CN110325777A - 氢气输送部件 - Google Patents
氢气输送部件 Download PDFInfo
- Publication number
- CN110325777A CN110325777A CN201880013610.1A CN201880013610A CN110325777A CN 110325777 A CN110325777 A CN 110325777A CN 201880013610 A CN201880013610 A CN 201880013610A CN 110325777 A CN110325777 A CN 110325777A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- transfer unit
- resin combination
- polyamide
- hydrogen transfer
- 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.)
- Pending
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 111
- 239000001257 hydrogen Substances 0.000 title claims abstract description 111
- 238000012546 transfer Methods 0.000 title claims abstract description 49
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 66
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 37
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 33
- 230000004888 barrier function Effects 0.000 claims abstract description 27
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 20
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 230000035699 permeability Effects 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 15
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 12
- -1 alkene Hydrocarbon Chemical class 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004959 Rilsan Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920006152 PA1010 Polymers 0.000 description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920001470 polyketone Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- HOPRNJQMMVAYIP-UHFFFAOYSA-N 1,2,5-trioxocane-6,8-dione Chemical compound C1(CC(=O)OOCCO1)=O HOPRNJQMMVAYIP-UHFFFAOYSA-N 0.000 description 1
- VTIMKVIDORQQFA-UHFFFAOYSA-N 2-Ethylhexyl-4-hydroxybenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(O)C=C1 VTIMKVIDORQQFA-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 150000008331 benzenesulfonamides Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FCGASPQFBJKTRO-UHFFFAOYSA-N n-cyclohexyl-1-phenylmethanesulfonamide Chemical compound C1CCCCC1NS(=O)(=O)CC1=CC=CC=C1 FCGASPQFBJKTRO-UHFFFAOYSA-N 0.000 description 1
- OHPZPBNDOVQJMH-UHFFFAOYSA-N n-ethyl-4-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(C)C=C1 OHPZPBNDOVQJMH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920006396 polyamide 1012 Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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Abstract
提供一种具有优异的氢气阻隔性的氢气输送部件,其在低温环境下可以展现改善的挠性,并且循序在低温环境下可以展现改善的耐久性。根据本发明的氢气输送部件,所述氢气输送部件包括由包含聚酰胺11和改性烯烃系弹性体的树脂组合物形成的氢气阻隔层、配置在氢气阻隔层的外侧的增强层、和包含聚酰胺树脂且配置在增强层的外侧的外覆盖层,所述氢气输送部件特征在于,相对于聚酰胺11的含量和改性烯烃系弹性体的含量的总计含量,树脂组合物中的改性烯烃系弹性体的含量为15~50质量%,并且树脂组合物基本上不包含增塑剂。
Description
技术领域
本公开涉及一种氢气输送部件。
背景技术
近年来,对于在高压下移送液体或气体的手段,正在开发具有增强层和配设在增强层的内部且由树脂组合物形成的内管的软管来代替金属管等。
例如,已经提出了一种多层耐压软管,其包括:用作内管的内层;层叠在该内层外周的由如聚氯乙烯等热塑性树脂形成的中间层;沿中间层螺旋状卷绕的增强线材;和层叠在中间层和增强线材的外周的外层(例如,见专利文献1)。
此外,近年来,对从氢气站等向汽车等的燃料电池供给氢气的软管的需求已在增加。在为改善填充效率的尽可能高的压力和尽可能低的温度下经由如软管等氢气输送部件移送氢气,因此需要氢气输送部件改善在低温环境下的挠性。此处,在耐压软管的领域中,目前主要研究了在常温环境下的气体阻隔性,在低温环境下的挠性和在低温环境下的耐久性仍有进一步改善的余地。
引用列表
专利文献
PTL 1:日本专利特开No.2016-212343
发明内容
发明要解决的问题
因此,本公开的目的是提供一种氢气输送部件,其氢气阻隔性优异,还可以改善在低温环境下的挠性,从而可以改善在低温环境下的耐久性。
用于解决问题的方案
具体地,本公开的氢气输送部件包括:由包含聚酰胺11和改性烯烃系弹性体的树脂组合物形成的氢气阻隔层;配设在所述氢气阻隔层的外侧的增强层;和包含聚酰胺树脂且配设在所述增强层的外侧的外覆盖层,其中相对于所述聚酰胺11和所述改性烯烃系弹性体的总量,所述树脂组合物中的所述改性烯烃系弹性体的含量为15质量%~50质量%;并且所述树脂组合物基本上不包含增塑剂。
发明的效果
根据本公开,可以提供一种氢气输送部件,其氢气阻隔性优异,还可以改善在低温环境下的挠性,从而可以改善在低温环境下的耐久性。
具体实施方式
以下,将会详细地描述本公开的具体实施方案,但本公开完全不限于以下实施方案,并且可以在本公开的目的的范围内在适当的修改下实施。
本说明书中的“软管”是指为挠性的且可以将移送对象(例如,如液体或气体等的流体)移送的管状体。
本说明书中的“树脂”为包括热塑性树脂和热固性树脂的概念,且不包括硫化橡胶。
本说明书中,使用“~”表达的数值范围意指包括“~”之前和之后记载的数值作为下限值和上限值的范围。
(氢气输送部件)
本公开中的氢气输送部件(以下,也简称为“输送部件”)至少包括:氢气阻隔层、增强层和外覆盖层;如有必要,进一步包括其他构件。
本公开的氢气输送部件没有特别限定,并且可以根据目的适当地选择;并且优选包括例如氢气输送软管。
<氢气阻隔层>
上述氢气阻隔层为成为对氢气的阻隔的层,并且由树脂组合物形成。此处,“由树脂组合物形成”意味着该组合物可以进一步包含除了树脂组合物以外的组分。
上述树脂组合物至少包括聚酰胺11和改性烯烃系弹性体,并且任选地包括其他组分,但基本上不包含增塑剂。
在本说明书中,“树脂组合物基本上不包含增塑剂”意味着(1)其中树脂组合物不包含任何增塑剂的情况,和(2)其中树脂组合物包含增塑剂,但增塑剂的含量相对于全部树脂组合物为3质量%以下,并且优选1质量%以下的情况。
通常,为了提高氢气阻隔性和挠性(从而提高耐久性)并且便于挤出成形,将增塑剂添加至用于上述氢气输送部件的氢气阻隔层中的树脂组合物。
认为的是,当将增塑剂添加至树脂组合物时,断裂伸长率的值通常增加。然而,根据发明人的研究,发现的是,根据树脂的种类,在树脂组合物基本上不包含增塑剂的情况下,与添加增塑剂的情况相比,在低温环境下的挠性趋于变得更高。
本说明书中的“增塑剂”意指出于改善树脂的如挠性等物性的目的而使用的化合物。
上述增塑剂没有特别限定,但可以根据目的适当地选择,并且增塑剂的实例包括:苯磺酰胺衍生物,如N-丁基苯磺酰胺(BBSA)、乙基甲苯磺酰胺和N-环己基甲苯磺酰胺;羟基苯甲酸的酯,如对羟基苯甲酸-2-乙基已基酯和对羟基苯甲酸-2-癸基己基酯;四氢糠醇的酯或醚,如低聚乙烯氧基四氢糠醇(oligo ethylene oxytetrahydrofurfuryl alcohol);柠檬酸、羟基丙二酸的酯,如低聚羟基丙二酸亚乙酯(oligo ethyleneoxy malonate)等;和酚系化合物。
通过如气相色谱法等已知的方法,可以确认增塑剂是否包含在上述树脂组合物中并且可以测量其量。
上述树脂组合物的-40℃下的储能模量指数没有特别限定,并且可以根据目的适当地选择,但是当后续将会描述的其中不添加改性烯烃系弹性体(柔软性组分)的树脂组合物的-40℃下的储能模量确定为100时,该指数优选为30以上且100以下,更优选30以上且85以下,进一步优选40以上且70以下,并且特别优选40以上且50以下。由于将上述树脂组合物的储能模量指数控制在上述范围内,在低温环境下的氢气输送部件中可以获得充分的挠性。
上述树脂组合物的-40℃下的储能模量没有特别限定,并且可以根据目的适当地选择,但优选为1400MPa以下,优选为600MPa以上,并且特别优选670MPa~820MPa。
当上述储能模量为1400MPa以下时,可以进一步改善在低温环境下的挠性,并且当储能模量为600MPa以上时,输送部件即使在弯曲时也不会崩坏。
如果上述弹性模量为670MPa以上且820MPa以下,当使用输送部件时,即使在产品弯曲或扭曲时,也可以使用该输送部件而不破坏树脂层。
可以使用由Hitachi High-Technologies Corporation制造的DMA 7100(用于动态粘弹性测量的试验机)来测量上述储能模量。具体地,将测量样品板(尺寸:10mm×40mm×1mm厚)安装在与试验用负荷传感器连接的夹具上,然后装入冷却加热炉中。其后,在-150℃~150℃的温度范围、3℃/min的升温速度、0.01%的应变量和1Hz的频率下,获得动态粘弹性的温度分散光谱(temperature dispersion spectrum)。从获得的在-150℃~150℃的温度范围内的动态粘弹性的温度分散光谱中可以获得-40℃下的储能模量。
上述树脂组合物的30℃下的氢气透过系数指数没有特别限定,并且可以根据目的适当地选择,但是当后续将会描述的其中不添加改性烯烃系弹性体(柔软性组分)的树脂组合物的30℃下的氢气透过系数指数确定为100时,该指数优选为500以下,更优选400以下,并且特别优选300以下。由于将上述树脂组合物的氢气透过系数指数控制在上述范围内,可以减少氢气输送部件的氢气泄漏量。
上述树脂组合物的30℃下的氢气透过系数没有特别限定,并且可以根据目的适当地选择,但该系数优选为3.74×10-10[cc×cm/cm2×s×cmHg]以下,并且更优选1.54×10-10[cc×cm/cm2×s×cmHg]以上且2.64×10-10[cc×cm/cm2×s×cmHg]以下。
当上述氢气透过系数为3.74×10-10[cc×cm/cm2×s×cmHg]以下时,可以改善氢气阻隔性。
当上述氢气透过系数为1.54×10-10[cc×cm/cm2×s×cmHg]以上时,可以进一步改善低温弹性模量而不大幅地损害氢气阻隔性,另外,当该系数为2.64×10-10[cc×cm/cm2×s×cmHg]以下时,进一步改善氢气阻隔性。
在湿度20%和温度30℃的条件下,使用由GTR-Tek制造的GTR-11A(气体透过测量装置),可以测量上述氢气透过系数。具体地,将测量样品(13mm的直径、0.2mm~0.3mm的厚度)设置在小室中,将小室内真空脱气,由此消除周围气体的影响。其后,使作为待测量气体的氢气通过并且设定在0.6MPa的压力下,并且使用气相色谱法(TCD方法、载气为Ar),通过校正曲线法来确定透过膜的氢气的量。其后,由透过面积、厚度和压力差来计算氢气透过系数。此外,上述氢气透过系数的值越小意味着结果越好。
<<聚酰胺11>>
在氢气输送部件的成形加工性、耐压性和抗重复脉冲性(resistance torepeated impulse)的方面,上述聚酰胺11(尼龙11)为优选的树脂。
通过使用上述聚酰胺11,与如聚酰胺6和聚酰胺66等具有短烷基链的聚酰胺相比,可以改善在低温下的挠性。此外,与使用其他树脂的情况相比,耐压性、抗重复脉冲性和低温环境下的耐久性可以改善至更高的水平。
<<改性烯烃系弹性体>>
上述改性烯烃系弹性体优选为其在23℃下的杨氏模量低于上述聚酰胺11的柔软性组分。
上述改性烯烃系弹性体的玻璃化转变温度(Tg)没有特别限定,并且可以根据目的适当地选择;但在改善低温下的挠性的方面,优选为0℃以下,并且更优选-20℃以下。
通过包括玻璃化转变温度为0℃以下的改性烯烃系弹性体,树脂组合物即使在低温环境下也可以维持骨架构件的适当的弹性,并且可以改善骨架构件的耐久性。
上述改性烯烃系弹性体没有特别限定,并且可以根据目的适当地选择;并且改性烯烃系弹性体的实例包括如聚乙烯、聚丙烯、乙烯-丙烯橡胶、乙烯-1-丁烯共聚物、聚-α-烯烃和苯乙烯-乙烯-丁烯-苯乙烯共聚物等烯烃系弹性体的改性产物。这些可以单独地使用或以两种以上的组合使用。
这些弹性体当中,在获得更优异的弹性和耐久性的方面,优选选自由乙烯-丙烯橡胶、聚-α-烯烃、苯乙烯-乙烯-丁烯-苯乙烯共聚物和乙烯-1-丁烯共聚物组成的组中的至少一种的改性产物,并且更优选乙烯-1-丁烯共聚物的改性产物。
另外,优选的是马来酸酐或环氧末端的(甲基)丙烯酸酯与上述改性烯烃系弹性体的至少一部分共聚或接枝。其中共聚或接枝这些化合物的改性烯烃系弹性体(柔软性组分)与聚酰胺树脂的末端基团反应,由此改善在树脂组合物中的分散性,因此进一步改善骨架构件的弹性和耐久性。此处,“(甲基)丙烯酸酯”是指丙烯酸酯和/或甲基丙烯酸酯。
上述树脂组合物中的上述改性烯烃系弹性体的含量没有特别限定,只要该含量相对于上述聚酰胺11和上述改性烯烃系弹性体的总量为15质量%~50质量%即可,并且可以根据目的适当地选择;但下限优选为20质量%以上;上限优选为40质量%以下,并且更优选30质量%以下。
当上述树脂组合物中的上述改性烯烃系弹性体的含量为15质量%以上时,即使在低温环境下,也可以确保适当的弹性;当含量为50质量%以下时,充分地展现了上述聚酰胺11的效果,此外,可以充分适当地维持氢气透过系数。
<<其他组分>>
上述树脂组合物可以包含其他组分,只要其他组分不损害本公开的效果即可。
上述其他组分没有特别限定,并且可以根据目的适当地选择,并且包括例如,防老剂、着色剂、填料、抗静电剂、热稳定剂和阻燃剂。这些可以单独地使用或以两种以上的组合使用。
<氢气输送软管>
上述氢气输送软管至少包括:由上述树脂组合物形成的氢气阻隔层;如有必要,软管的内管、增强层、外覆盖层和其他构件。
应用上述氢气阻隔层的部位没有特别限定,并且可以根据目的适当地选择,但优选为软管的内管。此处,“软管的内管”意指氢气输送软管的内侧的树脂层,并且在该软管的内管的内侧可以进一步具有另外的层。
更优选的是,由上述树脂组合物形成的氢气阻隔层在软管中在与作为待移送对象的氢气接触的位置处存在。由上述树脂组合物形成的氢气阻隔层在软管中在与作为待移送对象的氢气接触的位置处配设;由此,即使当软管在低温环境下使用或经由其中移送作为低温的待移送对象的氢气时,软管也可以改善挠性,从而可以改善在低温环境下的耐久性。
<<软管的内管>>
优选的是,上述软管的内管为在-40℃的环境下具有20%以上的断裂伸长率并且基本上不包含增塑剂的树脂组合物的成形产物。
当上述软管的内管在低温环境下的耐久性优异时,内管适合作为在低温环境下使用的氢气输送软管或用于移送作为低温的待移送对象的氢气的氢气输送软管的构件。
优选的是,上述软管的内管使用上述树脂组合物来形成。上述树脂组合物的物性和组分等如上所述。
上述软管的内管的形成方法没有特别限定,并且可以根据目的适当地选择;内管可以通过已知方法来形成。
优选的是,上述软管的内管在与氢气输送软管中移送的且作为待移送对象的氢气接触的位置处存在。上述软管的内管可以由仅一层或两层以上形成。
上述软管的内管的内径(具体地,软管的内管的截面中的中空部分的最大直径)没有特别限定,并可以根据期望的强度和耐久性等适当地选择,但优选为3.0mm以上,更优选4.0mm以上,此外,优选为51.0mm以下,更优选25.4mm以下。
上述软管的内管的厚度(具体地,软管的内管的截面中的由树脂组合物形成的部分的厚度)没有特别限定,并可以根据期望的强度和耐久性等适当地选择,但优选为0.05mm以上,更优选0.5mm以上,此外,优选为10mm以下,更优选5mm以下。
<<增强层>>
上述氢气输送软管具有配设在软管的内管的外侧的增强层。上述氢气输送软管具有增强层,由此即使当在高压下移送作为待移送对象的氢气时,也可以获得充分的强度。在这种情况下的氢气输送软管可以在增强层和软管的内管之间具有另外的层,并且可以在增强层的外侧具有除了后续将会描述的外覆盖层以外的另外的层。上述增强层可以为仅一层或两层以上。
上述增强层的材料没有特别限定,并可以根据期望的强度和耐久性等适当地选择。材料的实例包括:有机材料如芳族聚酰胺、聚对苯撑苯并双噁唑(PBO)、聚酮(PK)、聚醚醚酮(PEEK)、尼龙(PA)、聚芳酯(polyarylate)、聚酰亚胺、聚乳酸和含氟树脂;无机材料如金属、玻璃和碳。
上述增强层的厚度没有特别限定,并可以根据期望的强度和耐久性等适当地选择;但优选0.2mm以上并且更优选1.0mm以上;优选20mm以下,并且更优选10mm以下。
上述增强层的形成方法没有特别限定,并且可以根据目的适当地选择。方法的实例包括:将纤维状或帘线状的增强层材料以螺旋状或叶片状围绕软管的内管的外侧卷绕的方法;和将已形成为布状或针织布筒(knitted fabric)的增强层材料围绕软管的外侧卷绕的方法。
<<外覆盖层>>
上述氢气输送软管进一步具有配设在增强层的外侧的外覆盖层。上述氢气输送软管可以通过具有外覆盖层而进一步改善软管的强度,并且可以保护软管免受外部环境(雨水和化学试剂等)的影响。
上述外覆盖层的材料没有特别限定,只要该材料包含聚酰胺树脂即可,并且可以根据目的适当地选择。
当外覆盖层的材料包含聚酰胺树脂时,外覆盖层可以保护增强层。
优选的是,作为外覆盖层的材料的聚酰胺树脂具有亚甲基链。具有亚甲基链的聚酰胺树脂的实例包括聚酰胺11、聚酰胺12、聚酰胺610和聚酰胺1010。
通过使用具有亚甲基链的聚酰胺树脂,在低温和常温下弯曲时,外覆盖层可以既保护增强层又防止开裂。
外覆盖层的除了聚酰胺树脂以外的其他材料的实例包括:树脂如聚氨酯、聚酯和聚烯烃;以及弹性体。
从在低温和常温下弯曲时防止开裂的观点来看,作为外覆盖层的材料的聚酰胺树脂优选在构成聚酰胺树脂的构成单元中包含具有7个以上的碳原子的亚甲基链,更优选包含具有9个以上的碳原子的亚甲基链。亚甲基链的碳数的上限没有特别限定,但优选30个以下。
此外,关于此处提到的亚甲基链,例如,当在构成聚酰胺树脂的构成单元中存在两种以上的亚甲基链(例如,在树脂具有5个碳原子的亚甲基链和8个碳原子的亚甲基链的情况下)时,会采用较大的亚甲基链的数。
<<其他构件>>
上述其他构件没有特别限定,并且可以根据目的适当地选择:并且构件的实例包括:配设在上述软管的内管的内侧的芯金属配件和配设在上述外覆盖层的外侧的金属紧固件。
如上所述,在根据本公开的氢气输送部件中,改性烯烃系弹性体为马来酸改性烯烃,由此聚酰胺结构和马来酸结构在形成酸酰胺键的状态下形成海-岛结构,因此可以防止使用中的两种结构间的相分离。
另外,在本公开的氢气输送部件中,改性烯烃系弹性体为乙烯和1-丁烯的共聚物的改性产物,由此可以通过少量的添加有效地实现低弹性模量。
另外,在本公开的氢气输送部件中,相对于聚酰胺11和改性烯烃系弹性体的总量,树脂组合物中的改性烯烃系弹性体的含量为20质量%~30质量%,由此可以改善氢气阻隔性并且还可以进一步改善在低温环境下的挠性。
另外,在本公开的氢气输送部件中,树脂组合物的-40℃下的储能模量为1400MPa以下,由此可以进一步改善在低温环境下的挠性。
另外,在本公开的氢气输送部件中,树脂组合物的-40℃下的储能模量为600MPa以上,由此改善输送部件中的内层材料的在低温下的挠性和耐动态疲劳特性,并且可以显著地延长产品寿命。
另外,在本公开的氢气输送部件中,树脂组合物的30℃下的氢气透过系数为3.74×10-10[cc×cm/cm2×s×cmHg]以下,由此可以改善氢气阻隔性。
另外,在本公开的氢气输送部件中,优选的是,上述氢气输送部件为氢气输送软管。
实施例
本公开将会参照实施例在以下更具体地描述,但本公开不以任何方式限于该描述,并且可以适当地改变而不改变本公开的主旨。
(实施例1~4和比较例1~4)
基于表1中提供的各配混内容来制备各树脂组合物。表1中的配方中的数字表示质量份。
表1中记载的各树脂组合物和各氢气输送软管进行了以下测量和评价,所述氢气输送软管包括:使用树脂组合物制造且为软管的内管的氢气阻隔层;配设在氢气阻隔层的外侧且由钢丝形成的增强层;和配设在增强层的外侧且由表1中提供的材料形成的外覆盖层。结果提供于表1中。
<-40℃下的储能模量的测量>
使用由Hitachi High-Technologies Corporation制造的DMA 7100(用于动态粘弹性测量的试验机)来测量“-40℃下的储能模量”的值。将使用表1中记载的各树脂组合物制造的测量样品板(尺寸:10mm×40mm×1mm厚)安装在与试验用负荷传感器连接的夹具上,然后装入冷却加热炉。其后,在-150℃~150℃的温度范围、3℃/min的升温速度、0.01%的应变量和1Hz的频率下,获得动态粘弹性的温度分散光谱。从在-150℃~150℃的温度范围内获得的动态粘弹性的温度分散光谱中获得-40℃下的储能模量。表1提供了实测值和在将比较例1的实测值设为100时的相对值。
<30℃下的氢气透过系数的测量>
在湿度20%和温度30℃的条件下,使用由GTR Tech制造的GTR-11A(气体透过测量装置)来测量“30℃下的氢气透过系数”的值。将使用表1中记载的各树脂组合物制造的测量样品(13mm的直径和0.2mm~0.3mm的厚度)设置在小室中,将小室内真空脱气,由此消除周围气体的影响。其后,使作为待测量气体的氢气通过并且设定在0.6MPa的压力下,并且使用气相色谱法(TCD方法、载气为Ar),通过校正曲线法来确定透过膜的氢气的量。其后,由透过面积、厚度和压力差来计算氢气透过系数。表1提供了实测值和在将比较例1的实测值设为100时的相对值。此外,上述氢气透过系数的值越小意味着结果越好。
<耐久性试验>
<<循环评价>>
在70MPa的压力和-40℃的氛围温度的条件下,当在低温下不冻结的氢气用作待移送对象时,对使用表1中记载的各树脂组合物制造的上述氢气输送软管,重复在大约0MPa和70MPa之间的加压和减压;测量加压和减压的重复次数(循环次数)直至软管的内管破坏;并且根据以下评价标准来评价结果。当评价为◎(优异)或〇(良好)时,即使当将待移送对象在低温和高压下移送时,耐久性也可以判断为充分的。
<<<评价标准>>>
◎:200000次以上的加压/减压循环
〇:100000次以上的加压/减压循环
×(不良):少于100000次的加压/减压循环
<<外观评价>>
对于外观评价,在上述耐久性试验后,根据以下评价标准来评价氢气输送软管的外观。
<<<评价标准>>>
◎:无异常
〇:存在外皮膨胀的痕迹,但无异常
△(一般):外皮膨胀
×:外皮破损/破裂
[表1]
*1:聚酰胺11(PA11);由Arkema Company制造,商品名:Rilsan BESNBKTL:不含有增塑剂
*2:由Mitsui Chemicals Co.,Ltd.制造,商品名:Tafmer MMH 7010
*3:聚酰胺11(PA11);由Arkema Company制造,商品名:Rilsan BESNP 40TL:含有9.2质量%的增塑剂
*4:聚酰胺610;由Arkema Company制造,商品名:Hiprolon 70NN
*5:聚酰胺6;由Toray Industries,Inc.制造,商品名:CM1041LO
*6:聚酰胺12;由Arkema Company制造,商品名:Rilsan AESNTL
*7:聚酰胺1010;由Arkema Company制造,商品名:Hiprolon 200NN
*8:聚酰胺1012;由Arkema Company制造,商品名:Hiprolon 400NN
如表1的结果所提供,在其中相对于聚酰胺11和改性烯烃系弹性体的总量,改性烯烃系弹性体的含量为15质量%~50质量%的实施例1~4中,在耐久性评价中,可以维持10万次以上的循环,并且也维持外观。
另一方面,在其中相对于聚酰胺11和改性烯烃系弹性体的总量,改性烯烃系弹性体的含量为小于15质量%或大于50质量%的比较例1~4中,在耐久性评价中,循环低于10万次的循环,和/或观察到外皮破损;并且耐久性不足。
从上述结果中发现,通过使用本公开的树脂组合物,可以制造在低温环境下的挠性优异的软管的内管以及软管。
Claims (9)
1.一种氢气输送部件,其包括:由包含聚酰胺11和改性烯烃系弹性体的树脂组合物形成的氢气阻隔层;配设在所述氢气阻隔层的外侧的增强层;和包含聚酰胺树脂且配设在所述增强层的外侧的外覆盖层,
其中相对于所述聚酰胺11和所述改性烯烃系弹性体的总量,所述树脂组合物中的所述改性烯烃系弹性体的含量为15质量%~50质量%;并且所述树脂组合物基本上不包含增塑剂。
2.根据权利要求1所述的氢气输送部件,其中所述改性烯烃系弹性体为马来酸改性烯烃。
3.根据权利要求1或2所述的氢气输送部件,其中所述改性烯烃系弹性体为乙烯和1-丁烯的共聚物的改性产物。
4.根据权利要求1至3中任一项所述的氢气输送部件,其中相对于所述聚酰胺11和所述改性烯烃系弹性体的总量,所述树脂组合物中的所述改性烯烃系弹性体的含量为20质量%~30质量%。
5.根据权利要求1至4中任一项所述的氢气输送部件,其中所述树脂组合物的-40℃下的储能模量为1400MPa以下。
6.根据权利要求1至5中任一项所述的氢气输送部件,其中所述树脂组合物的-40℃下的储能模量为600MPa以上。
7.根据权利要求1至6中任一项所述的氢气输送部件,其中所述树脂组合物的30℃下的氢气透过系数为3.74×10-10[cc×cm/cm2×s×cmHg]以下。
8.根据权利要求1至7中任一项所述的氢气输送部件,其中所述外覆盖层中的聚酰胺树脂为具有亚甲基链的聚酰胺树脂。
9.根据权利要求1至8中任一项所述的氢气输送部件,其中所述氢气输送部件为氢气输送软管。
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FR3106648B1 (fr) | 2020-01-28 | 2022-05-27 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
FR3106525B1 (fr) | 2020-01-28 | 2021-12-31 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
FR3106646B1 (fr) | 2020-01-28 | 2022-06-24 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
FR3106647B1 (fr) | 2020-01-28 | 2021-12-31 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
FR3114768B1 (fr) * | 2020-10-01 | 2023-09-29 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
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CN115413292A (zh) * | 2020-04-16 | 2022-11-29 | 阿科玛法国公司 | 用于运输或存储氢的多层结构体 |
CN116457413A (zh) * | 2020-11-17 | 2023-07-18 | 横滨橡胶株式会社 | 氢填充用软管 |
CN112646362A (zh) * | 2020-12-14 | 2021-04-13 | 江苏金发科技新材料有限公司 | 一种聚酰胺聚偏氟乙烯合金及其制备方法 |
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JPWO2018155491A1 (ja) | 2020-01-09 |
US20190375182A1 (en) | 2019-12-12 |
EP3587882A1 (en) | 2020-01-01 |
EP3587882B1 (en) | 2022-02-16 |
WO2018155491A1 (ja) | 2018-08-30 |
JP7041663B2 (ja) | 2022-03-24 |
EP3587882A4 (en) | 2020-02-26 |
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