CN107922661A - 可热膨胀的泡沫 - Google Patents
可热膨胀的泡沫 Download PDFInfo
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Abstract
本发明公开了一种用于可膨胀的密封剂的组合物,其包括至少一种聚合物材料,和化学发泡剂,所述聚合物材料优选选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLPDE)、乙烯‑乙酸乙烯酯(EVA)、乙烯‑甲基丙烯酸酯(EMA)和乙烯‑丙烯酸丁酯(EnBA),其中所述组合物基本上不含交联剂。
Description
技术领域
本公开涉及可热膨胀(heat expandable)的泡沫。
背景技术
这个部分提供与本公开相关的背景技术信息,其不必然是现有技术。
可以将可热膨胀密封剂和挡板组合物成形为希望的形状,使得当将所述密封剂插入到空腔(例如汽车或其它车辆的中空柱结构)中,随后进行其热诱导膨胀时,其在那个空腔内起到高效密封剂和隔音板的作用。
特别地,热膨胀性(expansible)密封剂和挡板组合物,其在被成形为希望的构型后,适合于放置在车辆柱内或其它车身空腔内,其位置使得当车身经历底漆(例如电涂层)和/或油漆烘烤操作或其它升高在所述车身周围的环境的温度的工艺时,所述成型的密封剂和挡板产品膨胀到一定程度,该程度为经膨胀的组件用于减弱噪声(例如道路噪声),所述噪声否则会穿过所述空腔。膨胀的产品还用于密封所述空腔,并且由此防止了湿气、灰尘、空气、其它不希望流体和声音的渗透。
上述可热膨胀密封剂和挡板组合物可包括基于弹性体或热塑性材料的材料和化学发泡剂。典型地,这些组合物还包括交联剂,所述交联剂当被加热时固化所述基于弹性体或热塑性材料的材料。然而,为了确保在所述组合物的加热过程中所述材料的适当膨胀,在固化所述基于弹性体或热塑性材料的材料中涉及的反应性化学和所述化学发泡剂的活化需要被适当定时,以使得所述发泡剂的固化和活化同时发生以实现所述组合物的最优膨胀。另外,如果在被插入到待被密封的空腔中之前未发泡的组合物不利地经历升高的温度或湿度,则所述材料的固化可能被过早地引发,这可能导致所述材料的降低的最终膨胀,或者可能导致不希望的开裂、结皮或不均匀的泡沫品质。
发明内容
概述
这个部分提供本公开的一般性概述,而不是其完全范围或所有其特征的全面公开。
本公开提供一种用于可膨胀密封剂的组合物,其包括至少一种聚合物材料,和化学发泡剂,所述聚合物材料优选选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLPDE)、乙烯-乙酸乙烯酯(EVA)、乙烯-甲基丙烯酸酯(EMA)和乙烯-丙烯酸丁酯(EnBA),其中所述组合物基本上不含交联剂。
本公开还提供用于密封空腔和为空腔提供隔音板的膨胀性密封剂和挡板组件,其在生产操作过程中经历预定的升高的温度。所述组件包括聚合物材料和化学发泡剂,所述聚合物材料优选选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLPDE)、乙烯-乙酸乙烯酯(EVA)、乙烯-甲基丙烯酸酯(EMA)、乙烯-丙烯酸丁酯(EnBA)和它们的混合物,所述化学发泡剂优选选自4,4’-氧代(oxy)双(苯磺酰肼)和碳酸氢钠;其中所述组件基本上不含交联剂。
另外的适用性的领域将从本文中提供的说明中变得显而易见。在这个概述中的说明和具体实例仅仅意图用于示例性说明的目的,而不意图限制本公开的范围。
附图说明
本文中描述的附图仅用于选择的实施方案而不是所有可能的执行方案的示例性说明的目的,并且它们不意图限制本公开的范围。
图1是示例性说明在根据本公开的原则的各种聚合物材料的零剪切粘度和分子量之间的关系的图。
图2包括在膨胀后的本发明组合物的照片(1a),其包括表面的增强视图(1b),以及在膨胀后的非本发明的参比组合物的照片(2a),其包括表面的增强视图(2b)。
详述
现在将参照附图更全面地描述例示实施方案。
本公开涉及用于车辆的可热膨胀密封剂或隔音板的组合物。根据本公开,所述组合物基本上不含交联剂,例如过氧化物。短语“基本上不含”意于是指如果在所述组合物中发现一定量的交联剂,则所述量是可忽略的以至于不可能获得所述交联剂的效果。换句话说,在所述组合物中发现的交联剂的量不能引起存在于所述组合物中的弹性体或热塑性聚合物的固化,或者引起基本上可忽略量的交联。优选地和有利地,本公开的组合物不包括任何交联剂(即,所述组合物含有0%的交联剂)。然而,如果将用于生产本公开的组合物的设备用于生产其它可能包括交联剂的非相关组合物,本发明的发明人承认可在本公开的组合物的生产过程中向其中添加非意图的可忽略量的交联剂。
根据本公开的组合物可各自包括聚合物材料和化学发泡剂。所述组合物还可包括抗氧化剂、乳化剂、增粘剂和填充材料。还可以包括其它添加剂,例如成核剂、表面活性剂、润滑剂和弹性体。如上所述的,所述组合物基本上不含交联剂。尽管所述组合物不包括交联剂,但所述组合物产生当加热时膨胀的密封剂或挡板。具体地,所述组合物当加热时形成具有蜂窝状结构的泡沫,其被构造用于密封所述车辆的空腔,并且防止湿气、灰尘、空气和其它不希望的流体渗透进入到所述空腔中。另外,所述泡沫有助于防止在所述车辆的空腔内的声音的衰减。
关于这一点,可以将所述组合物的成分预混合和随后注塑成尺寸和形状适合在所述车辆的希望的空腔(例如在车辆的中空A-柱、B-柱、C-柱、发动机导轨或脚踏板(rockerpanel))内的零件,然后将所述车辆涂漆和在油漆烘烤循环中加热以在范围为140摄氏度(284华氏度)和210摄氏度(410华氏度)之间的温度下固化所述油漆。当所述车辆在所述油漆烘烤循环过程中被加热时,所述零件发泡并膨胀以填充和密封所述空腔。优选地,当加热时,所述组合物膨胀约400%至约1300%。因此,尽管所述组合物基本上不含交联剂,但本公开的组合物膨胀到与包括交联剂的组合物类似的量,而没有增加所述交联剂的成本和没有包括交联剂时的缺点,例如开裂、结皮、非均匀泡沫品质或所述组合物在被加热前的过早固化。
本公开的组合物包括聚合物材料。优选地,所述聚合物材料是热塑性材料,例如低密度聚乙烯(LDPE)、乙烯-乙酸乙烯酯(EVA)、乙烯(ethyl)-丙烯酸甲酯(EMA)、乙烯-丙烯酸正丁酯(EnBA)、乙烯-甲基丙烯酸缩水甘油基酯(EnGMA)和它们的混合物。所述LDPE可包括高熔体流动的LDPE和线性低密度聚乙烯(LLDPE)的组合。可添加到本公开的组合物中的其它聚合物材料包括弹性体,例如乙烯-丙烯-二烯单体(EPDM)和丁苯橡胶(SBR)。所选择的聚合物或弹性体材料必须具有在所述油漆烘烤循环中所述组合物的加热过程中足以防止分解的发泡剂逃逸的熔体强度。所述聚合物材料的熔体强度是当在熔融状态时它的抗拉伸性。影响所述抗拉伸性的材料的性能是分子量和分子支化。当每种性能提高时,在低剪切速率下熔体强度被改进。
关于分子量,优选所述聚合物材料,例如LDPE,具有在约100’000g/mol至1’000’000g/mol范围内的分子量(Mw)。对于诸如EVA、EMA和EnBA的材料,优选所述分子量在约100’000g/mol至约360’000g/mol范围内。尤其优选的分子量范围,对于LDPE为150’000至400’000g/mol,对于EMA为200’000至350’000g/mol,对于LLDPE为100’000至200’000g/mol,对于EVA为150’000至350’000g/mol,对于EnBA为200’000至350’000g/mol,和对于EnGMA为150’000至250’000g/mol。所有这些分子量值指在140℃下,在1,2,4-三氯苯中,在1mL/min的流速下,和相对于聚苯乙烯标准物获得的Mw测量值。
关于分子支化,在所述聚合物材料中的长链支化(LCB)的量对于所述聚合物材料的熔体流变学具有显著作用,其在加热根据本公开的组合物的过程中防止了分解的发泡剂的逃逸。用于测定在所述聚合物材料中的长链支化的量的方法包括测定所述材料的零剪切粘度(η0),其有时出于实验原因也称为“低剪切粘度”。在本文中,零剪切粘度和低剪切粘度含义相同。通常,当零剪切粘度增加时,聚合物的熔体强度增加。例如,参见本申请的图1,与线性聚乙烯(PE)相比,示例性说明了各种LDPE和EVA材料的零剪切粘度。在代表所述线性PE的曲线下面的数据点具有大量的LCB,并代表根据本公开可用的令人满意的LDPE和EVA聚合物材料。特别地,优选所述聚合物材料的零剪切粘度在100Pa-s至10000000Pa-s范围内。优选地,适合于本发明的聚合物的零剪切粘度在100Pa s和50’000Pa s之间,更优选在500Pas和25’000Pa s之间,最优选在1’000Pa s和20’000Pa s之间。
限定聚合物用于本发明的适用性的另外的重要的粘度参数可通过ASTM D4440-15标准方法测定。特别地,参数δ(delta)(意指损耗模量除以储能模量)和参数η*(eta)(意指复数粘度)对于适合于本发明的聚合物是重要的。优选在本发明中使用的聚合物具有在-0.2和0.2之间,更优选在-0.1和0.1之间的δ的正切的对数值,即log(tanδ)。还优选相同的聚合物材料具有在3和4之间,更优选在3.25和3.75之间的η*的对数值,即log(η*)。对于本发明而言最优选的聚合物材料在这个参数范围内。
示例性的可商购LDPE包括得自Dow Chemical的621i、772、993i和1017,和得自ExxonMobil的LD100BW。示例性的可商购LLDPE包括得自ExxonMobil的LL1102。示例性的可商购EMA包括得自Arkema的Lotryl 24MA005和18MA02N。示例性的可商购EVA包括得自DuPont的Elvax 240、265、460和470。示例性的可商购EnBA包括得自Arkema的Lotryl30BA02N和Lotryl 35BA40。示例性的可商购EnGMA包括得自Arkema的Lotader ADX 1200S。示例性的可商购EPDM包括可得自Dow Chemical的Nordel 4725。
如果选择的聚合物材料是LDPE自身,本公开的组合物可包括量的范围在75重量%至90重量%之间的LDPE。相反,如果选择的聚合物材料是LDPE和LLDPE的混合物,则所述组合物可包括量的范围在15重量%至90重量%之间的LDPE,和包括量的范围在25重量%和80重量%之间的LLDPE。如果选择的聚合物材料是EVA,则所述组合物可包括量的范围在80重量%至95重量%之间的EVA。如果选择的聚合物材料是EMA,则所述组合物可包括量的范围在80重量%至90重量%之间的EMA。如果选择的聚合物材料是EnBA,则所述组合物可包括量的范围在70重量%至90重量%之间的EnBA。还应理解的是,也可以使用LDPE、LLDPE、EVA、EMA和EnBA的各种共混物而不背离本公开的范围。
本公开的组合物包括至少一种化学发泡剂。化学发泡剂是例如在升高的温度条件下分解并能够产生气态分解产物的物质,所述气态分解产物可经由发泡过程在所述热塑性基体中形成蜂窝状结构。具体地,当所述发泡剂被加热时,所述发泡剂经历化学反应和/或分解,其导致一种或多种气体的释放。当所述气体被释放时,如上所述的聚合物材料的熔体强度使得能实现熔融材料拉伸而不会破裂和允许所述一种或多种气体逸出。这导致形成泡沫。可在本公开的组合物中使用的化学发泡剂包括例如碳酸氢盐,例如碳酸氢钠,4,4’-氧代双(苯磺酰肼)(OBSH),对甲苯磺酰(sulfunyl)肼(TSH),苯磺酰(sulfunyl)肼(BSH)、二硝基五亚甲基四胺(DMPT),对甲苯磺酰氨基脲(PTSS),氨基甲酸酯和偶氮二甲酰胺。
特别优选的发泡剂是OBSH和碳酸氢盐,尤其是碳酸氢钠。适合作为碳酸氢盐的是式XHCO3的那些,其中X代表一般的阳离子,特别是碱金属离子,优选Na+或K+,其中Na+是特别优选的。其它合适的阳离子可选自NH4 +、1/2Zn2+、1/2Mg2+、1/2Ca2+和它们的混合物。
在优选的实施方案中,将所述碳酸氢盐与多元羧酸(polycarbonic acid)组合。合适的多元羧酸包括有机二-、三-或四-酸,其优选在室温(23℃)下是固体。优选的是羟基官能的或不饱和的多元羧酸,例如柠檬酸、酒石酸、苹果酸、马来酸或富马酸。尤其优选的是柠檬酸。还适合的是如上提及的酸的盐,尤其是具有如下阳离子的盐:Na+、K+、NH4 +、1/2Zn2+、1/2Mg2+、1/2Ca2+和它们的混合物。最优选的是Na+或K+的盐。碳酸氢盐发泡剂和多元羧酸的最优选组合是碳酸氢钠与柠檬酸和/或柠檬酸盐(特别是柠檬酸Na+或K+)的组合。所述多元羧酸,特别是柠檬酸,可以例如30重量%直到90重量%的量包含在所述碳酸氢盐中。
本公开的组合物包括量的范围在5重量%至20重量%之间的发泡剂。可以在有或没有活化剂的情况下使用所述化学发泡剂,所述活化剂例如脲、咪唑或金属氧化物,例如氧化锌。
所述发泡剂优选以粉末形式使用。这意味着用作发泡剂的物质优选在环境条件(环境压力,23℃)下是固体,并且优选以精细分散的粉末形式。
对于优选的发泡剂OBSH,这意味着OBSH优选以粉末形式,其包含如下颗粒,所述颗粒具有1至15μm(微米),优选4至13μm,非常优选6至10μm的D50的平均(mean)颗粒尺寸和由0.1至3.0μm,优选0.5至2μm,更优选1至1.5μm的D10和3至40μm,优选5至30μm,更优选15至25μm的D90表征的颗粒尺寸分布。
对于另一优选的发泡剂碳酸氢钠,优选的形式也是粉末形式,其中优选的平均颗粒尺寸D50在1和30μm之间,优选在5至25μm之间,更优选在10和20μm之间,和颗粒尺寸分布优选由0.1至4μm,优选在1和3.5μm之间,更优选在2和3μm之间的D10和5至100μm,优选15至80μm,更优选25至75μm的D90表征。
所述“平均颗粒尺寸”指的是通过激光衍射颗粒尺寸分析测定的体积平均值。D50是对于体积分布的平均颗粒尺寸,其中基于体积计的颗粒的一半低于该值。
术语“颗粒尺寸分布”指的是由D10和D90表征的分布的宽度,其中D10描述了其中所述分布的10%低于其的基于体积计的颗粒尺寸,和D90描述了其中所述分布的90%低于其的基于体积计的颗粒尺寸。在D10和D90之间的差较小意味着较窄的尺寸分布。
本公开的组合物可包括用于耐UV性、阻燃性、抗氧化性和作为加工助剂的各种添加剂。关于抗氧化性,应理解的是实践中所有的聚合物材料都经历氧化降解反应,其可能发生在生产、加工和最终使用阶段中的一个或全部中。抗氧化剂在将这种降解防止到如下程度方面是高度有效的:在发泡之前和之后,物理和机械性能损失被保持在可接受限度内。可在本公开的组合物中使用的示例性商业抗氧化剂是得自BASF的Irganox 1010,其是空间位阻酚类抗氧化剂。本公开的组合物可包括量的范围在0.1重量%至0.5重量%之间的抗氧化剂。
本公开的组合物可包括聚乙烯蜡作为乳化剂(例如作为加工助剂)。作为所述聚乙烯蜡乳化剂,可使用例如Marcus Wax的商业化产品。本公开的组合物可包括量的范围在2重量%至10重量%之间的聚乙烯蜡。
本公开的组合物可任选包括增粘树脂。增粘树脂的应用增加了预成形零件的粘性,该粘性有助于在所述油漆烘烤循环过程中加热所述零件之前和之后将所述预成形零件保持在所述空腔中在希望的位置。关于这一点,用于生产车身的金属(例如钢、铝等)基材在经历所述油漆烘烤循环之前可以是油性的。因此所述增粘树脂有助于防止在发泡之前在所述预成形零件和所述金属基材之间的脱离。然而,所述增粘树脂是任选的,因为所述增粘树脂可能增加在所述零件的存储和运输过程中所述预成形零件彼此粘附的倾向。可包括在本公开的组合物中的示例性树脂包括烃树脂、C5树脂、C9树脂、酚醛树脂、饱和树脂、不饱和树脂和部分饱和树脂。本公开的组合物可包括量的范围在0重量%至5重量%之间的增粘树脂。
根据本公开的组合物可包括填充材料。示例性填充材料包括碳酸钙和氧化钙,其通常是非反应性的并降低了与制造所述组合物相关的成本,因为需要较少的聚合物材料。可商购碳酸钙包括Quincy 325。可商购氧化钙包括Polycal OS325。所述填料可包括由例如硬脂酸的材料形成的涂层。可商购的被涂覆的填料包括硬脂酸涂覆的碳酸钙填料,例如Winnofil SPT。本公开的组合物可包括量的范围在0重量%至15重量%之间的填充材料。其它示例性填充材料包括滑石、二氧化硅、粘土、纳米粘土、氧化钛、硅灰石和芳族聚酰胺纤维。
本发明组合物的一个优选实施方案包含基于在膨胀之前的总组合物计15-85重量%的LDPE和7.5-75重量%的LLDPE,其中LDPE和LLDPE的总量优选为75-90重量%。另外,这个实施方案包含在5和10重量%之间的发泡剂,优选OBSH。这个实施方案具有在150℃和210℃之间的整个温度范围内的格外高的膨胀值。
另一个优选的实施方案包含70-92重量%的EVA,或不同EVA的混合物。另外,这个实施方案包含在5和12重量%之间的发泡剂,优选OBSH。这个实施方案具有在150℃和210℃之间的整个温度范围内的格外高的膨胀值。
另一个优选的实施方案包含70-90重量%的EMA,或不同EMA的混合物。另外,这个实施方案包含在5和12重量%之间的发泡剂,优选OBSH。这个实施方案在150℃和210℃之间的整个温度范围内具有格外高的膨胀值。
另一个优选的实施方案包含在30和45重量%之间的EVA,和在30和45重量%之间的EnBA。另外,这个实施方案包含在10和20重量%的发泡剂,优选碳酸氢钠,其任选包含基于所述发泡剂的重量计的在30和90重量%之间的柠檬酸。这个实施方案特别在180℃和210℃之间的高温范围下具有格外高的膨胀值。
另一个优选的实施方案包含在15和25重量之间的EVA,在30和50重量%之间的EnBA,在5和15重量%之间的EMA和在5和15重量%之间的EnGMA。另外,这个实施方案包含在10和20重量%之间的发泡剂,优选碳酸氢钠,其任选包含基于所述发泡剂的重量计的在30和90重量%之间的柠檬酸。这个实施方案尤其在180℃和210℃之间的高温范围下具有格外高的膨胀值,以及在例如油性金属的基材上具有优异的粘附性。
本发明的另一个方面是这样的可热膨胀的组合物用于生产挡板和/或增强元件或组件的用途。这样的元件用于将中空结构,例如在汽车的中空结构零件中的空腔密封、设置挡板和/或增强。在小汽车中的中空零件可包括车身组件(例如面板)、框架组件(例如液压成形管)、柱结构(例如A、B、C或D柱)、保险杠、车顶或类似组件。
本发明的这个方面因此是用于密封空腔和为空腔提供隔音板的膨胀性密封剂和挡板组件,其在生产操作过程中经历预定的升高的温度,所述组件包含:
聚合物材料,其选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLPDE)、乙烯-乙酸乙烯酯(EVA)、乙烯-甲基丙烯酸酯(EMA)、乙烯-丙烯酸丁酯(EnBA)和它们的混合物;和
化学发泡剂,其选自4,4’-氧代双(苯磺酰肼)和碳酸氢钠;和
任选的载体元件;
其中所述组件基本上不含交联剂。
关于当在机动车制造中使用时根据本发明的可热膨胀的组合物的活化,有利的是将所述组合物的热活化与另一个涉及热处理的方法步骤耦合。这样的方法步骤的一个实例是底盘或车身的电涂覆(阴极浸渍涂漆/涂覆)。
在一个优选的实施方案中,这样的用于中空结构的挡板和/或增强元件主要由可热膨胀的组合物组成。在这种情况下,有利的是以如下方式设计所述元件的形状:其可被容易地适合到待被设置挡板和/或增强的中空结构的壁中并附装于其上。在这种情况下,制造优选通过如下方式完成:注塑、冲切或冲压,或挤出穿过形状模板。
在另一个优选的实施方案中,这样的用于中空结构的挡板和/或增强元件除了所述可热膨胀的组合物之外还包含载体元件,在该载体元件上沉积或附接了本发明的可热膨胀的组合物。这样的设计可能是更加成本有效的,并且其可以便利于例如通过在所述载体元件上并入别针、螺栓或钩子,实现所述挡板和/或增强元件在待被设置挡板和/或增强的结构的壁上的固定。另外,在合适设计所述载体元件的情况下,可提高根据本发明的挡板和/或增强元件的机械性能和稳定性。
所述载体元件可由任何能够被加工成能够用于本发明的实施方案的形状的材料组成。优选的材料是聚合物材料,例如塑料、弹性体、热塑性材料、热固性聚合物、它们的共混物或其它组合或类似物。优选的热塑性材料包括但不限于聚合物,例如聚氨酯、聚酰胺、聚酯、聚烯烃、聚砜、聚(对苯二甲酸乙二醇酯)、聚氯乙烯、氯化聚烯烃或类似物。尤其优选的是高温稳定的聚合物,例如聚(苯醚)、聚砜、聚醚砜、聚酰胺,优选聚酰胺6、聚酰胺6,6、聚酰胺11、聚酰胺12或它们的混合物。其它合适的材料包括金属,尤其是铝或钢,或天然生长的有机材料,例如木材或其它(压制)的纤维质材料。还可以使用玻璃质或陶瓷材料。可以使用这些材料的任意组合。另外考虑的是,这些材料可被填充(例如被纤维、矿物、粘土、硅酸盐、碳酸盐、它们的组合或类似物填充)或被发泡。
所述载体元件可进一步具有任何形状或几何形状。其还可以由多个不直接连接的零件组成。例如,其可以是实心的、中空的或发泡的,或者其可具有格栅状结构。根据所述挡板和/或增强元件的预期用途,所述载体元件的表面典型地可以是光滑的、粗糙的或被结构化的。
根据本发明的挡板和/或增强元件的生产方法很大程度上取决于所述载体元件的材料。如果所述载体元件的材料可被(注射)模塑或挤出,则整个挡板和/或增强元件可在两步注塑方法中或在所述载体元件和可热膨胀的组合物的共挤出方法中制备。
本发明的另一方面是如上所述的挡板和/或增强元件用于将陆上车辆、船舶或飞行器(优选机动车)的空腔或中空结构和/或建筑物的空腔密封、设置挡板或增强,以使得噪声、振动、湿度和/或热的传输被降低和/或围绕所述空腔的物体被机械增强的用途。
本发明的另一个方面是将空腔或中空结构密封、设置挡板和/或增强的方法,其特征在于将包含根据如上所述的可热膨胀的组合物的元件引入到所述空腔或中空结构中,和随后将其热膨胀,使得所述空腔或中空结构至少部分地被所述膨胀的组合物填充。用于热膨胀过程的优选温度在140℃和210℃之间。所述组合物的优选烘烤时间在5分钟和30分钟之间。
具体实施方式
现在将关于各个实施例组合物(实施例1-32)和对比组合物(实施例A-L)描述本公开的组合物。所述实施例组合物基本上不含交联剂,而所述对比实施例包括过氧化物交联剂(可得自Akrochem的DC40C)。在实施例组合物和对比组合物中每种组合物的材料的量以基于在膨胀之前的总组合物计的重量百分比计列出。对于实验1-20和A-G,参见如下表1和2。
所述实施例组合物和对比组合物各自通过如下过程制备:称重其材料和将所述材料放置在容器中,随后将所述容器连续旋转预定的时间段(例如1至24小时)以满意地混合所述材料。然后,将材料的混合物要么进料到料斗中并使用双螺杆挤出机(例如Buss捏合机)挤出,要么使用小批量混合器(其包括Banbury桨叶)混合并然后压制到1mm至5mm的厚度。然后将挤出的混合物造粒并注塑以形成模塑的零件。然后将所模塑的或压制的零件在范围为150℃和210℃之间的温度下烘烤以将所述零件发泡。然后测定与在烘烤之前每个零件相比在发泡后所述每个零件的体积膨胀率。在表1和2中可看出所述实施例组合物、对比组合物和它们在各种温度下产生的体积膨胀率。
这些结果进一步由在表3和4中呈现的结果证实。这些实验包括本发明的实施例(21-31)和非本发明的参比实施例(H-K)二者。同样在这些表中,还示出了组成(以基于膨胀之前的总组合物计的重量%表示)和体积膨胀率数据(以基于原始未膨胀组合物的体积计的%表示)。
原材料 | 实施例A | 实施例B | 实施例C | 实施例D | 实施例E | 实施例F | 实施例G |
LDPE(621i) | 81.9 | 83.29 | 74.67 | 89.17 | 76.25 | 86 | |
LDPE(772) | |||||||
LLDPE(LL 1002) | |||||||
EMA(Lotryl 24MA005) | |||||||
EMA(Lotryl 18MA02N) | |||||||
EVA(Elvax 460) | |||||||
EVA(Elvax 470) | |||||||
EVA(Elvax 240) | |||||||
EVA(Elvax 265) | |||||||
EMBA(Lotryl 30BA02) | 77 | ||||||
过氧化物(DC40C) | 0.25 | 3.46 | 1.28 | 0.77 | 0.9 | 0.52 | 0.5 |
EPDM(Nordel 4725) | |||||||
碳酸钙 | 7 | 4.06 | 14.6 | 15 | 8.5 | 7 | |
氧化钙 | |||||||
涂覆的CaCO3 | |||||||
OBSH(发泡剂) | 7.5 | 9.2 | 9.46 | 10.06 | 7.85 | 5 | |
碳酸氢钠 | 15 | ||||||
抗氧化剂(Irganox 1010) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
增粘树脂(Wingtack 86) | |||||||
聚乙烯蜡 | 3 | ||||||
体积膨胀率 | 实施例A | 实施例B | 实施例C | 实施例D | 实施例E | 实施例F | 实施例G |
在150℃下20分钟 | 682 | 739 | 814 | 749 | 712 | 710 | 481 |
在163℃下20分钟 | 953 | 845 | 928 | 1004 | 1120 | 1045 | 527 |
在191℃下20分钟 | 928 | 857 | 936 | 916 | 999 | 1003 | 493 |
在210℃下20分钟 | 905 | 819 | 923 | 830 | 916 | 942 | 404 |
表2
表3:本发明(数字)和非本发明(字母)的实验的组成数据(以重量%表示)和膨胀率数据(以%表示)
表4:本发明(数字)和非本发明(字母)的实验的组成数据(以重量%表示)和膨胀率数据(以%表示)
如可在表1至4中看出,尽管本公开的组合物不包括交联剂,但所述组合物仍各自表现出满意的膨胀率。即,所述样品各自预料不到地以与采用交联剂的对比组合物类似的量膨胀。然而,由于本申请的组合物不包括交联剂,制备本申请的组合物的成本被降低,并且与使用交联剂相关的缺点被消除。另外,由于没有使用交联剂,实现了对人和环境有潜在危害的化学品的应用的减少。
为了证实经膨胀的本发明组合物的泡沫表面品质与类似的根据现有技术的经交联的组合物相当,制备了两种模型配制剂。这些模型配制剂的组成细节示于表5中。
原材料 | 实施例32 | 实施例L |
LDPE(LD100BW) | 77.7 | 74.7 |
碳酸钙 | 7 | 7 |
碳酸氢钠(37重量%柠檬酸) | 15 | 15 |
过氧化物(DC-40C) | 1.5 | |
抗氧化剂(Irganox 1010) | 0.3 | 0.3 |
二季戊四醇五丙烯酸酯 | 1.5 | |
100 | 100 | |
体积膨胀率 | 实施例32 | 实施例L |
在180℃下20分钟 | 326 | 428 |
表5:本发明实验32和非本发明实验L的组成数据(以重量%表示)和膨胀率数据(以%表示)。
在20分钟的过程中,使表5的两个模型组合物在180℃下膨胀。拍摄所得泡沫的照片,并将其在图2中对比显示。上面两个照片显示了在膨胀后的本发明的组合物32。照片1a显示了经膨胀的泡沫的约一半的视图,而照片1b是表面的放大视图。下面两个照片显示了在膨胀后的非本发明的组合物L。照片2a显示了经膨胀的泡沫的约一半的视图,而照片1b是表面的放大视图。显而易见的是,根据本发明的泡沫的表面是光滑得多,并包含与非本发明的经交联的参比实施例相比更少的不希望的表面缺陷,例如大孔。
已经为了示例性说明和描述的目的提供了所述实施方案的上述说明。其不意图是详尽无遗的或者限制本公开。具体实施方案的单独要素或特征通常不限于具体实施方案,而是,即使没有明确示出或描述,如果合适,它们是可互换的并且可用在选择的实施方案中。其还可以许多方式变化。这样的变化不应被认为背离本公开,并且所有这样的改良意于包括在本公开的范围内。
Claims (15)
1.用于可膨胀密封剂的组合物,其包含:
至少一种聚合物材料,该聚合物材料选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLPDE)、乙烯-乙酸乙烯酯(EVA)、乙烯-甲基丙烯酸酯(EMA)和乙烯-丙烯酸丁酯(EnBA);和
化学发泡剂,
其中所述组合物基本上不含交联剂。
2.根据权利要求1的组合物,其中所述聚合物材料是LDPE,其量的范围在75重量%至90重量%之间。
3.根据权利要求2的组合物,其中所述化学发泡剂是4,4’-氧代双(苯磺酰肼)或碳酸氢钠。
4.根据权利要求1的组合物,其中所述聚合物材料包含EMA,其量的范围在75重量%至90重量%之间。
5.根据权利要求4的组合物,其中所述化学发泡剂是4,4’-氧代双(苯磺酰肼)。
6.根据权利要求1的组合物,其中所述聚合物材料包含EVA,其量的范围在75重量%至92重量%之间。
7.根据权利要求6的组合物,其中所述化学发泡剂是4,4’-氧代双(苯磺酰肼)。
8.根据权利要求1的组合物,其中所述聚合物材料的零剪切粘度在100Pa-s至50000Pa-s的范围内。
9.用于密封空腔和为空腔提供隔音板的膨胀性密封剂和挡板组件,其在生产操作过程中经历预定的升高的温度,所述组件包含:
聚合物材料,其选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLPDE)、乙烯-乙酸乙烯酯(EVA)、乙烯-甲基丙烯酸酯(EMA)、乙烯-丙烯酸丁酯(EnBA)和它们的混合物;和
化学发泡剂,其选自4,4’-氧代双(苯磺酰肼)和碳酸氢钠;和
任选的载体元件;
其中所述组件基本上不含交联剂。
10.根据权利要求9的组件,其中所述聚合物材料是LDPE,其量的范围在75重量%至90重量%之间。
11.根据权利要求9的组件,其中所述聚合物材料是EMA,其量的范围在75重量%至90重量%之间。
12.根据权利要求9的组件,其中所述聚合物材料是EVA,其量的范围在75重量%至92重量%之间。
13.根据权利要求9的组件,其中所述聚合物材料是在30和45重量%之间的EVA,和在30和45重量%之间的EnBA。
14.根据权利要求9的组件,其中所述聚合物材料的零剪切粘度在100Pa-s至50000Pa-s范围内。
15.根据权利要求9的密封剂或挡板组件用于将陆上车辆、船舶或飞行器的空腔或中空结构和/或建筑物的空腔密封、设置挡板或增强以使得噪声、振动、湿度和/或热的传输被降低和/或围绕所述空腔的物体被机械增强的用途。
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US10899902B2 (en) | 2021-01-26 |
JP2018527440A (ja) | 2018-09-20 |
EP3344689B1 (en) | 2020-07-22 |
JP7007260B2 (ja) | 2022-01-24 |
CN107922661B (zh) | 2021-06-01 |
EP3344689A1 (en) | 2018-07-11 |
WO2017036624A1 (en) | 2017-03-09 |
US20180223065A1 (en) | 2018-08-09 |
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