CN102939329B - 生产发泡pvc的改进方法与由其获得的基于发泡pvc的塑料材料 - Google Patents

生产发泡pvc的改进方法与由其获得的基于发泡pvc的塑料材料 Download PDF

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CN102939329B
CN102939329B CN201180028721.8A CN201180028721A CN102939329B CN 102939329 B CN102939329 B CN 102939329B CN 201180028721 A CN201180028721 A CN 201180028721A CN 102939329 B CN102939329 B CN 102939329B
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L·劳里
E-L·M·彼得森
R·布雷山
S·M·哈米德
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Abstract

包括在封闭模具中加热聚合物混合物物质(13)的类型的制造发泡PVC的方法，所述方法包括：(a)控制由于在具有由所述封闭模具(10)限定的恒定体积的环境中热模制过程造成的所述物质(13)的膨胀，所述控制通过在所述在聚合物混合物物质(13)中存在可压缩材料的微粒来获得，所述可压缩材料的微粒适于在通过该物质(13)中的发泡气体微孔(20)的形成和膨胀所产生的压力作用下从体积较大的初始形式(A)收缩到体积较小的形式(B)；和(b)使模制的膨胀材料中含有的所述微粒(16)从它们的构型B膨胀到体积较大的初始构型(A)，由此获得的所述膨胀的材料的密度上述所得发泡性材料的密度由所述膨胀的材料的物质(13c)同时存在的发泡气体微孔(20)和具有它们较大体积的构型(A)的所述微粒(16)确定。相较制造发泡塑料材料的已知技术，本发明的方法不仅避免了成型方法中熔融体流失的形成，还使获得的发泡PVC具有期望的密度值，但只使用比此类现有方法中使用的量少得多的化学发泡剂。

Description

生产发泡PVC的改进方法与由其获得的基于发泡PVC的塑料材料
本发明涉及制造发泡PVC的改进方法，尤其是由聚酰胺、聚酰亚胺、聚氯乙烯、多异氰和聚脲组成的IPN(互穿网络)聚合物泡沫体。
本发明的领域是用于制备发泡PVC的方法，该方法包括加热在盖子封闭的恒定体积模具中的起始混合物，以及随后使所获得的胚料膨胀。
特别是在由聚酰胺-聚酰亚胺-聚氯乙烯-多异氰和聚脲组成的IPN聚合物泡沫体的制造中(参见D.Klempner,L.H.Sperling,L.A.Utracki在“Interpenetrating Polymer Networks”，vol239；AmericanChemical Society；Ed.1994中对IPN概念的描述)，聚合、表面活性剂、化学发泡剂、异氰酸酯等的的初始混合物被注入模具。一旦模具通过合适的盖子封闭，将混合物加热，由此产生吹泡气体，聚合物凝胶并发生期望的交联反应，气体进入由此获得的交联IPN分子内。该方法的这部分具体来说发生在封闭的模具内并处于恒定反应体积，通过气体的形成和热膨胀在模具内产生压力。
然而，此处所述的已知技术存在弊端：由于通过吹泡气体的形成和塑料材料的加热引起的膨胀，聚合物熔体与试剂的物质往往会膨胀，与由封闭模具的盖子施加的作用相反。因此，该压缩的熔融物质往往会膨胀，从模具上盖子的封闭区域泄漏。结果，在采用此种成型技术的传统制造方法中，会形成大量废料，导致总体生产成本不期望地增加，而且还带来与机械和环境冲击相关的维护问题。
除这些缺陷之外，还存在成品的微孔结构劣化，尤其是与模具中塑料材料的渗漏相关。
制造发泡PVC的现有方法的另一缺点在于使用的大量化学发泡剂，这除了对环境有危害，而且还由于这些产品的制造、运输和储存复杂性而昂贵。
出版物EP 2039496 Al披露了制造橡胶的方法，其使用微球，它适于在硫化模具中起始混合物体积增加的作用下被破碎。根据该与发泡塑料材料无关的已知技术，模制的产品将微球以它们最终的并且必然是破碎的或坍塌的状态掺入，这也是基于橡胶的最终产品的状态。
因此，本发明的主要目的是提供一种制造发泡PVC、尤其是IPN聚合物泡沫体的新方法，其中，除了避免了成型过程期间熔融产物的损失，还甚至可以以比已知技术中用量少得多的化学发泡剂量来获得具有期望密度值的发泡PVC。
本发明的另一目的是提供一种上述类型的方法，其能够显著减少成型阶段出口处的废品，因而使总体工厂管理成本和塑料材料生产对环境的冲击都最小化。
本发明的目的还在于，通过避免与模具封闭区域相关的塑料材料微孔结构的强劣化，提高最终产品的质量。
这些和其它目的分别通过权利要求1的方法得以实现。本发明的优选实实施方式在其余权利要求中表示。
相较生产发泡塑料材料的已知技术，本发明的方法不仅避免了在成型期间熔融产品的损失，而且还使获得的发泡PVC具有期望的密度值，但使用的化学发泡剂量比此类现有方法中使用的那些低得多。
尤其是，由于本发明方法中使用的化学发泡剂量显著减少，本发明的方法不但减少了该类产品对环境的破坏，亦降低了发泡塑料材料的生产成本，因为化学发泡剂的生产、运输和储存成本对发泡塑料材料有显著影响。
本发明的另一项优点表现在所获得的塑料材料的质量改进，这是基本上没有微孔结构的劣化，以及通过封闭模具而形成。
本发明的方法还提供了这样的优点：由于在压缩的聚合物物质中微粒的暂时收缩引起的体积补偿，该方法可在比用于模具的一般值低的压力下进行，随之而来的优点也有该方法的操作条件相关。
此外，由于基本上没有从模具损失塑料材料，废产品的回收处理成本降低，并且废产品对环境影响大大减少。
这些和其它目的、优点及特点由本发明的方法优选实施方式的以下描述得到证明，所述实施方式在附图中以阐述和非限制性的目的显示。
在附图中：
-图1示意性地展示了聚合物IPN泡沫体的结构；
-图2展示了根据已知技术的发泡塑料材料在封闭模具中的加工实例的示意图；
-图3展示了发明方法中所使用的可压缩材料的微粒的实例的详细情况；
-图4展示了本发明方法的示意图。
如上图1所示，本发明方法制造的聚合物IPN泡沫体通过使PVC的直链C穿入聚酰胺、聚酰亚胺、多异氰酸酯与聚脲的网状结构R而获得。
根据图2所示的已知技术的方法，将起始聚合混合物的物质13a(PVC树脂、酸酐、异氰酸酯、化学发泡剂、表面活性剂与催化剂)被注入由盖子11封闭的模具10，盖子11由压板12激活，当被加热板14、15加热并由于板12对过程反应引起的膨胀(尤其是由发泡气体的微孔20的形成引起)施加的反向作用而压缩时，混合物趋于强烈膨胀，直至克服模具10本体上的盖子11的封闭作用。结果，模制产品的形成物质13b的聚合材料的一部分趋于随着模具10本体上的盖子11的封闭抵抗而排出(图2箭头F)。
既而最终产品13c具有由发泡气体独有的微孔20限定的密度，因此发泡气体必须在起始混合物13a中以该目的所必要的高剂量存在。
根据本发明，为避免聚合物混合物从模具10的所述损失，并显著降低用于在发泡聚合物中产出上述气体微孔20的化学发泡剂的量，将中空微粒16以及在方法条件下可弹性与可逆压缩的材料一起加入起始混合物中。在如图3所示的实例中，这些微料由微球组成，所述微球由在方法条件下可弹性形变材料的外壳17形成，其内限定了填充有气体18(优选异戊烷)的空腔19，所述可弹性形变材料优选聚丙烯腈(PAN)或聚甲基丙烯腈(PMAN)。使用上述可弹性形变材料形成微粒子16具有使它们能可逆压缩的特别优点，从而使它们在起始聚合混合物的热模制过程完成时恢复到它们的初始构造。这样一来，微粒16以它们的膨胀或最高的体积构型，在发泡塑料材料中，帮助提高最终制成品的密度与机械特性。
由于外壳17的弹性形变性质，以及空腔19内收集的气体18的内在压缩性，上述微粒16可在外部压力作用下暂时收缩，从较大尺寸的初始形式A到较小尺寸的形式B，从模具10中提取出时，通过在湿度下加热模制的IPN物质，恢复到它们的初始构型A(图3)。尤其是，上述微粒16为优选具有35-55μm直径的微球的形式，对于本发明的应用，甚至是直径10-110μm的微球也可以有利地使用。
如图4所更好显示的，将聚合物混合物的初始物质13与可压缩微粒一同以它们较大体积的初始构型16A注入或浇注入模具。所述微粒尤其是与起始聚合物混合物的其它组分一起均匀分散在聚合物混合物13的上述物质中。
从这样的初始构型开始，然后对注入模具10中的处于通过封闭盖子11而具有恒定体积的环境中的物质13加热，由此通过化学发泡剂分解，并还通过IPN聚合物的凝胶化和交联反应而获得气体微孔20。
与具有恒定体积的模具10上的盖子11的封闭作用反向的由此发生在物质13上的膨胀导致压力升高，这导致分散在图4的初始物质13内分散的上述微粒16暂时收缩。
由于与具有恒定体积的模具10中收集的聚合物质量13中压力提高的响应的如上所述微粒16的收缩，这些从它们具有较大体积的初始构型16A转化为体积减少的构型16B，后者被称为从模具10提取的聚合物物质13b(也称为“胚料13b”)。
此时在湿度环境(在炉21内在水蒸气存在下，或通过浸入沸水浴)加热胚料13b，直至通过恢复微粒16的初始体积A，以及由于发泡气体微孔20形成的化学膨胀，获得具有期望密度的IPN聚合物的物质13c。
根据优选实施方式，本发明的用于制造IPN聚合物泡沫体的起始混合物由以下组成(按重量百分比计)：
Figure GDA00002560383600051
其中加入0.05-0.5%微球16。
作为与已知技术的比较，具有以下成分：
Figure GDA00002560383600052
的起始混合物第一次仅用5.5%的发泡剂处理(图2的已知技术)，第二次在0.2%微球存在下用2.5%的发泡剂处理(本发明的方法，图4)。在两种情况下都获得了密度为45kg/m3的发泡IPN聚合物材料13c。但本发明的方法使具有期望密度水平的获得的发泡材料(图4的13c)，其中化学发泡剂的用量仅是现有方法(图2的发泡产品13c)所使用的一半，但是保持了最终成品机械性能不变，并且其在制得产品物质内的分布更加均匀。

Claims (7)

1.制造发泡PVC的方法，该方法是包括在封闭模具中加热聚合物混合物物质(13)的类型，特征在于，该方法包括：
(a)控制所述物质(13)的膨胀，所述膨胀是由于在具有由所述封闭模具(10)限定的恒定体积的环境中热模制过程造成的，所述控制通过在所述聚合物混合物物质(13)中存在可压缩材料的微粒(16)来获得，所述可压缩材料的微粒适于在由该物质(13)中的发泡气体的微孔(20)的形成和膨胀所产生的压力作用下从体积较大的初始形式(A)收缩到体积较小的形式(B)；和
(b)使模制的膨胀材料的物质中含有的所述微粒(16)从它们的构型(B)膨胀到体积较大的初始构型(A)，由此获得的所述膨胀材料的密度由在所述膨胀材料的物质(13c)中同时存在的发泡气体的微孔(20)和具有它们较大体积的构型(A)的所述微粒(16)确定。
2.根据权利要求1所述的方法，特征在于，所述膨胀阶段(b)在潮湿条件下进行。
3.根据权利要求1所述的方法，特征在于，所述微粒(16)为微球的形式，所述微球由可形变塑料材料的外壳(17)组成，在所述外壳内限定含有气体(18)的空腔(19)。
4.根据权利要求3所述的方法，特征在于，所述微粒(16)的外壳(17)由聚丙烯腈或聚甲基丙烯腈组成，所述空腔(19)由异戊烷填充。
5.根据权利要求3所述的方法，特征在于，所述微球的直径为10-110μm。
6.根据权利要求4所述的方法，特征在于，所述微球的直径为10-110μm。
7.根据前述权利要求任一项所述的方法，特征在于，所述聚合物混合物是用于制造互穿网络聚合物泡沫体的具有以下重量百分比起始组成的混合物：
Figure FDA0000440217960000021
存在0.05-0.5%的微球(16)。
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