CN114364740A - 可生物降解的vci包装组合物 - Google Patents
可生物降解的vci包装组合物 Download PDFInfo
- Publication number
- CN114364740A CN114364740A CN202080048391.8A CN202080048391A CN114364740A CN 114364740 A CN114364740 A CN 114364740A CN 202080048391 A CN202080048391 A CN 202080048391A CN 114364740 A CN114364740 A CN 114364740A
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- Prior art keywords
- biodegradable
- polyesters
- weight
- corrosion inhibitor
- volatile corrosion
- Prior art date
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Classifications
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Abstract
一种透气的可生物降解的挥发性腐蚀抑制剂聚酯组合物,其包含一种或更多种可生物降解的均聚物聚酯和/或一种或更多种可生物降解的无规共聚物聚酯、一种或更多种挥发性腐蚀抑制剂(VCI)、以及一种或更多种填料,其中所述组合物具有比聚乙烯更高的水蒸气透过率。
Description
技术领域
一种透气的可生物降解的挥发性腐蚀抑制剂组合物,其包含:含一种或更多种均聚物聚酯和/或一种或更多种无规共聚物聚酯的可生物降解的聚酯组合物与一种或更多种挥发性腐蚀抑制剂(VCI,volatile corrosion inhibitor);以及出乎意料地改善组合物的各种物理特性的至少一种或更多种填料。基于排除所述填料的所有可生物降解的聚酯的总重量,所述一种或更多种VCI的总量通常为约0.1重量%至约10重量%。
背景技术
由于沉积在土地垃圾场、垃圾坑、和市政和政府垃圾场中的经常污染和/或允许危险和/或有毒的化合物进入地下水的废塑料和聚合物的量不断增加,因此世界上存在对可生物降解的组合物的迫切需求。在海洋和大海中,增长的废物量被证明对消耗这些废物并经常因此而死亡的鱼类和哺乳动物构成危险,从而消除了重要的食物来源。包装是防腐蚀的一个组成部分,因为环境元素在与金属部件接触时会引起腐蚀,但在货物到达后,主要由LDPE和LLDPE薄膜制成的包装需要被处理,而许多回收设施不接受由LDPE和LLDPE制成的柔性包装。因此,包装材料最终进入垃圾填埋场等。鉴于目前消费者的意识,使企业减少其塑料足迹的压力越来越大,其中一种减少塑料足迹的方法是在产品的适用期和其他因素允许使用可生物降解的材料的情况下使用可生物降解袋来包装金属。
Cortec Corporation的美国专利6,028,160涉及主要由聚乙烯、淀粉、聚酯例如聚乳酸或其他合适的聚酯的聚合物树脂组成的可生物降解的树脂产品。与树脂混合的为颗粒状气相腐蚀抑制剂,所述颗粒状气相腐蚀抑制剂选自胺盐、苯甲酸铵、***衍生物、妥尔油咪唑啉、碱金属钼酸盐、碱性二元酸式盐、及其混合物,并且以聚合物树脂的1重量%至3重量%的量存在。
Cortec Corporation的美国专利6,156,929涉及主要由淀粉、聚乳酸和聚己内酯的聚酯的聚合物树脂组成的可生物降解的树脂产品。与树脂混合的是颗粒状气相腐蚀抑制剂,所述颗粒状气相腐蚀抑制剂选自胺盐、苯甲酸铵、***衍生物、妥尔油咪唑啉、碱金属钼酸盐、碱性二元酸式盐、及其混合物,并且以聚合物树脂的1重量%至3重量%的范围的量存在。
Cortec Corporation的美国专利6,617,415涉及主要由淀粉、聚酯例如聚乳酸或其他合适的聚酯的聚合物树脂组成的可生物降解的树脂产品。与树脂混合的是颗粒状气相腐蚀抑制剂,所述选颗粒状气相腐蚀抑制剂选自胺盐、***衍生物、碱性二元酸式盐、以及其混合物,并且以聚合物树脂的1重量%至3重量%的范围的量存在,并且其被成型为成型制品。
Cortec公司的美国专利6,984,426涉及可成型为可生物降解袋的可生物降解膜,其包括聚乳酸和合适的可生物降解的聚合物树脂的共混产品。共混产品包含约5重量%至约50重量%的聚乳酸。
Purac Biochem B.V.的美国公开2014/0235777涉及包含聚-D-乳酸(PDLA,poly-D-lactic acid)聚合物和聚-L-乳酸(PLLA,poly-L-lactic acid)聚合物的组合物。其还涉及用于生产模制部件的方法,所述方法包括以下步骤:加热模具,并将包含聚-D-乳酸(PDLA)聚合物和聚-L-乳酸(PLLA)聚合物的组合物供应至所述模具。其进一步涉及用于注射成型、热成型和/或膜吹塑的包含聚-D-乳酸(PDLA)聚合物和聚-L-乳酸(PLLA)聚合物的组合物。其还涉及可以通过对包含聚-D-乳酸(PDLA)聚合物和聚-L-乳酸(PLLA)聚合物的组合物进行加热而获得的组合物。
Northern Technologies International Corporation的美国专利8,008,373涉及包含至少一种可生物降解的热塑性聚合物的共混物的可生物降解的热塑性聚合物母料组合物,所述至少一种可生物降解的热塑性聚合物包含均匀分散在其中的高负载颗粒状填料。基于一种可生物降解的聚合物和至少一种填料的总量,可生物降解的热塑性聚合物的量通常为约25重量%至约50重量%,以及填料的量为约75重量%至约50重量%。填料的均匀分散通过将小颗粒的填料添加到可生物降解聚合物的熔体中并使用具有特殊螺杆几何形状的高剪切设备进行共混来获得。然后将母料组合物与另外的可生物降解的热塑性聚合物物理共混并将挤出加工成最终制品,例如吹塑膜和流延膜、模制产品等。与相同量的可生物降解的热塑性聚合物和填料的随后被加热成型为最终产品的一步共混物的物理特性和成本相比,母料多阶段方法产生具有改善的物理特性和较低的成本的产品。
发明内容
本发明的一个方面是减轻上述污染和/或毒性问题。另一方面是提供呈膜形式的组合物,所述组合物可以通过评估材料在工业堆肥设施中的及时可堆肥性(composability)的EN 13432和ASTM D6400。与上述产品不同,所述组合物与PE相比具有优异的机械特性和挥发性腐蚀抑制特性,因此其可以在缓蚀领域真正替代基于PE的材料。本发明的另一个重要方面是提供有效地防止包括机器、工具、和金属部件的各种物品的腐蚀的可生物降解的VCI包装组合物。由于腐蚀的主要成分中的一者为水,因此通常认为VCI包装组合物例如包含VCI的包装材料的较低水蒸气透过率(WVTR,water-vapor transmissionrate)导致更好的腐蚀抑制。然而,我们的结果表明,尽管可生物降解袋的WVTR比PE袋高,但当其中包含相同量的VCI时,可生物降解组合物(例如呈可生物降解的聚酯塑料袋形式)比聚乙烯(PE)袋表现得更好。VCI化学物质如亚硝酸钠、羧酸盐、或铵盐与水反应以释放VCI,因此,如果更多的水分更快地渗透通过袋,则更多的VCI化学物质将在更短的时间段内被激活,并且化学物质到达金属的表面将比在具有较低的水蒸气透过率的袋中更快。
本发明的包含填料的VCI包装组合物具有改善的透气性,表现出增加的水蒸气透过率(WVTR)、改善的在挤出设备中的加工能力、更少的粘连(这使得用该材料制成的袋更容易被打开)、较低的成本而不牺牲产品机械特性,并且比其中包含相同数量和类型的VCI但不包含填料的组合物更好的耐腐蚀性。
本发明的这些和其他方面通过利用PLA和/或芳族脂族聚酯共聚物与一种或更多种VCI化合物和一种或更多种填料的共混物来实现。
一种可生物降解的挥发性腐蚀抑制剂聚酯组合物,其包含一种或更多种可生物降解的无规共聚物聚酯和/或一种或更多种可生物降解的均聚物聚酯;基于100总重量份的所述一种或更多种可生物降解的无规共聚物聚酯和/或所述一种或更多种可生物降解的均聚物聚酯,约0.1重量%至约10重量%的一种或更多种挥发性腐蚀抑制剂;以及基于100重量份的所述一种或更多种可生物降解的无规共聚物聚酯和/或所述的一种或更多种可生物降解的均聚物聚酯,约3重量份至约53重量份的至少一种填料。
具体实施方式
本发明涉及可生物降解的VCI组合物,其适用于许多用途,包括各种物品、设备、机器、部件等的包装。这样的物品包含在、包围在、包裹在或以其他方式存在于本发明的可生物降解的VCI包装组合物中。包装材料优选呈可以用于形成容器、外壳、或盒的片形式或膜形式来保护上述物品免受腐蚀。
可生物降解的VCI组合物的基本组分是一种或更多种可生物降解的均聚物聚酯或者一种或更多种无规共聚物聚酯,或者二者。可以用作一种或更多种均聚物聚酯的聚合物例如聚丙交酯,聚己内酯,聚羟基链烷酸酯(PHA)、聚乙交酯、或者聚己内酯和PLA的共混物,或其任意组合,期望是相对纯的,即其中不包含污染物或聚合物。即,其通常包含小于约3重量%或约1重量%的任何污染物,期望地小于约0.5重量%,并且优选地小于约0.1重量%或零,没有任何污染物存在。
可以使用商业聚丙交酯均聚物或其他均聚物聚酯的典型分子量,其中其重均分子量为约100,000g/mol至约175,000g/mol,期望地约110,000g/mol至约150,000g/mol,并且优选地约125,000g/mol至约140,000g/mol。可以使用分子量不同的和/或从不同制造商获得的一种或更多种聚丙交酯。仅作为实例的方式,可以用于本发明的合适的聚丙交酯为由Natureworks制造的PLA 3052D。
除了一种或更多种可生物降解的均聚物聚酯之外,或者将其代替,可以使用一种或更多种无规共聚物聚酯,例如脂族-芳族无规共聚酯或无规脂族共聚酯。无规共聚酯的数量和种类广泛,并且通常具有下式:
其中,x独立地为约2至约10、或约34的整数(二聚脂肪酸),其中y独立地为2至约8的整数。
期望地,-(CH2)x-可以衍生自己二酸、癸二酸、或壬二酸,以及-(CH2)y-可以衍生自1,4-丁二醇或乙二醇。
重复单元的数量“m”和“n”使得无规共聚物的总重均分子量如下所示。
合适的可堆肥无规共聚物聚酯的实例包括聚癸二酸丁二醇酯-共聚-对苯二甲酸丁二醇酯(PBST),优选聚己二酸丁二醇酯-共聚-对苯二甲酸丁二醇酯(PBAT)。一种或更多种无规共聚物聚酯的重均分子量可以独立地在约80,000至约175,000的范围内,其中期望的重均分子量为约90,000至约150,000,优选地约100,000至约130,000。
上述聚丙交酯均聚物聚酯以及无规共聚物聚酯的重均分子量通过凝胶渗透色谱(GPC)来确定,其中将聚合物溶解在氯仿中,GPC的溶剂为四氢呋喃,以及温度为23℃。
本发明的一个重要方面是无规共聚酯不包含任何衍生自琥珀酸的重复单元。通常发现此类组合物具有差的物理特性,例如低的抗撕裂性以及低透明度,这两者对于腐蚀抑制组合物均是重要的特性。此外,通常脂族-共聚酯例如PBS(聚)(琥珀酸丁二醇酯)具有差的机械特性以及/或者也是昂贵的。因此,如果使用,基于共聚物中的重复基团的总数,衍生自琥珀酸的任何重复单元的量非常小,例如小于约10%,并且期望地小于2%。优选为零,即基于本发明的一种或更多种可生物降解的聚酯的总重量,无论如何都不使用衍生自琥珀酸的共聚酯。
当一种或更多种无规共聚物聚酯的混合物与一种或更多种均聚物聚酯一起使用时,基于100总重量份的所有可生物降解的聚酯,其(即,共聚物)的量为约50重量%至约95重量%,期望地约60重量%至约90重量%,并且优选地约70重量%至约85重量%。基于100总重量份的所有可生物降解的聚酯,一种或更多种均聚物-聚酯的量为约5重量%至约50重量%;期望地约10重量%至约40重量%,并且优选地约15重量%至约30重量%。如果聚酯抑制剂组合物不是共混物,则均聚物或无规共聚物的量当然为100重量%。
作为实例,已经发现一种或更多种无规共聚酯与一种或更多种均聚酯例如PLA的量的高比率对于提高产品的机械性能和适用期是重要的。
根据本发明,可生物降解的VCI包装组合物可以由一种或更多种如上所述的均聚物、或者由一种或更多种如上所述的共聚物、或者由包含一种或更多种均聚物与一种或更多种共聚物的共混物制成。此外,通常总是将一种或更多种填料与上述三种共混物中的任一种一起使用,因为已经出人意料地发现这些填料改善其如下所述的特性。
可以使用的本发明的一种或更多种挥发性腐蚀抑制剂包括各种***及其衍生物,例如苯并***和甲苯***;各种苯甲酸盐/酯,例如苯甲酸铵;各种铵盐;各种氨基甲酸盐/酯;各种磷酸盐/酯;和各种碱性酸成盐,例如美国专利4,973,448;5,139,700;5,715,945;6,028,160;6,156,929;6,617,415;和6,787,065中所述的,在此通过引用完全并入。本发明有用的VCI优选包括:各种无机亚硝酸盐或碱金属亚硝酸盐,其中优选地亚硝酸钾和亚硝酸钠;以及各种钠盐例如辛酸钠、苯甲酸钠;各种苯甲酸衍生物例如2-羟基苯甲酸或3-羟基苯甲酸或4-羟基苯甲酸、苯甲酸铵;以及脂族羧酸(例如山梨酸或二羧酸)的各种碱金属(例如钠或钾)盐。这种酸具有约5至约18个碳原子。
填料是本发明的一个重要方面,以提供易于加工(例如挤出树脂)、对于由这种材料制成的袋的防粘连效果、降低成本、保持拉伸强度、降低最终产品的密度、以及更高的刚度。还发现各种一种或更多种填料例如滑石、碳酸钙、碳酸钠、硅酸盐、粘土、和重晶石、或其任意组合有助于调节WVTR率。即,将其混合到整个可生物降解的VCI包装组合物中改善孔隙率,因此促进更多水分子对各种一种或更多种VCI化合物的期望的接近。还发现,可生物降解聚酯膜的比基于聚乙烯(PE)的膜的水蒸气透过率(WVTR)更高的水蒸气透过率(WVTR)对于本发明的可生物降解的VCI包装组合物的短期应用允许较低的VCI化合物负载。滑石是优选的填料。基于100总重量份的一种或更多种均聚物聚酯和/或一种或更多种无规共聚物聚酯,一种或更多种填料的总量通常为约3重量份至约53重量份,期望地约5重量份至约33重量份,并且优选地约5重量份至约18重量份。根据所添加的填料的纵横比,它们可以降低或增加透气性,从而有助于基于所使用的填料的类型为不同的应用定制期望的适用期和使用寿命。本发明不含淀粉作为填料,即不具有淀粉。
由于有助于本发明的高WVTR的各种因素,本发明的独特优在于仅需要使用少量的此类VCI化合物。即,基于总重量例如100总重量份的一种或更多种均聚物聚酯和/或一种或更多种无规共聚物聚酯,各种一种或更多种VCI化合物的范围为约0.1重量%至约10重量%,期望地约0.3重量%至约5重量%,并且优选地约0.5重量%至约2重量%或约0.9重量%。换言之,本发明中使用的一种或更多种VCI的总量可以变化很大。
本发明的可生物降解的VCI包装组合物的各种不同制剂的制备通常可以以本领域和文献中已知的任何方式进行。对于本发明,最初制备各种预母料,然后随后在高于可生物降解化合物(例如上文公开的各种类型的聚酯)的熔点的温度下将所有混合在一起。例如,向约20重量份的本发明的一种或更多种无规聚酯和/或一种或更多种均聚物聚酯聚合物中添加约1重量份至约10重量份的一种或更多种VCI以形成VCI母料。由于基于一种或更多种均聚物聚酯和/或一种或更多种共聚物聚酯的总重量,最终组合物中的VCI的最终总量小于10重量%,随后将一定量的VCI母料添加到已有的大量可生物降解的聚酯中以产生可生物降解聚酯组合物,如上所述,即基于仅所述聚酯的总重量,其中的VCI为约0.1重量%至约10重量%,期望地约0.3重量%至约5重量%,并且优选地约0.5重量%至约2重量%。VCI母料的制备通常可以在任何加热和混合装置例如挤出机、密炼机、或者优选地双螺杆挤出机中进行,其中混合温度高于无规共聚酯的熔点。
填料母料通常以相同的方式制备,其中将按重量计少量的填料添加到大量一种或更多种无规共聚酯和/或一种或更多种均聚物聚酯聚合物中。随后,将少量填料母料添加至大量可生物降解的聚酯中以形成其中具有期望量的填料的最终组合物。当然,形成填料母料的一种或更多种填料的共混温度为高于一种或更多种无规共聚酯的熔点的温度。
换言之,为了制备本发明的制剂,制备包含100重量份的一种或更多种均聚物聚酯和/或一种或更多种无规共聚物聚酯的组合物。向其中添加适量的VCI,使得基于100重量份的期望的可生物降解的聚酯的最终总量,VCI的量为如上所述的其约0.1重量%至约10重量%。然后以适当的量添加填料母料,使得一种或更多种可生物降解的聚酯的最终总量为100重量份并且一种或更多种填料的量在上述重量范围内。即,一旦针对一种或更多种VCI化合物、一种或更多种填料化合物制备了各种期望的母料,就将所有必需的母料与额外量的可生物降解的无规共聚酯和/或期望量的一种或更多种可生物降解的均聚酯一起混合以形成最终的可生物降解的VCI包装组合物。混合可以在任何期望的混合装置例如压延机、挤出机等中进行,并成形为丸粒、颗粒等,或者直接成型为最终产品,例如具有期望厚度的片材、袋或包裹物。对于本发明,厚度为约0.5密耳至约8密耳,并且期望地约0.8密耳至约5.0密耳,并且优选地约1.5密耳至约2.5密耳厚度的片材随后可以用于形成容器、外壳等以通常保护金属制品或物品免受腐蚀。此外,本发明的包装组合物可以为其中具有一个或更多个片材的一种或更多种层合体。例如,第一片材可以包含其中包含VCI且其中包含上述填料中的一者的上述一种或更多种无规共聚物聚酯和一种或更多种均聚物聚酯聚合物。层合体的第二片材可以仅包含任选地包含填料并且任选地包含VCI的所述一种或更多种可生物降解的无规共聚物聚酯。明显的是,许多其他不同类型的层合体可以由本发明的可生物降解的挥发性腐蚀抑制剂聚酯组合物制成。
根据本发明,可以制备具有如下宽范围的WVTR的透气的可生物降解的挥发性腐蚀抑制剂包装组合物:例如,根据ASTM F1249标准化为1密耳,在38℃/90%RH下为例如约100[g/(m2 d)]至约2000[g/(m2 d)]、期望地约300[g/(m2 d)]至约1000[g/(m2 d)]、优选地约400[g/(m2 d)]至约600[g/(m2 d)]。
通过参照以下用于说明本发明的实施例将更好地理解本发明,但不限制本发明。为了确定现有技术以及本发明的特性,实现了以下标准测试。
实施例1:将PBAT丸粒在50℃下干燥最少2小时,并与经研磨的亚硝酸钠粉末(VCI#1)以70比30的比例混合。然后将混合物进给至L/D为44且螺杆直径为26mm的双螺杆反向旋转挤出机的进料口,其中将大部分区域的温度控制在约270°F至290°F的范围内。模具温度保持在300°F。电机速度为约150rpm,并产生“线材”,将其在水浴中冷却,制粒成约3.18mm(0.125英寸)的丸粒并干燥。
然后将VCI MB与类似干燥的表1中所述的PBAT和PBAT/填料丸粒和/或PLA混合,并经由吹膜生产线挤出成膜,以5英尺/分钟以60微米厚度运行。
对照组样品由LDPE和LLDPE的共混物制成,其中VCI水平相当,用于比较。
在接触腐蚀测试中,当根据IEC 68-2-30循环室测试进行测试时,具有较低WVTR的基于PE的树脂内部的面板显示出沿边缘的几个腐蚀区域和在面板主体上的大于三个点。在7次循环后,作为对照组的PE袋中的面板获得3级,而本实施例中的具有可生物降解树脂、PBAT/填料、和PBAT/PLA/填料共混物的面板没有表现出腐蚀并且被评级为5。
LDPE/LLDPE(对照组)样品的WVTR与所述以上实施例1在38℃/90%RH下的高于300[g/(m2.d)]相比低于11[g/(m2.d)]。
根据NACE标准TM0208的VCI测试对于本发明的可生物降解的样品显示为3级,而对于具有相当的VCI含量的基于PE的对照样品显示为2级。
实施例 | PBAT | PLA | 填料 | VCI 1 |
1 | 100 | 0 | 8.18777 | 0.98253 |
1 | 100 | 5.77367 | 8.18777 | 0.98253 |
对于这里包括的所有实施例,使用相同的干燥步骤和混合设备以及混合步骤。
实施例2
以类似的过程制备另一个样品:首先制备MB,然后将MB与其中使用了不同的粉末混合物化学物质并评估了化学物质的有效性的膜树脂共混。粉末混合物由68%辛酸钠、7%4-羟基苯甲酸酯、3%苯并***、和22%苯甲酸铵组成。该混合物接着被称为VC1#2。然后将该混合物与PBAT丸粒以70%比30%的比例混合以制备母料。
将其与被称为VCI#3的87%辛酸钠、9%4-羟基苯甲酸盐/酯、4%苯并***进行比较。然后将各粉末混合物与PBAT丸粒以70份比30份的比例混合以制备母料。之后,通过将以上MB以下面的负载与PLA、PBAT和填料通过MB混合而制成膜,其余部分作为PBAT包含。
对于两个实施例的根据(IEC 68-2-30)运行的循环大气室中的接触测试表明:与获得2级评级的VCI#3相比,第一混合物VCI#2获得4级至5级保护。
NACE标准TM0208测试对第一种制剂显示为3级,而对于第二组显示为1级。
实施例 | PBAT | PLA | 填料 | VCI 2 | VCI 3 |
2 | 83.89 | 16.11 | 6.44468 | 1.15237 | 0 |
2 | 83.89 | 16.11 | 6.44468 | 0 | 1.15237 |
实施例3
与实施例1类似并且仅具有不同的VCI化学物质,在一种情况下以类似负载的PBAT/填料添加VCI#2,在另一种情况下添加到LDPE/LLDPE共混物作为对照组。在测试1周(7个循环(IEC 68-2-30))后,PBAT/VCI膜未显示出腐蚀(5级),而在对照组(具有相当的VCI浓度的LDPE/LLDPE膜)中观察到相当多的点(3级)。
实施例 | PBAT | PLA | 填料 | VCI 2 |
3 | 100 | 0 | 8.188 | 0.98253 |
实施例4
将VCI#2以相同的负载添加到PBAT/填料混合物中,其中两组之间的差异为填料水平,一组处于较低填料水平,一组处于较高填料水平。
具有较高填料水平的组在两周(14个循环)后在根据(IEC 68-2-30)运行的循环室测试中显示出更好的保护。较高填料的评级为4至5,而较低填料样品的评级为3至4。与在38℃/90%RH下测试的323[g/(m2 d)](经标准化)的低负载的WVTR相比,较高填料膜的水蒸气透过率为412[g/(m2 d)]。
实施例 | PBAT | PLA | 填料 | VCI 2 |
4 | 100 | 0 | 17.417 | 1.06635 |
4 | 100 | 0 | 8.18777 | 0.98253 |
实施例5
在实施例#2中,VCI#3显示出较弱的结果,然而,当以更高的填料水平使用时,显示出改善的结果。虽然含较低填料的样品在(IEC 68-2-30)测试的14次循环后显示为2级,但较高填料样品显示为3级。
实施例 | PBAT | PLA | 填料 | VCI 3 |
5 | 100 | 0 | 17.417 | 1.06635 |
5 | 100 | 0 | 8.18777 | 0.98253 |
虽然根据专利法规,已经阐述了最佳实施方式和优选实施方案,但本发明的范围不限于此,而是由所附权利要求的范围限制。
Claims (20)
1.一种可生物降解的挥发性腐蚀抑制剂聚酯组合物,包含:
一种或更多种可生物降解的无规共聚物聚酯和/或一种或更多种可生物降解的均聚物聚酯;
基于100总重量份的所述一种或更多种可生物降解的共聚物聚酯和/或所述一种或更多种可生物降解的均聚物聚酯,约0.1重量%至约10重量%的一种或更多种挥发性腐蚀抑制剂;和
基于100重量份的所述一种或更多种可生物降解的共聚物聚酯和/或所述一种或更多种可生物降解的均聚物聚酯,约3重量份至约53重量份的至少一种填料。
3.根据权利要求2所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述挥发性腐蚀抑制剂包括以下中的一者或更多者:***或其衍生物;苯甲酸盐/酯;氨基甲酸盐/酯;磷酸盐/酯;碱性酸成盐,涵盖无机亚硝酸盐或碱金属亚硝酸盐;脂族羧酸或二羧酸的碱金属盐;以及其中所述一种或更多种填料包括滑石、碳酸钙、硅酸盐、碳酸钠、粘土、或重晶石、或其任意组合。
4.根据权利要求3所述的可生物降解的挥发性腐蚀抑制剂组合物,其中当所述组合物为共混物时,其中基于所述一种或更多种均聚物和所述一种或更多种共聚物的总量,所述一种或更多种均聚物聚酯的量为约5重量%至约50重量%,以及其中所述一种或更多种共聚物聚酯的量为约50重量%至约95重量%;其中基于100总重量份的所述一种或更多种均聚物聚酯和所述一种或更多种共聚物聚酯,所述一种或更多种填料的量为约5重量份至约33重量份,以及其中基于一种或更多种均聚物聚酯和所述一种或更多种共聚物聚酯的总量,所述一种或更多种腐蚀抑制剂的量为约0.3重量%至约5重量%。
5.根据权利要求4所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种共聚物聚酯的重均分子量为约90,000至约150,000,以及其中所述一种或更多种均聚物聚酯的重均分子量为约125,000至约140,000。
6.根据权利要求5所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述均聚物聚酯为所述聚丙交酯,其中所述一种或更多种挥发性腐蚀抑制剂包括亚硝酸钠、辛酸钠、苯甲酸铵、苯甲酸钠、苯并***、辛酸、4-羟基苯甲酸、苯甲酸、山梨酸、或其任意组合;以及其中所述填料包括滑石。
7.根据权利要求6所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种聚丙交酯均聚物的量为约15重量%至约30重量%,其中所述一种或更多种共聚物聚酯的量为约70重量%至约85重量%,以及其中所述一种或更多种共聚物聚酯具有不是衍生自琥珀酸的重复单元。
8.根据权利要求1所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述聚酯包括一种或更多种所述可生物降解的共聚物聚酯。
10.根据权利要求9所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述挥发性腐蚀抑制剂包括以下中的一者或更多者:***或其衍生物;苯甲酸盐/酯;氨基甲酸盐/酯;磷酸盐/酯;碱性酸成盐,涵盖无机亚硝酸盐或碱金属亚硝酸盐;脂族羧酸或二羧酸的碱金属盐;以及其中所述一种或更多种填料包括滑石、碳酸钙、硅酸盐、碳酸钠、粘土、或重晶石或其任意组合。
11.根据权利要求10所述的可生物降解的挥发性腐蚀抑制剂组合物,其中基于100总重量份的所述一种或更多种共聚物聚酯,所述一种或更多种填料的量为约5重量份至约33重量份;以及其中基于所述一种或更多种共聚物聚酯的总量,所述一种或更多种腐蚀抑制剂的量为约0.3重量%至约5重量%。
12.根据权利要求11所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种共聚物聚酯的重均分子量为约90,000至约150,000。
13.根据权利要求12所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种挥发性腐蚀抑制剂包括亚硝酸钠、辛酸钠、苯甲酸铵、苯甲酸钠、苯并***、辛酸、4-羟基苯甲酸、苯甲酸、山梨酸、或其任意组合;以及其中所述填料包括滑石。
14.根据权利要求13所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种共聚物聚酯具有不是衍生自琥珀酸的重复单元。
15.根据权利要求1所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述聚酯包括所述一种或更多种可生物降解的均聚物聚酯。
16.根据权利要求15所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种均聚物聚酯包括聚丙交酯、聚己内酯、聚乙交酯、聚羟基链烷酸酯、或其任意组合;以及其中所述一种或更多种均聚物聚酯的重均分子量为约100,000至约175,000。
17.根据权利要求16所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述挥发性腐蚀抑制剂包括以下中的一者或更多者:***或其衍生物;苯甲酸盐/酯;氨基甲酸盐/酯;磷酸盐/酯;碱性酸成盐,涵盖无机亚硝酸盐或碱金属亚硝酸盐;脂族羧酸或二羧酸的碱金属盐;以及其中所述一种或更多种填料包括滑石、碳酸钙、硅酸盐、碳酸钠、粘土、或重晶石或其任意组合。
18.根据权利要求17所述的可生物降解的挥发性腐蚀抑制剂组合物,其中基于100总重量份的所述一种或更多种均聚物聚酯,所述一种或更多种填料的量为约5重量份至约33重量份;以及其中基于所述一种或更多种均聚物聚酯的总量,所述一种或更多种腐蚀抑制剂的量为约0.3重量%至约5重量%。
19.根据权利要求18所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述一种或更多种均聚物聚酯的重均分子量为约125,000至约140,000。
20.根据权利要求19所述的可生物降解的挥发性腐蚀抑制剂组合物,其中所述均聚物聚酯为所述聚丙交酯,其中所述一种或更多种挥发性腐蚀抑制剂包括亚硝酸钠、辛酸钠、苯甲酸铵、苯甲酸钠、苯并***、辛酸、4-羟基苯甲酸、苯甲酸、山梨酸、或其任意组合;其中所述填料包括滑石;以及其中所述一种或更多种聚丙交酯均聚物不具有衍生自琥珀酸的重复单元。
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6028160A (en) * | 1998-10-01 | 2000-02-22 | Cortec Corporation | Biodegradable vapor corrosion inhibitor products |
US6033599A (en) * | 1998-10-13 | 2000-03-07 | Interwrap Industries Inc. | Vapor phase corrosion inhibitors |
US6156929A (en) * | 1998-10-01 | 2000-12-05 | Cortec Corporation | Biodegradable film |
EP1281790A1 (de) * | 2001-07-30 | 2003-02-05 | EXCOR Korrosionsforschung GmbH | Dampfphasen-Korrosionsinhibitoren und Verfahren zu deren Zubereitung |
US6617415B1 (en) * | 2002-06-17 | 2003-09-09 | Cortec Corporation | Biodegradable corrosion inhibitor packages |
US20040173779A1 (en) * | 2002-01-22 | 2004-09-09 | Gencer Mehmet A. | Biodegradable shaped article containing a corrosion inhibitor and inert filler particles |
TW200516173A (en) * | 2003-01-22 | 2005-05-16 | Northern Technologies Int | Corrosion inhibiting composition and article containing it |
JP2007308726A (ja) * | 2006-05-16 | 2007-11-29 | Aicello Chemical Co Ltd | 金属用防錆剤組成物、それを含む樹脂組成物及びその成形体 |
US20090151598A1 (en) * | 2007-12-12 | 2009-06-18 | Georg Reinhard | Vapor phase corrosion inhibitors and method for their production |
KR100934197B1 (ko) * | 2009-04-14 | 2009-12-29 | 주식회사 러스트케미칼 | 생분해성 방청 수지용 방청제, 이를 포함하는 생분해성 방청 수지 조성물과 방청 필름, 및 방청 필름의 제조방법 |
CN103429428A (zh) * | 2010-12-01 | 2013-12-04 | 北方科技国际股份有限公司 | 用于保护金属免于腐蚀性气体的层板 |
CN109265935A (zh) * | 2018-09-06 | 2019-01-25 | 维希艾防锈新材料(上海)有限公司 | Vci纳米拦截式防锈膜 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4973448A (en) | 1986-11-18 | 1990-11-27 | Cortec Corporation | Vapor phase corrosion inhibitor product and method containing a desiccant |
US5139700A (en) | 1988-08-23 | 1992-08-18 | Cortec Corporation | Vapor phase corrosion inhibitor material |
US5715945A (en) | 1996-03-18 | 1998-02-10 | Cortec Corporation | Vapor phase corrosion inhibitor package utilizing plastic packaging envelopes |
FR2774995B1 (fr) | 1998-02-17 | 2002-07-19 | Cfpi Ind | Composition ou premelange a base d'inhibiteurs de corrosion volatils, articles comportant cette composition et leur procede de preparation |
US8008373B2 (en) * | 2002-01-22 | 2011-08-30 | Northern Technologies International Corp. | Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties |
US6984426B2 (en) | 2003-06-02 | 2006-01-10 | Cortec Corporation | Biodegradable bag |
WO2005068559A1 (ja) * | 2004-01-19 | 2005-07-28 | Chubu Chelest Co., Ltd. | 気化性防錆剤、これを用いた成形材料及び成形品 |
KR100825277B1 (ko) * | 2006-06-07 | 2008-04-28 | (주)알티아이엔지니어링 | 기화성 방청제 및 그 제조 방법 |
EP2748256B1 (en) | 2011-10-24 | 2017-06-14 | PURAC Biochem BV | A compound comprising plla and pdla |
US9034983B2 (en) * | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
US11193236B2 (en) * | 2015-02-06 | 2021-12-07 | Avintiv Specialty Materials Inc. | Vapor-permeable, substantially water-impermeable, corrosion-inhibiting composites and methods of making the same |
US11987696B2 (en) * | 2018-08-07 | 2024-05-21 | Northern Technologies International Corporation | Biobased polyester blends with enhanced performance properties |
-
2020
- 2020-06-30 MX MX2021015980A patent/MX2021015980A/es unknown
- 2020-06-30 WO PCT/US2020/040277 patent/WO2021003146A1/en unknown
- 2020-06-30 BR BR112021026101A patent/BR112021026101A2/pt unknown
- 2020-06-30 CN CN202080048391.8A patent/CN114364740B/zh active Active
- 2020-06-30 JP JP2021577934A patent/JP2022538354A/ja active Pending
- 2020-06-30 CA CA3142161A patent/CA3142161A1/en active Pending
- 2020-06-30 KR KR1020227003567A patent/KR20220033496A/ko unknown
- 2020-06-30 EP EP20834605.6A patent/EP3994005A4/en not_active Withdrawn
- 2020-06-30 US US17/254,680 patent/US11939423B2/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6028160A (en) * | 1998-10-01 | 2000-02-22 | Cortec Corporation | Biodegradable vapor corrosion inhibitor products |
US6156929A (en) * | 1998-10-01 | 2000-12-05 | Cortec Corporation | Biodegradable film |
US6033599A (en) * | 1998-10-13 | 2000-03-07 | Interwrap Industries Inc. | Vapor phase corrosion inhibitors |
EP1281790A1 (de) * | 2001-07-30 | 2003-02-05 | EXCOR Korrosionsforschung GmbH | Dampfphasen-Korrosionsinhibitoren und Verfahren zu deren Zubereitung |
US20040173779A1 (en) * | 2002-01-22 | 2004-09-09 | Gencer Mehmet A. | Biodegradable shaped article containing a corrosion inhibitor and inert filler particles |
US6617415B1 (en) * | 2002-06-17 | 2003-09-09 | Cortec Corporation | Biodegradable corrosion inhibitor packages |
TW200516173A (en) * | 2003-01-22 | 2005-05-16 | Northern Technologies Int | Corrosion inhibiting composition and article containing it |
JP2007308726A (ja) * | 2006-05-16 | 2007-11-29 | Aicello Chemical Co Ltd | 金属用防錆剤組成物、それを含む樹脂組成物及びその成形体 |
US20090151598A1 (en) * | 2007-12-12 | 2009-06-18 | Georg Reinhard | Vapor phase corrosion inhibitors and method for their production |
KR100934197B1 (ko) * | 2009-04-14 | 2009-12-29 | 주식회사 러스트케미칼 | 생분해성 방청 수지용 방청제, 이를 포함하는 생분해성 방청 수지 조성물과 방청 필름, 및 방청 필름의 제조방법 |
CN103429428A (zh) * | 2010-12-01 | 2013-12-04 | 北方科技国际股份有限公司 | 用于保护金属免于腐蚀性气体的层板 |
CN109265935A (zh) * | 2018-09-06 | 2019-01-25 | 维希艾防锈新材料(上海)有限公司 | Vci纳米拦截式防锈膜 |
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WO2021003146A1 (en) | 2021-01-07 |
CN114364740B (zh) | 2024-04-30 |
US20220185953A1 (en) | 2022-06-16 |
KR20220033496A (ko) | 2022-03-16 |
BR112021026101A2 (pt) | 2022-02-15 |
US11939423B2 (en) | 2024-03-26 |
EP3994005A1 (en) | 2022-05-11 |
JP2022538354A (ja) | 2022-09-01 |
EP3994005A4 (en) | 2023-08-09 |
MX2021015980A (es) | 2022-04-12 |
CA3142161A1 (en) | 2021-01-07 |
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