CN112739751A - 具有热塑性基材的复合材料 - Google Patents
具有热塑性基材的复合材料 Download PDFInfo
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Abstract
本发明涉及具有改性PVDF基材的连续纤维‑增强的复合材料。该复合材料可以是尤其制成的半成品或产品或成品件。根据本发明的产品是粒状长纤维材料,而根据本发明的成品件尤其是热塑性复合材料管。
Description
本发明涉及具有改性PVDF基材的连续纤维增强的复合材料。该复合材料可以是半成品或由其制成的产品或成品件。根据本发明的产品是粒状的长纤维材料,而根据本发明的成品件尤其是热塑性复合管。
具有PVDF基材的复合材料是已知的;具有玻璃纤维或碳纤维增强的相应类型可以市购。但是,纤维与PVDF基材之间的粘合性并不令人满意,这导致机械性能不足。另一个缺点是,在复合材料和复合材料中包括的组分之间不能实现直接的粘合。US 2011/0166278和WO 2016/142630描述了具有PVDF基材的复合材料,其通过制备PVDF和不饱和单体的混合物、用高能辐射对其进行辐照、然后除去未反应的不饱和单体部分而制备。然而,这种制备模式并不方便且昂贵,不能轻易地转化为生产规模。
潜在问题的一个方面是提供具有PVDF基材和良好的纤维-基材粘合性的更容易生产的复合材料。
由于PVDF的阻燃作用,这种复合材料引起了极大兴趣,例如用于飞机或机动车辆的制造。它们在用作热塑性复合材料管(TCP)中的增强层中也特别令人感兴趣,这是因为与具有聚酰胺基材的复合材料相比,它们从环境或所输送的介质中吸收更少的碳氢化合物、水或甲醇,特别是在所述物质的存在下,它们也可以经受较高的热应力。与具有聚烯烃基材的复合材料相比,情况相似。
柔性热塑性复合材料管至少由热塑性聚合物的内衬管、施加到其上的连续纤维带的多层缠绕层、热塑性材料的外部保护层而组成,其中所述多层纤维带已浸渍有热塑性基材。如果这些层相互粘结在一起的话,这也称为粘结的复合柔性管。这种管通常用于海上石油生产。特别是在较大的水深处使用,并且还为了将这种管可靠地连接到相应的连接元件上,例如端部配件,以及组装和铺设操作,将所述所有层相互粘结在一起是非常有利的。
TCP例如在WO 1995/007428和WO 1999/067561中描述。在WO 2002/095281、WO2006/107196、WO 2012/118378、WO 2012/118379和WO 2013/188644中还额外公开了其生产。在现有的TCP中,内衬管的材料(或在多层衬管的情况下为外衬层的材料)、所述带的基材材料和外保护层的材料(“外套”或“盖板”)通常由相同的聚合物而组成,以便因此能够实现缠绕层彼此以及与衬层和保护层之间的非常好的融合和粘附。根据最高使用温度和应用,这些通常是基于聚乙烯、聚丙烯或PA12/PA11的TCP。在较低的使用温度下,例如低于50℃,通常使用聚烯烃,以及高于PA11或PA12。在要引导的流体的温度超过80℃的应用中,PVDF均聚物或PVDF共聚物通常在高达约135℃的温度下用作衬里。如果使用聚合物内层的限制不是由操作温度而导致,而是由聚合物的化学稳定性而导致,则仅仅对流体稳定的薄的内保护层就足以作为内衬,该内衬同样可以由PVDF均聚物-或共聚物组成。
在当前开发的TCP中,优选使用PA12或PEEK的单层内衬,并且与它们结合使用具有相同聚合物基材的玻璃或碳纤维带。由于其特殊的性能以及高昂的材料成本,PEEK仅在对热和化学稳定性有极高要求的地方而使用。在中等的温度范围内,使用由PVDF或PA12和带有PA12基材的带而组成的内衬。然而,PA12带并不易于以所需的粘合力而粘附到PVDF内衬。该问题可以通过例如生产具有PVDF的内层、粘合促进剂层和PA12的外层的多层衬里而得以解决。但是,在该结构的情况下,形成了三个层界面(PVDF/粘合促进剂、粘合促进剂/PA12、PA12/带),其在极端操作条件下会成为薄弱点(尤其参见DNV-GL Recommended PracticeRP F119“Thermoplastic Composite Pipes”)。因此,该目标必须是将该TCP中的关键层界面的数量减少到最低。
因此,潜在问题的另一方面在于提供一种热塑性复合材料管,其具有最少的层界面,并具有易于制造的具有PVDF基材和良好的纤维-基材粘合性的复合材料的一个或多个增强层。
在下文中通过举例的方式描述了本发明的复合材料、本发明的成形体,例如包含本发明的复合材料的热塑性复合管(TCP)以及本发明的用途,而并无任何意图将本发明限于这些说明性实施方案。当在下面指定范围、通式或化合物类别时,它们不仅旨在涵盖明确提及的相应范围或化合物基团,而且还包括可以通过省略各个值(范围)或化合物而获得的所有子范围和化合物的子组。在本说明书的上下文中引用文件的情况下,其全部内容旨在作为本发明的公开的一部分。除非另有说明,否则在下文中给出百分比数字时,其以重量%计。在组合物的情况下,除非另外说明,否则百分比数字是基于整个组合物。在下文中给出平均值的情况下,除非另有说明,否则它们是质量平均值(重量平均值)。在下文中给出测量值的情况下,除非另有说明,否则这些测量值是在101 325Pa的压力和25℃的温度下而测定。
潜在问题的第一个方面通过本申请的主题而解决,该主题是由聚合物基材和嵌入其中的连续纤维组成的复合材料,
其中聚合物基材由至少80重量%,优选至少85重量%,更优选至少90重量%,特别优选至少95重量%的混合物组成,所述混合物包含以下组分:
a)低粘度PVDF作为主要成分,即含量至少为50重量份,和
b)1至50重量份,优选1.5至40重量份,更优选2至30重量份,特别优选2.5至20重量份,特别优选3至10重量份的丙烯酸酯共聚物,其中所述丙烯酸酯共聚物包含1-30重量%,优选2-25重量%,更优选4-20重量%,特别优选5-15重量%的具有羧酸酐单元的单元,
其中a)和b)的重量份之和为100,并且
其中连续纤维在复合材料中的体积比例另外为10%至80%,优选15%至75%,更优选20%至70%,甚至更优选25%至65%,特别优选30%至60%,特别优选35%至55%;
其中聚合物基材和连续纤维的百分比各自是基于复合材料的总质量或总体积。
EP 0673762A2(US 5554426A)公开了PVDF和丙烯酸酯共聚物是相容的并且彼此可均匀混溶,并且作为共混物,其对聚酰胺层具有良好的粘合性。其中还提到可以使该模塑(molding)化合物导电,特别是通过添加炭黑、碳纤维等。所述导电添加剂不能起到增强作用;在实施例中仅使用炭黑。没有公开纤维-基材粘附性。因此,EP 0673762A2中所讨论的层并不是本发明意义上的复合材料。
根据本发明的复合材料是纤维复合材料,其可以呈半成品或由其制成的成品件的形式。生产后直接的半成品为可具有任何所需几何形状的形状。例如,它可以是片、带、板、圆形形材、矩形形材或复杂形材。
连续纤维是长度大于50mm的那些。通常,它们明显更长。在本发明的上下文中,它们以粗纱或编织的形式而使用。原则上,合适的纤维是具有足够长度的所有纤维,其具有高于基材模塑配混物的加工温度约250℃的软化温度和热稳定性;可以使用无机纤维、聚合物纤维和天然纤维,以及彼此的组合物。合适纤维的实例是金属纤维、玻璃纤维,优选S1玻璃、S2玻璃的玻璃纤维、碳纤维、金属化碳纤维、硼纤维、陶瓷纤维(例如Al2O3或SiO2)、玄武岩纤维、碳化硅纤维、钛酸钾纤维、芳族聚酰胺纤维、液晶聚酯纤维、聚丙烯腈纤维和聚合物纤维,例如聚酰亚胺、聚醚酰亚胺、聚苯硫醚、聚对苯撑苯并双噁唑(PBO)、聚醚酮、聚醚醚酮等。玻璃纤维优选不应包含任何氧化硼或二氧化钛,这是因为它们可能导致PVDF的自催化降解。同样优选,玻璃纤维不含具有类似性质的物质。
纤维的横截面可以例如是圆形、矩形、椭圆形、椭圆或茧形的。所述直径优选为5μm至25μm。特别优选纤维具有直径为5至25mm的圆形横截面。
通过横截面偏离圆形的纤维(例如平板玻璃纤维),可以在成品件中获得更高的纤维填充水平,从而获得更高的强度。可市购的纤维通常在其表面上具有提供键合至聚合物基材的官能团的尺寸。为了本发明的目的,尺寸可能是有帮助的,但是原则上不是必需的。优选使用上浆纤维;该尺寸更优选对聚合物基材具有反应性。优选碳纤维;更优选上浆碳纤维。特别优选的上浆的碳纤维是其中尺寸为环氧基的那些。
更优选,所述复合材料包括基于复合材料为20%至60体积%,特别优选30%至55体积%,并且特别优选40%至50体积%的碳纤维。甚至更优选,所述复合材料包括基于复合材料为30%至55体积%的具有环氧尺寸的碳纤维。
PVDF作为聚偏二氟乙烯对本领域技术人员而言是已知的,并且可以以多种类型而市购。PVDF可以是均聚物或共聚物。根据本发明,所使用的聚偏二氟乙烯可以是基于偏二氟乙烯的共聚物,其包含至多40重量%的衍生自单体三氟乙烯、氯三氟乙烯、乙烯、丙烯和六氟丙烯的单元。优选,所述聚偏二氟乙烯是偏二氟乙烯的均聚物。
PVDF优选是低粘度的PVDF;优选,所述低粘度PVDF的熔体流动指数(MFI)优选为18至50克/10分钟,优选20至45克/10分钟,使用2.16kg(230℃)并根据ASTM D1238-13确定MFI。
具有较低的MFI的PVDF会导致纤维材料的浸渍较差并且导致聚合物基材的孔隙率增加。另外,在复合材料中只能实现较小比例的纤维材料。总体而言,较低的MFI会导致复合材料的机械性能下降。这些性质可以例如借助ASTM D2344-16而确定。
丙烯酸酯共聚物b)优选包含以下单元:
I.14%至80重量%,优选20%至70重量%,更优选30%至65重量%,特别优选40%至60重量%的下式的酯单元:
R=甲基、乙基、丙基或丁基,R1=氢或甲基;
II.10%至75重量%,优选20%至65重量%,更优选25%至50重量%,特别优选30%至40重量%的下式的酰亚胺单元:
R4=独立地为具有1至8个碳原子,优选具有1至4个碳原子的脂族或脂环基,更优选氢或甲基,和
R3=独立地为甲基、乙基、丙基、丁基或苯基;
R3和R4均为甲基;
m=0或1;
III.1%至20重量%,更优选1.5%至15重量%,特别优选2%至5重量%的下式的酸单元:
R2=氢或甲基;
IV.1%至30重量%,优选2%至25重量%,更优选4%至20重量%,特别优选5%至15重量%的下式的酸酐单元:
R5=独立地为具有1至8个碳原子,优选具有1至4个碳原子的脂族或脂环基团,更优选氢或甲基;
n=0或1;
其中,单元I、II、III和IV相加总和为100重量%。
所述丙烯酸酯共聚物b)可以另外包含其他单元,例如衍生自马来酸酯、富马酸酯、衣康酸酯、乙酸乙烯酯、乙烯基吡咯烷酮、氯乙烯、丙烯腈、丙烯酰胺、苯乙烯或乙烯的那些,只要并不显著损害与PVDF的相容性和所需的增粘效果。
取代基R1、R2、R4和R5的链长受到限制的原因是更长的烷基会导致下降的玻璃化转变温度,并因此降低了耐热变形性。在个别情况下,这可以接受;这样的实施方案至少在本发明的等同范围内。
酯单元I例如衍生自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸正丙酯或甲基丙烯酸异丁酯,优选甲基丙烯酸甲酯。
在m=0的情况下,酰亚胺单元II衍生自任选取代的马来酰亚胺,例如马来酰亚胺、N-甲基马来酰亚胺、N-乙基马来酰亚胺、N-苯基马来酰亚胺或N-甲基柠康酰亚胺。在m=1的情况下,它们源自在聚合物中相邻的两个式I或III的单元与氨或伯胺的反应以形成酰亚胺。
所述酸单元III衍生自丙烯酸或甲基丙烯酸。
所述酸酐单元IV(当n=0时)优选衍生自不饱和二羧酸酐,例如马来酸酐、甲基丙烯酸酐和丙烯酸酐,更优选衍生自甲基丙烯酸酐。在n=1的情况下,它们来自在具有闭环的聚合物中两个相邻单元III中的水的消除。
其他酸酐单元可以衍生自衣康酸酐和乌头酸。
更优选,丙烯酸酯共聚物b)仅具有单元I、II、III和IV。
优选,丙烯酸酯共聚物中的R1、R2、R4和R5基团全部相同,更优选全部为甲基。
由于单元II的存在,所述共聚物称为聚丙烯酰亚胺或聚甲基丙烯酰亚胺,或者有时也称为聚戊二酰亚胺。这些是从聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯衍生的产物,其中两个相邻的羧酸酯基团已转化为环酰亚胺。酰亚胺的形成优选在水的存在下,使用氨或伯胺而进行,例如甲胺,同时通过水解伴随形成了单元III和IV。
该产品及其制备方法是已知的(Hans R.Kricheldorf,Handbook ofPolymerSynthesis(聚合物合成手册),Part A,Verlag Marcel Dekker Inc.,New York-Basle-Hong Kong,223页之后;H.G.Elias,Makromoleküle[Macromolecules],Hüthig und WepfVerlag Basle-Heidelberg-New York;US2 146 209,US 4 246 374)。
所述丙烯酸酯共聚物优选具有40%至60重量%的单元I,30%至40重量%的单元II,2%至5重量%的单元III和5%至15重量%的单元IV。
所述聚合物基材优选包含低粘度PVDF以及基于聚合物基材为2%至30重量%,更优选2.5%至20重量%,特别优选3%至10重量%的丙烯酸酯共聚物,其中丙烯酸酯共聚物包括40%至60重量%的单元I,30%至40重量%的单元II,2%至5重量%的单元III和5%至15重量%的单元IV,其中单元I、II、III和IV合计为100。
优选,根据本发明的复合材料包括基于所述该复合材料基材为30%至55体积%的在由低粘度均聚PVDF组成的聚合物基材中具有环氧树脂尺寸(size)的碳纤维,并且包括基于所述该复合材料基材为5%至10重量%的丙烯酸酯共聚物,其中丙烯酸酯共聚物包括40%至60重量%的单元I,30%至40重量%的单元II,2%至5重量%的单元III和5%至15重量%的单元IV,其中I、II、III和IV单元总计为100。
聚合物基材以及低粘度PVDF和丙烯酸酯共聚物可包含常规助剂和添加剂,例如抗冲击改性剂(例如丙烯酸酯橡胶)、阻燃剂、稳定剂、增塑剂、加工助剂、染料、颜料等。所提及的试剂的量的剂量应使特别是与纤维材料与基材的粘合有关的期望性能不会明显受损。
聚合物基材通过常规和已知的方法,通过在有效捏合的混合单元中,例如双螺杆挤出机中,在组分的熔点所指导的温度下,通常是在200-300℃的温度下,将组分的熔体进行混合而制备。
本发明的复合材料可以通过现有技术方法而生产。单向连续纤维-增强带的生产在例如EP 0056703A1、US 5002712A、US 4883625A、US 2014/0191437A1、US 2013/0333788A1和WO 2014/140025中有详细描述。从粗纱或编织物开始的可能的生产方法例如熔融施加、用聚合物溶液浸渍和除去溶剂、膜浸渍或粉末浸渍(US 2018001516A1、WO 2016/156222、WO 2016/173886)。
以这种方式获得的复合材料的合适形式可以是最终产品。在其他情况下,它是半成品,可以借助适当的成型方法而进一步加工以得到成品件。说明性的成品件是飞机、火箭或机动车辆的建筑部件、或包含诸如复合材料作为增强层的热塑性复合材料管。
另外,可以将获得的复合材料切割成股以得到加长的长纤维-增强的粒料,长度为4至60mm,优选5至50mm,特别优选6至40mm,特别优选5至30mm,非常特别优选6至25毫米。在这些加长的长纤维-增强粒料中,增强纤维沿轴向排列,并从第一切割面延伸至第二切割面。
这些粒料然后可以用于通过注射成型、挤出、压缩成型或其他熟悉的成型方法而生产模制品,并且在此使用温和的加工方法而获得了特别好的模制品性能。在本文中,术语“温和”尤其应理解为在大大避免了不适当的纤维断裂和随之而来的纤维长度的严重减少。在注射成型的情况下,这意味着优选使用大直径和低的压缩比的螺丝,以及中等尺寸喷嘴通道和闸门沟道。应确保的补充条件是,在借助较高的料筒温度(接触加热)下,细长的粒料迅速融化,并且纤维不会因过高的剪切力而过分粉碎。当观察这些措施时,获得的模制品具有比由短纤维增强的模制组合物生产的对比的模制品更高的平均纤维长度。这实现了性能上的显著改善,特别是拉伸弹性模量、最大拉伸强度和缺口抗冲击强度。
优选的半成品是胶带;优选它们用连续纤维而单向增强。优选,所述带的宽度为5至600mm,并且优选宽度为8至300mm,而厚度通常为0.05至2mm,优选0.1至1mm,更优选0.125至0.5mm,特别优选0.15至0.35mm。
优选的复合材料由连续纤维-增强的带层组成,具有1至100的多个单独层,更优选5至90个单独层,其中该复合材料通过施加压力和升高的温度,更优选通过固结而形成,例如如实施例中所示,各个层可以具有任何期望的纤维取向。
潜在问题的第二个方面通过本发明主题的另一部分而解决,热塑性复合材料管(TCP)从内向外包括以下组件:
I.具有一层或多层的管状内衬,其外表面由聚酰胺模塑配混物或PVDF模塑配混物组成;
II.由聚合物基材和嵌入其中的连续纤维组成的复合材料而组成的增强层,其中该聚合物基材由至少80重量%,优选至少85重量%,更优选至少90重量%,特别优选至少95重量%的混合物组成,其中所述混合物包含以下组分:
a)以低粘度PVDF为主要成分,即含量至少为50重量份,和
b)1至50重量份,优选1.5至40重量份,更优选2至30重量份,特别优选2.5至20重量份,特别优选3至10重量份的丙烯酸酯共聚物,其中丙烯酸酯共聚物包含1至30重量%,优选2至25重量%,更优选4至20重量%,特别优选5至15重量%的具有羧酸酐基团的单元,
其中a)和b)的重量份之和为100,
并且,其中连续纤维在复合物中的体积比例另外为10%至80%,优选15%至75%,更优选20%至70%,甚至更优选25%至65%,特别优选30%至60%,特别优选35%至55%,
其中聚合物基材和连续纤维的百分比各自基于增强层的总质量或总体积;
III.任选,由聚酰胺基材和嵌入其中的连续纤维组成的复合材料的其它增强层,
其中,聚酰胺基材由至少80重量%,优选至少85重量%,更优选至少90重量%,特别优选至少95重量%的聚酰胺组成,
并且,其中连续纤维在复合材料中的体积比另外为10%至80%,优选15%至75%,更优选20%至70%,甚至更优选25%至65%,特别优选30%至60%,特别优选35%至55%,
其中,聚酰胺基材和连续纤维的百分比分别基于增强层的总质量或总体积;
IV.任选,由聚合物材料组成的外覆盖层。
优选,层II是由所述的根据本发明的复合材料而组成的增强层。
管状内衬的内径通常为10至500mm,优选12至425mm,并且更优选15至300mm。其壁厚通常为2至40mm,优选2.5至30mm,并且更优选3至20mm。所述内衬可以具有单层或多个层。
在TCP的生产中,通过施加接触压力而将带状的本发明的复合材料施加到内衬的外表面上。必要的接触压力可以通过缠绕张力或借助接触体而实现。在此,在一个实施方案中,两个接触面例如借助红外辐射、热空气、热气、激光辐射、微波辐射或直接通过接触加热而在表面上熔化。然后将部分熔融的接触表面彼此压在一起。然后应保持所述接触压力,直到熔融区域固化为止。在另一个实施方案中,所述带进行缠绕,然后借助可加热的接触体而间接或直接地从外部熔化。必须对加热输出进行校准,以使内衬的外表面在此也开始熔化。此后,保持所述接触压力直到熔化的区域已经固化。所述带的缠绕和任何其他带帘布层的缠绕是现有技术。任选,可以以相同的方式将一种或多种具有聚酰胺基材的带状帘布层施加到由此获得的结构上。这在某些情况下是可取的,这是因为TCP的外部区域以较小程度而暴露于要输送的介质及其温度下,以此方式可以使材料成本保持更低,并使整个管道更轻。聚酰胺是本领域技术人员已知的非常耐冲击的聚合物,因此提供了更好和额外的对环境影响的保护;此外,聚酰胺的密度低于PVDF。
整个复合材料层,即所有带状层的总和,在此为1至100mm,优选5至90mm,更优选为10至80mm。对于不同的带层,可以使用不同的带的几何形状和缠绕角度。所使用的带可以具有任何合适的横截面。
为了保护外部的带帘布层,任选,最终可以施加聚合物材料的外覆盖帘布层。它可以是热塑性模塑配混物,也可以是热塑性或可交联或交联的弹性体。覆盖层优选牢固地粘附到外带层上。此时,覆盖层可以例如借助十字头挤压模而施加,并且因此粘性地粘合到带层上。还可以通过可交联的弹性体的交联而产生粘附力。
根据本发明的TCP的具体设计例如是:
a)聚酰胺模塑配混物的内衬/本发明的PVDF复合材料层/聚酰胺模塑配混物的覆盖层;
b)PVDF模塑配混物的内衬/本发明的PVDF复合材料层/PVDF模塑配混物的覆盖层;
c)PVDF模塑配混物的内衬/本发明的PVDF复合材料层/聚酰胺模塑配混物的覆盖层;
d)聚酰胺模塑配混物的内衬/本发明的PVDF复合材料层/PVDF模塑配混物的覆盖层;
e)两层内衬,其具有聚酰胺模塑配混物的内层以及PVDF/丙烯酸酯共聚物共混物的外层/本发明的PVDF复合材料层/PVDF/丙烯酸酯共聚物共混物的层/聚酰胺模塑配混物的覆盖层;
f)两层内衬,其具有聚酰胺模塑配混物的内层和PVDF/丙烯酸酯共聚物共混物的外层/本发明的PVDF复合材料层/PVDF模塑配混物的覆盖层;
g)PVDF或聚酰胺模塑配混物的内衬/本发明的PVDF复合材料层/具有聚酰胺基材的复合材料层/PVDF或聚酰胺模塑配混物的覆盖层。
设计e和f中的丙烯酸酯共聚物具有与根据本发明的复合材料的丙烯酸酯共聚物b)相同的组成。
合适的聚酰胺例如是PA6、PA66、PA610、PA88、PA8、PA612、PA810、PA108、PA9、PA613、PA614、PA812、PA128、PA1010、PA10、PA814、PA148、PA1012、PA11、PA1014、PA1212和PA12,或基于这些聚酰胺的聚醚酰胺或聚醚酯酰胺,或聚邻苯二甲酰胺,例如PA66/6T、PA6/6T、PA6T/MPMDT(MPMD代表2-甲基五亚甲基二胺)、PA9T、PA10T、PA11T、PA12T、PA14T、PA6T/6I、PA6T/10T、PA6T/12、PA10T/11、PA10T/12或PA612/6T。
具有由本发明的复合材料组成的增强物的根据本发明的TCP的优点在于,与聚烯烃或聚酰胺的基材相比,由于烃、水或甲醇的吸收,聚合物基材的软化程度较小。因此,与由聚烯烃或聚酰胺制成的可比较的管相比,根据本发明的TCP具有更高的外部抗压强度。良好的纤维-基材粘合性是额外特别有利的,其显著有助于高的增强和长的使用寿命。如实施例中所述,根据ASTM D2344-16,纤维-基材粘合性的量度可以认为是三点弯曲测试。
根据本发明的TCP的另一个优点是,在根据本发明的PVDF复合材料层和存在的任何聚酰胺层之间不需要额外的粘合增强。
根据本发明的TCP特别适合于石油或天然气生产中的海上应用,例如用于将产品运输到平台上、用于连接到钢管,作为运输管并且尤其是作为脐管、作为立管、作为跨接管、作为流送管、作为干预管、作为下水管、注入管或压力管。它可用于运输可能受压的碳氢化合物或其混合物,例如原油、原煤气、三相(即油/气/水混合物)、加工油(已在海床进行部分加工)、加工气、汽油或柴油、注入介质,诸如水(例如,保持洞穴中的压力)、油田化学品、甲醇或CO2、以及用于传导液压油(例如,用于海底的执行器)。此外,根据本发明的TCP也适合作为陆上领域或其他工业应用中的压力导管,特别是必须在轴向管道上传递的较高的力且在管道和连接元件之间具有力-配合结合的那些。
实施例:
在由95%重量的低粘度均聚PVDF(Solef 1006)与5%重量的丙烯酸酯共聚物混合而制成的聚合物基材中,胶带由45%体积的碳纤维(Grafil 34-700D)组成,其中所述丙烯酸酯共聚物包括10.1重量%的酸酐(IV)、2.9重量%的酸基(III)、35重量%的酰胺基(II)和52重量%的甲基丙烯酸酯基(I)而没有其他添加剂。
在将上述胶带的八个单向层凝固以形成半成品(10bar,240℃,保持时间5分钟)后,根据ASTM D2344-16在平面试样上测得的层间剪切强度为59MPa。
直至规定的值,在试样中均未观察到基材与碳纤维的脱落;因此,该测试就基材和连续纤维的粘合性做出了陈述。
为了比较,类似于操作实施例而构造了半成品,但是没有使用丙烯酸酯共聚物。在对该半成品进行可比的凝固后,发现根据ASTM D2344-16测得的层间剪切强度为17MPa。
Claims (9)
1.由聚合物基材和嵌入其中的连续纤维组成的复合材料,其中所述聚合物基材由至少80重量%的混合物组成,所述混合物包含以下组分:
a)低粘度PVDF作为主要成分,即至少50重量份,和
b)1至50重量份的丙烯酸酯共聚物,其中所述丙烯酸酯共聚物包含1-30重量%的具有羧酸酐单元的单元,
其中a)和b)的重量份之和为100,并且
其中连续纤维在复合材料中的体积比例为10重量%至80重量%,
其中聚合物基材和连续纤维的百分比分别是基于复合材料的总质量或总体积。
2.权利要求1的复合材料,其特征在于所述PVDF为均聚物或共聚物。
3.根据前述权利要求任一项的复合材料,其特征在于所述丙烯酸酯共聚物包含以下单元:
I.14%至80重量%的下式的酯单元:
R=甲基、乙基、丙基或丁基,R1=氢或甲基;
II.10%至75重量%的下式的酰亚胺单元:
R4=独立地为具有1至8个碳原子的脂族基或脂环基,优选具有1至4个碳原子的脂族基或脂环基,更优选氢或甲基,和
R3=独立地为甲基、乙基、丙基、丁基或苯基;
m=0或1;
III.1重量%至20重量%的下式的酸单元:
R2=氢或甲基;
IV.1重量%至30重量%的下式的酸酐单元:
R5=独立地为具有1至8个碳原子的脂族基或脂环基;
n=0或1;
其中,单元I、II、III和IV相加总和为100重量%。
4.根据前述权利要求中任一项的复合材料,其特征在于它是单向连续的纤维增强带。
5.通过切割根据前述权利要求中任一项的呈线料形式的复合材料制备的长度为4至60mm的伸长的长纤维增强的粒料。
6.热塑性复合材料管(TCP),其从内向外包括以下组件:
I.具有一层或多层的管状内衬,其外表面由聚酰胺模塑配混物或PVDF模塑配混物组成;
II.由聚合物基材和嵌入其中的连续纤维组成的复合材料构成的增强层,其中该聚合物基材由至少80重量%的混合物组成,其中所述混合物包含以下组分:
a)50至99重量份的PVDF,和
b)1至50重量份的丙烯酸酯共聚物,其中所述丙烯酸酯共聚物包含1至30重量%的具有羧酸酐基团的单元,
其中a)和b)的重量份总和为100,并且
其中连续纤维在复合材料中的体积比例为10重量%至80重量%,
其中聚合物基材和连续纤维的百分比分别基于增强层的总质量或总体积;
III.任选存在的由聚酰胺基材和嵌入其中的连续纤维组成的复合材料的其它增强层,其中,所述聚酰胺基材由至少80重量%的聚酰胺组成;并且其中,连续纤维在复合材料中的体积比例另外为10重量%至80重量%,
其中,聚酰胺基材和连续纤维的百分比分别基于增强层的总质量或总体积;
IV.任选存在的由聚合物材料组成的外覆盖层。
7.根据权利要求6的热塑性复合材料管,其特征在于TCP的设计选自以下组中:
a)聚酰胺模塑配混物的内衬/本发明的PVDF复合材料层/聚酰胺模塑配混物的覆盖层;
b)PVDF模塑配混物的内衬/本发明的PVDF复合材料层/PVDF模塑配混物的覆盖层;
c)PVDF模塑配混物的内衬/本发明的PVDF复合材料层/聚酰胺模塑配混物的覆盖层;
d)聚酰胺模塑配混物的内衬/本发明的PVDF复合材料层/PVDF模塑配混物的覆盖层;
e)具有聚酰胺模塑配混物的内层和PVDF/丙烯酸酯共聚物共混物的外层的两层内衬/本发明的PVDF复合材料层/PVDF/丙烯酸酯共聚物共混物的层/聚酰胺模塑配混物的覆盖层;
f)具有聚酰胺模塑配混物的内层和PVDF/丙酸酯共聚物共混物的外层的两层内衬/本发明的PVDF复合材料层/PVDF模塑配混物的覆盖层;
g)PVDF或聚酰胺模塑配混物的内衬/本发明的PVDF复合材料层/具有聚酰胺基材的复合材料层/PVDF或聚酰胺模塑配混物的覆盖层。
8.根据权利要求6和7中任一项所述的热塑性复合材料管,其特征在于,所述TCP为脐管、立管、跨接管、流送管、介入管、下水管、注入管或压力管。
9.根据权利要求6至8中任一项所述的热塑性复合材料管用于运输原油、原煤气、三相物、经加工的油、经加工的气、汽油或柴油、注入介质或用于传导液压油中的用途。
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CN110603284B (zh) | 2017-05-10 | 2022-04-19 | 大金工业株式会社 | 片、层积体、管、立管和流送管 |
CN108214980B (zh) * | 2017-12-12 | 2021-08-03 | 华东理工大学 | 一种制备连续纤维增强热塑性预浸带的设备及方法 |
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2018
- 2018-09-21 EP EP18195870.3A patent/EP3626764B1/de active Active
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- 2019-09-19 CN CN201980061459.3A patent/CN112739751A/zh active Pending
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Patent Citations (3)
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US5554426A (en) * | 1994-03-24 | 1996-09-10 | Huels Aktiengesellschaft | Multilayer plastic pipe |
CN105984192A (zh) * | 2015-03-17 | 2016-10-05 | 赢创德固赛有限公司 | 包含含氟聚合物层的多层复合件 |
CN108286627A (zh) * | 2017-01-10 | 2018-07-17 | 赢创德固赛有限公司 | 具有多层中间片层的热塑性复合管 |
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CA3112965C (en) | 2023-09-05 |
BR112021004961B1 (pt) | 2024-01-02 |
EP3626764A1 (de) | 2020-03-25 |
US20220041849A1 (en) | 2022-02-10 |
TWI826528B (zh) | 2023-12-21 |
JP2022500538A (ja) | 2022-01-04 |
KR20210065129A (ko) | 2021-06-03 |
WO2020058403A1 (de) | 2020-03-26 |
JP7395573B2 (ja) | 2023-12-11 |
BR112021004961A2 (pt) | 2021-06-08 |
EP3626764B1 (de) | 2021-02-24 |
CA3112965A1 (en) | 2020-03-26 |
TW202030236A (zh) | 2020-08-16 |
MX2021003211A (es) | 2021-09-23 |
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