CN1723380A - 多层复合聚酰胺制品及其制备方法 - Google Patents
多层复合聚酰胺制品及其制备方法 Download PDFInfo
- Publication number
- CN1723380A CN1723380A CNA2003801055980A CN200380105598A CN1723380A CN 1723380 A CN1723380 A CN 1723380A CN A2003801055980 A CNA2003801055980 A CN A2003801055980A CN 200380105598 A CN200380105598 A CN 200380105598A CN 1723380 A CN1723380 A CN 1723380A
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- Prior art keywords
- layer
- polyamide
- temperature
- aliphatic
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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Images
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Abstract
本发明公开了多层聚酰胺复合制品,包括含有脂族和半芳族聚酰胺并且可以更好地在高温下长期保持其机械性能的至少三层。含有脂族聚酰胺的层可以任选含有氧化稳定剂。这些制品可以引入到换热器中的管的形式存在。本发明还提供了它们的制备方法。
Description
发明领域
本发明涉及可以更好地在高温下长期保持其机械性能的多层聚酰胺复合材料制品。本发明更具体地涉及三层或三层以上的聚酰胺制品,以及引入了管形式的这种制品的装置比如换热器。
背景技术
聚酰胺是用于许多要求高的应用的有吸引力的材料,因为它们的机械性能和耐化学品性。这些应用的许多涉及在高温下使用。例如,在汽车发动机机舱中应用的组件比如导管,风扇,风扇罩,歧管,管等需要在高温下换热器操作。在涉及使用可以在高温下操作的用于制造换热器的塑料管、板和其它结构的专利文献中具有大量的证据。换热器可以采取各种形式;一种这样的结构采取以平行方式排列和在它们的游离端固定,使得流体可以流经其中形成的通道的多个管的形式。在所有这些应用中,希望这些结构和组件在高温下保持它们的机械性能比如劲度,强度和耐蠕变性。
聚合物的性能随温度的改变通过它的玻璃化转变温度来控制。它是当分子经历从玻璃状态到橡胶状态的转变时聚合物的分子结构的温度特性。玻璃状态的聚合物所显示的机械性能比如劲度和强度一般明显高于橡胶状态的那些性能。
在高温下使用塑料组件的另一个问题是氧化降解的速度是较高的,导致了以更快的速度损失机械性能。在氧化降解过程中,氧扩散到暴露的聚合物表面,并且与聚合物分子起反应。降解因此被引发并且更集中在暴露部件的表面附近,并且引起表面变脆。表面变脆对于整个部件的物理性能具有严重影响,因为外部弯曲和折曲负荷通常导致了表面的高应力集中。
阻止聚合物的氧化分解的通用方法是使用抗氧化添加剂。它们以低水平使用,并且常常定制用于特定聚合物。它们正常分散在整个聚合物基质中,并且均匀分布用来提供总体稳定性。
在聚酰胺中使用的氧化稳定剂一般分为三类:(i)以芳族胺类为基础的有机稳定剂,(ii)以时常与磷型化合物结合的以位阻酚为基础的有机稳定剂,和(iii)以铜和卤素化合物为基础的无机稳定剂。有机稳定剂常常不适于引入到需要在接近300℃或更高的温度下加工的聚酰胺中,因为它们倾向于挥发或分解。铜基无机稳定剂也是不适合的,因为它们在这些高温下导致了降解反应。在涉及聚合物熔体接触大气条件的挤出、吹塑、流延、薄膜吹塑等方法中,情况尤其如此。
US专利5,258,213描述了包含聚酰胺层,聚酯层,和增粘剂的多层热塑性复合材料。该复合材料不具有任何特定热或氧化稳定性。US专利5,425,817描述了多层塑料管,包括至少一种聚酰胺的内层和外层以及含有结晶聚酯的至少一中间层。再次,没有热或氧化稳定性的特定优点归因于该管。EP专利申请0 470 605公开了具有低温抗冲击性的管,由至少三层的互相相容的聚酰胺组成,其至少一层是玻璃增强的。没有描述氧化稳定性和在连续接触高温的情况下的长期性能保持的优点。US专利5,219,003公开了适合于输送机动车辆发动机燃料并且包括由至少两种互相相容的聚酰胺制备的三层的具有低温抗冲击性的管。内层和外层含有冲击改性剂和中层基本上不含任何物质。
可以看出,还不能获得由同时提供了在高使用温度下能保持改进机械性和对氧化降解稳定的聚酰胺制造的制品。本发明的目的是提供包括多个聚酰胺层的多层复合制品和制造这些制品的方法,其中同时避免了与在制品中引入了通常利用的氧化稳定剂和在高使用温度下的制品的机械性能的保持有关的问题。在参考本发明的详细描述之后,可以更好地理解本发明的这些和其它目的、特征和优点。
本发明的概述
本文公开和作为权利要求了包括多个聚酰胺层并且排列成包括两个表面层和一个或多个内层的多层制品,其中所述表面层进一步包括一种或多种脂族聚酰胺和其中所述内层的至少一个包括由至少大约25mol%的芳族单体衍生的半芳族聚酰胺。
本发明还公开和作为权利要求了制造本发明的多层制品的方法。此类方法包括在适于各层的加工条件下熔融挤出所述多层聚酰胺的每一层,和此后将所述层结合于选择的多层构型上。
在参考了如下所示的图例之后,可以更好地理解本发明。
附图简述
图1是描绘了本发明和对比实施例的管样品的随温度而变的杨氏模量变化的图。
图2是描绘了本发明和对比实施例的管样品随温度而变的拉伸强度的变化的图。
本发明的详细描述
本发明提供了显示了提高的在高温下机械性能保持性的可以用氧化稳定剂稳定和由含有聚酰胺的聚合物组合物制备的多层复合制品。所谓“多层复合制品”是指包括多个聚酰胺层压层,并且排列成包括两个表面层和一个或多个内层的制品。各表面层包括一种或多种脂族聚酰胺和至少一个内层包括由至少大约25mol%的芳族单体衍生的半芳族聚酰胺。
制品的高使用温度取决于应用。例如,几种汽车机罩下应用要求制品在100℃或更高的温度下运行。在加热、通风和空调以及需要热水或其它热流体的工业应用中的换热器也需要在70℃或更高的温度下操作。在高温下的机械性能的保持度取决于聚酰胺的分子组成。具体地说,相对于脂族基团的它的芳族基团的含量是重要的,因为该比率影响了该聚酰胺表现了从玻璃状态到橡胶状态的转变的温度窗,它被定义为聚酰胺的玻璃化转变温度(Tg)。在牵涉本发明中的聚酰胺的选择在以下叙述中可以更好地理解这些考虑。
本发明的复合多层制品的各表面层包括可以在使得通常利用的氧化稳定剂的引入不会导致在加工操作过程中过度降解反应或稳定剂损失的温度下加工的一种或多种脂族聚酰胺。复合制品还包括不接触这些表面之一的至少一内层。至少一个内层由半芳族聚酰胺制备。如果具有一个以上的内层,其它层可以由脂族和/或半芳族聚酰胺制备。
所谓“脂族聚酰胺”是指由脂族和脂环族单体比如二胺,二羧酸,内酰胺,氨基羧酸,和它们的反应性等效物形成的聚酰胺。在本发明的上下文中,该术语还表示由两种或多种此类单体衍生的共聚物和两种或多种脂族聚酰胺和/或共聚酰胺的共混物。可以使用线性、支化和环状单体。优选的脂族二胺的实例包括六亚甲基二胺,2-甲基五亚甲基二胺,1,4-二氨基丁烷,2,2,4-三甲基六亚甲基二胺,2,2,4-三甲基五亚甲基二胺,5-氨基-1,3,3-三甲基环己烷甲基胺,和双氨基甲基环己烷。优选的脂族二羧酸的实例包括己二酸,壬二酸,癸二酸,和十二烷二酸。优选的脂族氨基羧酸的实例包括11-氨基癸酸,和4-氨基环己基乙酸。优选的脂族内酰胺的实例是己内酰胺和月桂内酰胺。在本发明中使用的脂族聚酰胺可以任选地由至多10mol%的芳族单体获得,只要它们满足以下关于加工温度的标准。以下给出了此类芳族单体的实例。在用于表面层的脂族聚酰胺的选择中的关键考虑是它们的加工温度。这些脂族聚酰胺具有低于280℃的熔点,意思是它们可以在低于295℃的温度下加工。这些温度使得可以引入通常利用的氧化稳定剂,不会在加工操作过程中引起过度降解反应或稳定剂损失。在表1b中给出了优选的脂族聚酰胺的实例。
所谓“半芳族聚酰胺”是指由芳族和任选的脂族和/或脂环族单体形成的聚酰胺,其中至少大约25mol%的单体是芳族单体。在本发明中,该术语还表示由两种或多种此类单体获得的共聚物和两种或多种半芳族聚酰胺和/或共聚酰胺的共混物。可以在聚酰胺的制备中使用的芳族单体的百分率没有上限,只要所得聚酰胺是可熔体加工的。优选的是含有至多大约65mol%芳族单体的聚酰胺和更优选的是含有至多大约55mol%芳族单体的聚酰胺。
所谓“芳族单体”是指含有至少一个取代芳族体系比如苯环,萘等的单体。此类单体一般是二胺,二羧酸,内酰胺,氨基羧酸,和它们的反应性等效物。以上给出了优选的脂族和脂环族单体的实例。优选的芳族二胺的实例是间苯二甲胺,对苯二甲胺,间亚苯基二胺,和对亚苯基二胺。优选的芳族二羧酸和它们的衍生物的实例是对苯二甲酸,间苯二甲酸,对苯二甲酸二甲酯,和2,6-萘二羧酸。优选的芳族氨基羧酸的实例包括对氨基甲基苯甲酸,4-氨基苯基乙酸。优选的芳族内酰胺的实例是羟吲哚(oxinadole)。由对苯二甲酸或间苯二甲酸和脂族二胺制备的聚苯二酰胺是尤其优选的。在表1a中给出了优选的半芳族聚酰胺的实例。
在半芳族聚酰胺的选择中的关键考虑是它显示从玻璃状态到橡胶状态的转变的温度窗(它的玻璃转变)。据信,该转变在一定温度范围内发生,并且用材料的机械和粘弹性能比如劲度,储能和损耗模量的显著改变来表示。因为该转变在一定温度范围内发生,所以它的测量一定程度取决于用于测量它的技术。动态力学分析(DMA)和差示扫描量热法(DSC)是鉴定该转变的代表性温度的常用技术。该转变温度越高,聚合材料在高使用温度下保持其机械性能的能力越好。对于本发明,选择在一个或多个内层中使用的半芳族聚酰胺和在表面层中使用的该一种或多种脂族聚酰胺,使得半芳族聚酰胺的玻璃化转变温度高于脂族聚酰胺的玻璃化转变温度。
在表1a和1b中给出了代表性Tg,由各种来源收集。本领域的那些技术人员很清楚,Tg的测量是有些不太精确的方法,因此,以下示出的数值是近似值,提供用于说明的目的。
表1a
代表性半芳族聚酰胺
聚酰胺1 | 以在括号内给出的相对摩尔量使用的单体 | Tg(℃) | 熔点(℃) |
6T/DT | HMD(50):2-MPMD(50):TPA(100) | 135 | 300 |
6T/66 | HMD(100):TPA(55):AA(45) | 85 | 310 |
6T/6 | HMD(70):TPA(70):Capro(30) | 105 | 295 |
6T/6I | HMD(100):TPA(70):IPA(30) | 125 | 320 |
6T/6I/66 | HMD(100):TPA(60):IPA(30):AA(10) | 125 | 315 |
9T | 1,9-二氨基壬烷:TPA(100) | 125 | 308 |
MXD6 | MXD(100):AA(100) | 75 | 245 |
10T | DMD(100):TPA(100) | 100 | 318 |
12T | DDMD(100):TPA(100) | 85 | 295 |
1在该栏中的共聚酰胺由以在各成分旁所示的相对摩尔量使用的在第二栏的相应行中给出的成分制备。
表1b
代表性脂族聚酰胺
聚酰胺 | 以在括号内给出的相对摩尔量使用的单体 | Tg(℃) | 熔点(℃) |
66 | HMD(100):AA(100) | 48 | 265 |
6 | Capro(100) | 41 | 220 |
612 | HMD(100):DDDA(100) | 45 | 220 |
11 | 氨基十一烷酸(100) | 42 | 190 |
12 | 月桂内酰胺(100) | 40 | 180 |
610 | HMD(100):DDA(100) | 50 | 226 |
612 | HMD(100):DDDA(100) | 46 | 220 |
在表1a和1b中使用了下列缩写:
HMD 六亚甲基二胺
2-MPMD 2-甲基-1,5-戊二胺
TPA 对苯二甲酸
AA 己二酸
DMD 十亚甲基二胺
DDMD 十二亚甲基二胺
Capro ε-己内酰胺
DDDA 十二烷二酸
DDA 癸二酸
IPA 间苯二甲酸
MXD 间苯二甲胺
TMD 三甲基六亚甲基二胺
6T 由HMD和TPA形成的聚合物分子单元
DT 由2-MPMD和TPA形成的聚合物分子单元
66 由HMD和AA形成的聚合物分子单元
10T 由DMD和TPA形成的聚合物分子单元
12T 由DDMD和TPA形成的聚合物分子单元
6 由Capro形成的聚合物分子单元
612 由HMD和DDDA形成的聚合物分子单元
610 由HMD和DDA形成的聚合物分子单元
在本发明的复合制品表面层中使用的脂族聚酰胺还可以任选含有通过利用普通引入方式比如熔体配混尽可能均匀分散在聚酰胺体积中的氧化稳定剂。因为这些聚酰胺的熔点较低和相应较低的熔体加工温度,可以容易地引入氧化稳定剂,它们本身不会遭受过度降解或挥发,它们也不会引起在引入步骤过程中或在制造制品所需的后续加工过程中的聚酰胺的过度降解。
聚酰胺的任何已知抗氧化剂可以用于该目的。如在由Gachter和Muller编写的Plastics Additives Handbook中所述,通常使用三种主要类型的稳定剂。一种类型是铜盐,尤其与卤素和磷化合物结合。例如,乙酸铜常常与碘化钾/磷酸以在最终聚合物组合物中提供大约10-200ppm的铜和1000-4000ppm的卤素的水平使用。第二类是芳族胺比如N,N’-二萘基-对亚苯基二胺或N-苯基-N’-环己基-对亚苯基二胺,它们以大约0.5-2wt%的加量使用。第三类是以0.3-2wt%的加量使用的位阻酚比如N,N’-六亚甲基-双-3-(3,5-二叔丁基-4-羟苯基)丙酰胺。
因为该一个或多个内层被屏蔽,防止了与大气接触,所以不需要在内层引入氧化稳定剂,和因此有可能使用具有高熔点和玻璃化转变温度并且在高温下保持它们的物理性能,但它们难以与抗氧化剂合并的半芳族聚酰胺。这提供了附加的益处,因为稳定剂是比较昂贵的材料和仅在表面层中使用它们可以是经济上合算的安排。
因为聚酰胺通常是化学相容的材料,所以不需要提供任何特殊粘合或粘结材料层来将相邻的不同聚酰胺层粘结在一起。它们在熔体共挤出形式中显示了强粘合力,使得各层不能被分开。据假定,酰胺基转移甚至可以在相邻层的聚合物链之间发生。酰胺基转移的程度尤其取决于在熔体加工步骤过程中熔态接触的持续时间和温度。
用于制备本发明的多层复合制品的聚酰胺组合物可以进一步包括其它成分。例如,一个或多个表面和/或内层可以由进一步包括填料和/或增强剂比如矿物或玻璃纤维的组合物制备。一个或多个内层可以由半芳族聚酰胺组合物制备,或者如果存在一个以上的内层,由进一步包括增韧剂的脂族聚酰胺组合物制备。一个或多个表面层可以由进一步包括增韧剂的组合物制备。
本发明还提供了制造复合制品的方法。在多层共挤出方法中,使用独立的挤出机来挤出各类聚酰胺。布置挤出机的温度设置和其它加工条件,使得它们适于所要挤出的聚酰胺。这避免了使低熔点聚酰胺在挤出步骤中接触高于正常加工温度的温度,同时使较高熔点聚酰胺在合适温度下挤出。
在适当设计的模头(die)内将来自挤出料流的各熔体结合在一起,并且以所需多层布局排列。只有模头需要保持在用于内层的半芳族聚酰胺所需的较高加工温度下。因为在模头中的停留时间是非常短的,所以在低熔点稳定聚酰胺中的不希望有的降解效应被有力地降低到最小。模头可以设计成提供各种形状的多层挤出物。例如,它可以是管,片材,薄膜或任何其它型材形式。挤出物在冷却或骤冷罐内固化。
因为它的高玻璃化转变温度和快速骤冷,内层不能通过该方法完全结晶。有必要增高内层的结晶度,以优化在高温下的物理性能的保持度。结晶度可以通过让制品经受在线或单独的退火步骤来增加。退火步骤可以包括将制品简短地再加热至稍高于内层的聚酰胺的玻璃化转变温度的温度,如果需要,可以在无氧环境中进行。
本发明的制品可以包括、但不限于管道,管,管料,以及其它中空制品和片材。所述管可以在换热器的制造中使用。
在参考以下实施例和附表以后,可以更好地理解本发明。
实施例
实施例1
制备具有3.7mm的外径和0.2mm的总壁厚的三层共挤出管。内和外表面层由高粘度挤出级聚酰胺66(由E.I.DuPont de Nemours,Wilmington,DE出售的Zytel42 NC010)制备。表面层含有由大约0.06wt%CuI和0.39wt%KI组成的铜型热稳定剂,其中两个重量百分数是以组合物的总重量为基准。这提供了标称200ppm的铜和3500ppm的碘。它们还含有基于组合物的总重量的大约0.05wt%的炭黑作为着色剂。单一表面层的厚度是0.05mm。通过DSC测定的该聚酰胺66的熔点是大约265℃。内层由增韧半芳族聚苯二甲酰胺制备,后者由用1摩尔当量的六亚甲基二胺,1摩尔当量的2-甲基-1,5-戊二胺和2摩尔当量的对苯二甲酸制备的原料聚酰胺制成,并配混了大约15wt%烯烃增韧剂。半芳族聚苯二甲酰胺的熔点是大约300℃,以及通过DSC测定的玻璃化转变温度是135℃。该内层的厚度是0.1mm。
挤出装置由连接于三层管形模头的三个单独的单螺杆挤出机组成。使用购自Polysystems的具有32mm单螺杆的挤出机来挤出对应于管的外面的表面层材料。使用购自Barmag的具有25mm单螺杆的挤出机来挤出对应于管的内部的表面层材料。使用购自Randcastle的具有16mm单螺杆的挤出机来挤出内层材料。
用于聚酰胺66表面层的挤出机用250-280℃的机筒温度设置运行。用于半芳族聚苯二酰胺内层的挤出机在305-330℃的套温度下运行。使用计量泵和转移管道来将熔体料流从挤出机输送到模头。在管挤出端,模头由外径7.85mm的内尖头和内径8.89mm的外主体组成。模头主体设定在300℃,以防止半芳族聚苯二甲酰胺过早固化。从模头出来的三层挤出物使用水槽固化,再通过带式引出机拖出。线速度是大约31m/min。
这样生产的管材样品的杨氏模量和拉伸强度使用英斯特朗试验机在23-190℃范围内的几种温度下测定。使用10cm长试件,其中在试验机的两个抓手之间具有5cm的计量距离。管件的末端使用特殊设计的V形槽颚板在抓手中握紧,再将短圆柱形钢钎插入管的末端,以防止在抓手中的管箍缩和压碎。使用5cm/min的试验机十字头速度进行试验,并产生应力/应变曲线。由负荷位移曲线的初始斜率测定杨氏模量,以及由在曲线上的最大应力点测定拉伸强度。
在水浴中在23-90℃的多个温度下还测量管的水压破裂应力。由Barbee Pump供应的破裂压力仪器用于该目的。该仪器引入了手工操作水泵。使用适当的Swagelok配件将管试样的一端连接于泵的卸料端。首先将水泵送到另一端开放的管内,以便取代空气。开放端然后用加压用封闭Swagelok配件封盖。然后通过在温度控制水浴中浸渍达足够的时间将样品升高到所需试验温度,这通过测量管表面温度来测定。然后通过操作泵以流体静压方式来加压样品,直到破坏为止。引起破坏的最大压力被记录为破裂压力。
管样品还通过在氮气环境中简短接触150℃来退火。如上所述表征退火管的性能。
在图1中示出了杨氏模量试验的结果。
在图2中示出了拉伸强度试验的结果。
在以下表2中示出了破裂压力试验的结果。
对比实施例1
为了对比目的,使用在实施例1中所用的稳定高粘度PA66用与在上述实施例1中所用相同总体尺寸制备单层管料。挤出生产线装置仅需要一个挤出机和单层管料模头。使用上述Polysystems挤出机用于该目的,其中机筒温度设定在250-280℃范围,以及模头温度设定在280℃。
通过在与实施例1所用相同温度下的拉伸和破裂试验来表征管料。
在图1和2以及以下表2中示出了该单层管料的试验的对比结果。
表2
随温度而变的管样品的破裂压力的改变
管 | 温度(℃) | 试验条件 | 破裂压力(巴) |
对比实施例1的单层管 | 23 | 干燥 | 50.6 |
23 | 在水浴中 | 54.9 | |
50 | 在水浴中 | 25.3 | |
89 | 在水浴中 | 12.2 | |
实施例1的多层管,制成后原样 | 23 | 干燥 | 57.1 |
23 | 在水浴中 | 58.1 | |
50 | 在水浴中 | 28.8 | |
89 | 在水浴中 | 13.3 | |
实施例1的多层管,退火 | 23 | 干燥 | 77.4 |
23 | 在水浴中 | 65.6 | |
50 | 在水浴中 | 37.9 | |
89 | 在水浴中 | 22.5 |
从结果可以看出,具有脂族聚酰胺66的表面层和半芳族聚苯二酰胺的内层的多层管比单层管表现了更好的劲度保持和随温度而变的破裂性能。还有,因为聚苯二甲酰胺层在适当稳定的聚酰胺66的表面层之间包封,所以不需要在内层引入稳定剂。
Claims (8)
1、多层制品,包括多个聚酰胺层并且排列成含有两个表面层和一个或多个内层,其中所述表面层进一步包括一种或多种脂族聚酰胺和其中所述内层的至少一个包括由至少大约25mol%的芳族单体衍生的半芳族聚酰胺。
2、权利要求1的多层制品,其中所述脂族聚酰胺进一步包括选自铜盐、芳族胺和位阻酚中的一种或多种氧化稳定剂。
3、权利要求1的多层制品,其中所述脂族聚酰胺具有低于280℃的熔点。
4、管形式的权利要求1或2的多层制品。
5、以管的形式引入权利要求1或2的多层制品的换热器。
6、制造包括多个聚酰胺层并且排列成含有两个表面层和一个或多个内层,其中所述表面层进一步包括一种或多种脂族聚酰胺和其中所述内层的至少一个包括由至少大约25mol%的芳族单体衍生的半芳族聚酰胺的多层制品的方法,包括:
(a)在适于各层的加工条件下熔融挤出所述多层聚酰胺的每一层,此后
(b)将所述层合并成选择的多层构型。
7、权利要求5的方法,其中所述脂族聚合物进一步包括选自铜盐、芳族胺和位阻酚中的一种或多种氧化稳定剂。
8、权利要求5或6的方法,进一步包括退火所述选择多层构型的步骤(c)。
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CN106414554A (zh) * | 2014-04-15 | 2017-02-15 | 阿科玛法国公司 | 由半晶态聚酰胺制成的热塑性材料的制造方法 |
CN114502376A (zh) * | 2019-09-26 | 2022-05-13 | 3M创新有限公司 | 多层膜及其制备方法 |
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KR101106406B1 (ko) * | 2003-08-19 | 2012-01-17 | 솔베이 어드밴스트 폴리머스 엘.엘.씨. | 충격 보강된 폴리아미드 필름 |
CN1922461B (zh) * | 2003-12-22 | 2012-12-26 | 安格斯公司 | 封装的交换装置及其制造方法 |
JP2007524531A (ja) * | 2004-02-06 | 2007-08-30 | クーパー−スタンダード オートモーティブ、 インコーポレイテッド | 車両に適用するための芳香族ポリアミド管状材料 |
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US20110139258A1 (en) * | 2009-12-16 | 2011-06-16 | E.I. Du Pont De Nemours And Company | Multilayer structures comprising a barrier layer and their use to convey fluids |
WO2012058368A1 (en) * | 2010-10-29 | 2012-05-03 | E. I. Du Pont De Nemours And Company | Polyamide composite structures and processes for their preparation |
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CN114502376A (zh) * | 2019-09-26 | 2022-05-13 | 3M创新有限公司 | 多层膜及其制备方法 |
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