.5kg/mol之间的聚四氢呋喃。单独地或以多种聚醚醇的混合物形式使用聚醚醇。
在一个替代性实施方案中,使用聚酯醇来制备热塑性聚氨酯。在一个优选的实施方案中,为此使用聚酯二醇。优选由己二酸和1,4-丁二醇制备聚酯二醇。聚酯醇的优选实施方案的分子量在0.6kg/mol至2.5kg/mol之间。
在其他优选的实施方案中,用于制备热塑性聚氨酯的多元醇的分子量为0.5kg/mol至8kg/mol,更优选0.6kg/mol至6kg/mol,且尤其是0.8kg/mol至4kg/mol。在其他优选的实施方案中,多元醇的平均官能度为1.8至2.3,更优选1.9至2.2,且尤其是2。在特别优选的实施方案中,多元醇为聚酯醇,在另一个优选的实施方案中,优选由聚四氢呋喃合成且具有的分子量在0.6kg/mol至2.5kg/mol之间。
当使用增链剂制备热塑性聚氨酯时,这些增链剂优选为脂族、芳族和/或脂环族化合物,在其他优选的实施方案中,其具有的分子量为0.05kg/mol至0.5kg/mol。增链剂为例如具有两个官能团的化合物,例如在亚烷基部分具有2至10个碳原子的二胺和/或烷二醇,尤其1,4-丁二醇、1,6-己二醇和/或具有3至8个碳原子的二-、三-、四-、五-、六-、七-、八-、九-和/或十烷二醇及相应的低聚二醇和/或聚丙二醇。制备热塑性聚氨酯的其他实施方案使用增链剂的混合物。
当使用链转移剂时,这些链转移剂的分子量通常为0.03kg/mol至0.5kg/mol。链转移剂为仅具有一个与异氰酸酯相关的官能团的化合物。链转移剂的实例为单官能醇、单官能胺,优选为甲胺和/或单官能多元醇。链转移剂可用于具体控制各个组分的混合物的流动特征。在优选的实施方案中,链转移剂的用量为0重量份至5重量份,更优选0.1重量份至1重量份,基于100重量份的具有至少两个异氰酸酯反应性的含氢基团的化合物计。除增链剂之外还可使用链转移剂,或替代增链剂使用。
其他实施方案使用至少一种催化剂来制备热塑性聚氨酯以尤其催化二异氰酸酯的异氰酸酯基团与异氰酸酯反应性化合物(优选具有至少两个异氰酸酯反应性的含氢基团的化合物、链转移剂和增链剂的羟基)之间的反应。在优选的实施方案中,催化剂选自叔胺,例如三乙胺、二甲基环己胺、N-甲基吗啉、N,N'-二甲基哌嗪、2-(二甲基胺基乙氧基)乙醇、二氮杂双环(2,2,2)辛烷及类似物质。在其他优选的实施方案中,至少一种催化剂选自有机金属化合物,并且例如提及的有钛酯、铁化合物(例如乙酰基丙酮酸铁(III))、锡化合物(例如二乙酸锡、二辛酸锡、二月桂酸锡或脂族羧酸的锡二烷基盐,诸如二乙酸二丁基锡、二月桂酸二丁基锡等)。
一些实施方案单独地使用催化剂,而其他实施方案使用催化剂的混合物。在一个优选的实施方案中,使用的催化剂为量为0.0001重量%至0.1重量%的催化剂的混合物,基于具有至少两个异氰酸酯反应性的含氢基团的化合物(优选多羟基化合物)计。
有用的助剂和/或掺合剂包括例如水解控制剂和阻燃剂。其他掺合剂和助剂可见于标准参考文献著作,例如上文所引用的Gerhard W.Becker和Dietrich Braun,Kunststoffhandbuch,第7卷,Polyurethane,Carl HanserVerlag,Munich,Vienna,1993。
除催化剂之外,以及在未使用催化剂的情况下,也可将水解控制剂(例如聚合物和低分子量碳二亚胺)添加至异氰酸酯和具有至少两个异氰酸酯反应性的含氢基团的化合物中来制备热塑性聚氨酯。
在另一个实施方案中,热塑性聚氨酯可包括磷化合物。
为设定热塑性聚氨酯的肖氏硬度(Shore hardness),具有至少两个异氰酸酯反应性的含氢基团的化合物和增链剂可在相对宽的摩尔比内变化。在优选的实施方案中,具有至少两个异氰酸酯反应性的含氢基团的化合物与所使用的总增链剂的摩尔比在10:1至1:10范围内,优选在5:1至1:8范围内,且更优选在1:1至1:4范围内,热塑性聚氨酯的硬度随着增链剂的含量提高而提高。肖氏硬度优选在A44至D30范围内,更优选在A62至A95范围内,最优选在A62至A85范围内。对于致密(即未膨胀)的热塑性聚氨酯而言,肖氏硬度根据DIN53505测定。
在其他优选的实施方案中,以常规指数进行形成热塑性聚氨酯的反应。指数定义为反应中使用的芳族、脂族和/或脂环族二异氰酸酯的异氰酸酯基团的总数与具有至少两个异氰酸酯反应性的含氢基团的化合物和增链剂中异氰酸酯反应性基团的总数(即,活性氢的数目)的比率。指数100意指芳族、脂族和/或脂环族二异氰酸酯的每个异氰酸酯基团存在一个活性氢原子,即,具有至少两个异氰酸酯反应性的含氢基团的化合物和增链剂的异氰酸酯反应性官能团。指数大于100意指存在的异氰酸酯基团大于存在的异氰酸酯反应性基团(例如羟基)。
在特别优选的实施方案中,形成热塑性聚氨酯的反应在介于60至120之间的指数下进行,更优选在介于80至110之间的指数下进行。
此外,热塑性模塑组合物可任选地包含至少一种添加剂。术语添加剂包括填料、助剂和掺合物以及上述链转移剂、增链剂和催化剂。添加剂可以以任何所需的混合物形式使用。添加剂占热塑性模塑组合物的总质量的分数优选在0重量%至80重量%范围内。
根据本发明,将用于制备热塑性聚氨酯的物质添加至聚合物加工机的第一阶段中。可将该物质通过在入口处的联合进料口添加至聚合物加工机中,或通过沿着聚合物加工机(尤其螺杆活塞机)的长度分布的两个以上的进料口添加至聚合物加工机中。优选首先添加单体和/或低聚物以及任选所需的催化剂,且在至少部分的单体和/或低聚物已反应产生聚合物后,在后续入口处加入用于设定聚合物特性的其他添加剂。
双螺杆挤出机为合适的用于制备膨胀粒料材料的聚合物加工机的实例。选择双螺杆挤出机的长度,使得单体和/或低聚物反应以产生聚合物的区域之后可为压力建立区域。为此,尤其有利的是在第二阶段的下游端的上游选择长度,使得压力可沿至少15L/D的长度建立,其中L/D描述长度与直径的比率。至少一个限制性输送元件或捏合元件,优选两个至三个限制性传输元件或捏合元件可用于将反应区域与压力建立区域彼此隔开。可例如通过螺杆元件的构造、过程参数(诸如螺杆速度)和/或在挤出机下游使用齿轮泵来确保在单体与/或低聚物之间的反应下游建立压力。此在双螺杆挤出机中产生不低于50巴,优选比环境压力高60巴至100巴的压力。在此压力主导的区域中,例如使用气体计量单元通过喷射阀添加物理发泡剂。在添加后,混合元件将物理发泡剂与聚合物熔体沿不小于5L/D,优选不小于10L/D的长度均匀地混合。为输送含有发泡剂的熔体,可进一步在双螺杆挤出机的至少一个螺杆上提供输送元件。
在一个替代性的实施方案中,聚合物加工机的第一阶段后接具有用于物理发泡剂的进料口的熔体通道作为第二阶段。在此情况下,第二阶段还包括熔体泵和静态混合器。熔体通道为例如可加热管道,聚合物熔体流过该可加热管道并且可向该可加热管道中导入物理发泡剂。可同样为此提供喷射阀及用于添加发泡剂的气体计量单元。熔体泵建立迫使含有所添加的物理发泡剂的聚合物熔体通过静态混合器和造粒工具所需要的必要压力。熔体泵可位于熔体通道与静态混合器之间,或者在第一阶段与熔体通道之间。当熔体泵安置在熔体通道与静态混合器之间时,有必要配置第一阶段以使得在单体和/或低聚物反应产生聚合物的过程中增大第一阶段中的压力,并进一步使得该压力还足以使聚合物熔体通过熔体通道输送。此外,为此有必要将熔体通道直接或经由管道线连接至第一阶段。
静态混合器用于将物理发泡剂均匀地分布于聚合物熔体中。为防止聚合物熔体的固化,静态混合器优选经加热且由例如具有至少1L/D的制程长度,优选至少5L/D的长度的混合元件构成,并且如此配置以使得聚合物熔体的停留时间大于0.5秒,优选大于3秒。
双螺杆挤出机或静态混合器随后为合适的用于制备粒料材料的系统,尤其是后接造粒装置。
实施例
实施例1
在距离用作反应挤出机以混合并合成热塑性聚氨酯的Coperion GmbH ZSK43双螺杆挤出机的加工部分的上游端6L/D的部位,添加2mol的4,4'-二苯基甲烷二异氰酸酯、1mol的摩尔质量为1000g/mol的聚丁二醇、1mol的1,4-丁二醇以及0.2重量份的滑石成核剂和30ppm的二辛酸亚锡(II)催化剂,在180℃至220℃之间的温度下混合并使其反应。选择6L/D的距离以防止回流单体进入驱动单元。螺杆再次夹带回流单体以沿输送方向运输。
将反应混合物从反应挤出机中转移至用作主挤出机的Coperion GmbH ZSK92双螺杆挤出机中。主挤出机的进料斗位于距离加工部分的上游端6L/D处。在主挤出机中,在200℃至240℃范围内的温度下进一步向前驱动反应。在距离主挤出机的下游端15L/D的部位,使用气体计量站将用作物理发泡剂的0.2重量份的氮气和1.5重量份的二氧化碳喷射至聚合物熔体中。熔体泵迫使含有发泡剂的聚合物熔体在200℃下通过经温度调节的造粒冲模进入其中有水流流过的造粒室。造粒冲模中的孔洞的直径为1.8mm。造粒室中的旋转刀片在造粒冲模的表面将聚合物熔体切碎成珠粒重量为20mg的粒料。压力为10巴且温度为30℃的水将粒料从造粒室中输出并将其输送至离心干燥器中。在离心干燥器中,将粒料与水分离并干燥。由此获得的膨胀粒料材料的堆积密度为140g/l。
实施例2
重复实施例1,不同之处在于所使用的物理发泡剂为0.2重量份的氮气和2重量份的二氧化碳。造粒冲模中的孔洞的直径为2.4mm。流过造粒室的水具有5巴的压力和20℃的温度。以此方式获得的粒料的珠粒重量为32mg且堆积密度为120g/l。
实施例3
重复实施例1,不同之处在于所使用的物理发泡剂为0.3重量份的氮气和2.5重量份的二氧化碳。主挤出机后接熔体通道,向该熔体通道中喷射物理发泡剂。熔体通道后接熔体泵,从而迫使含有物理发泡剂的聚合物熔体在240℃下进入经温度调节的静态混合器,其用作分散组件。静态混合器后接造粒冲模,其具有直径为1毫米的孔洞,且通过该造粒冲模将聚合物熔体压入造粒室中。将由此获得的粒料材料调节为5mg的珠粒重量。流过造粒室的水具有20巴的压力和35℃的温度。由此获得的粒料材料的堆积密度为100g/l。
Claims (15)
1.一种制备膨胀热塑性弹性体的方法,所述方法包括以下步骤:
(a)在存在或不存在另一种原料的情况下,将用于制备热塑性弹性体的单体和/或低聚物添加至聚合物加工机的第一阶段中,
(b)在聚合物加工机的第一阶段中,将所述单体和/或低聚物以及任选添加的另一种原料混合,并使所述单体和/或低聚物反应以产生聚合物熔体,
(c)将所述聚合物熔体传送至聚合物加工机的第二阶段中,并在存在或不存在另一种原料的情况下添加物理发泡剂以获得包含发泡剂的聚合物熔体,
(d)将包含发泡剂的聚合物熔体模塑成膨胀热塑性弹性体。
2.权利要求1的方法,其中所述聚合物加工机为螺杆活塞机。
3.权利要求2的方法,其中螺杆活塞机的第一阶段和螺杆活塞机的第二阶段为挤出机的区段。
4.权利要求2的方法,其中螺杆活塞机的第一阶段为串列式挤出机的第一挤出机,且螺杆活塞机的第二阶段为串列式挤出机的第二挤出机。
5.权利要求2的方法,其中聚合物加工机的第二阶段包含熔体泵,任选地具有熔体筛或静态混合器。
6.权利要求1的方法,其中所述膨胀热塑性弹性体为膨胀粒料材料。
7.权利要求6的方法,其中所述粒料材料通过以下方法来获得:在步骤(d)中迫使所述聚合物熔体通过温度调节在150℃至280℃范围内的造粒冲模;使用切割设备将迫使通过经温度调节的造粒冲模的聚合物熔体切割成各个膨胀粒料;并使用液体料流从造粒室中输出所述粒料。
8.权利要求7的方法,其中以料流形式流过造粒室的经温度调节的液体具有介于10℃至60℃范围内的温度和比环境压力高0.7巴至20巴范围内的压力。
9.权利要求6的方法,其中所述膨胀粒料材料的珠粒重量在1mg至40mg范围内。
10.权利要求1的方法,其中所述发泡剂包括二氧化碳、氮气或二氧化碳与氮气的混合物。
11.权利要求10的方法,其中所述发泡剂包含50重量%至100重量%的二氧化碳和0重量%至50重量%的氮气且无其他发泡剂。
12.权利要求1的方法,其中所述发泡剂包括选自烷烃、卤代烃或其混合物的有机发泡剂。
13.权利要求1的方法,其中所述热塑性弹性体为热塑性聚氨酯。
14.权利要求1的方法,其中所述膨胀热塑性弹性体的密度在30g/l至350g/l范围内。
15.权利要求1的方法,其中所述膨胀热塑性弹性体具有不间断表皮。
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-
2014
- 2014-10-01 TW TW103134155A patent/TWI667285B/zh not_active IP Right Cessation
- 2014-10-17 PL PL14786180T patent/PL3058018T3/pl unknown
- 2014-10-17 CN CN201480057303.5A patent/CN105637021B/zh not_active Expired - Fee Related
- 2014-10-17 US US15/029,686 patent/US11142625B2/en active Active
- 2014-10-17 ES ES14786180.1T patent/ES2651851T3/es active Active
- 2014-10-17 WO PCT/EP2014/072309 patent/WO2015055811A1/de active Application Filing
- 2014-10-17 BR BR112016008207-9A patent/BR112016008207B1/pt not_active IP Right Cessation
- 2014-10-17 JP JP2016524415A patent/JP6496722B2/ja not_active Expired - Fee Related
- 2014-10-17 EP EP14786180.1A patent/EP3058018B1/de not_active Revoked
- 2014-10-17 KR KR1020167013113A patent/KR102374907B1/ko active IP Right Grant
- 2014-10-17 PT PT147861801T patent/PT3058018T/pt unknown
Also Published As
Publication number | Publication date |
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PL3058018T3 (pl) | 2018-02-28 |
KR20160073996A (ko) | 2016-06-27 |
TWI667285B (zh) | 2019-08-01 |
ES2651851T3 (es) | 2018-01-30 |
KR102374907B1 (ko) | 2022-03-16 |
WO2015055811A1 (de) | 2015-04-23 |
EP3058018B1 (de) | 2017-09-13 |
JP6496722B2 (ja) | 2019-04-03 |
CN105637021A (zh) | 2016-06-01 |
US20160244587A1 (en) | 2016-08-25 |
EP3058018A1 (de) | 2016-08-24 |
JP2016533418A (ja) | 2016-10-27 |
TW201527421A (zh) | 2015-07-16 |
BR112016008207B1 (pt) | 2022-02-22 |
PT3058018T (pt) | 2017-12-21 |
BR112016008207A2 (zh) | 2017-08-01 |
US11142625B2 (en) | 2021-10-12 |
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