CN113650386A - 阻氧膜及其制备方法及包含该阻氧膜的沥青防水卷材 - Google Patents

阻氧膜及其制备方法及包含该阻氧膜的沥青防水卷材 Download PDF

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CN113650386A
CN113650386A CN202110986952.5A CN202110986952A CN113650386A CN 113650386 A CN113650386 A CN 113650386A CN 202110986952 A CN202110986952 A CN 202110986952A CN 113650386 A CN113650386 A CN 113650386A
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layer
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李卓
胡全超
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Dezhou Keshun Building Mat Co ltd
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Abstract

本发明提供一种阻氧膜及其制备方法及包含该阻氧膜的沥青防水卷材,涉及防水卷材技术领域。一种阻氧膜,包括由上往下依次布置的第一PE膜层、第一PVA层、粘合剂层、第二PVA层、第二PE膜层。本发明所提供的阻氧膜,在制备过程中通过在膜内侧涂布PVA涂布液,有效降低成型材料聚乙烯薄膜的氧气渗透率,有利于延长沥青防水卷材的保质期。本方案通过采用本发明所提供的阻氧膜替代普通的PE膜制备了一种沥青防水卷材,实现了不改变原有沥青防水卷材的生产工艺参数和原有沥青涂盖料配方,切换顺畅,不影响正常生产,一方面大大提高了生产效率,另一方面,能够明显提升沥青防水卷材热老化后的低温柔性与剥离强度,适用于大范围推广使用。

Description

阻氧膜及其制备方法及包含该阻氧膜的沥青防水卷材
技术领域
本发明涉及防水卷材技术领域,更具体地,涉及一种阻氧膜及其制备方法及包含该阻氧膜的沥青防水卷材。
背景技术
沥青防水卷材因具有优良的防水性能、粘接性能及力学性能被广泛应用。现有的沥青防水卷材一般由涂盖料与成型材料组成。
如一种无胎复合层沥青防水卷材(申请号:201822213254.8,公开日:2020.01.17)公开了:包括如上往下依次排布的面膜层、上表面涂盖层及底膜层,所述上表面涂盖层为由高聚物进行改性的沥青涂盖料,在所述上表面涂盖层与底膜层之间还设有与上表面涂盖层相容的下表面功能层。
但上述沥青防水卷材存在热老化性能较差的问题,即使是中、高档的沥青防水卷材也是容易热氧老化的材料,老化后的低温柔性、剥离强度等指标衰减明显,按照国标检测,结果不合格。即使在常温条件下存储,沥青防水卷材保质期也很短,一般配方生产10天后老化性能就已经衰减至不合格,即使是中、高档的沥青防水卷材,保质期延长至3个月也十分困难。沥青老化通常表现为沥青变硬、变脆、易开裂、粘性与延伸性降低。随着沥青防水卷材的老化,沥青防水卷材的使用性能及寿命均出现了明显的下降,严重影响了其在建筑防水、道路建设等领域中的使用。而针对热老化的改进,通常是改变涂盖料配方,配方的改变牵一发而动全身,容易引起其他性能的改变,且生产线上实验成本巨大,每个涂盖料配方的调整切换需要10~12小时方可生产,耗时费力。
不同配方之间也可能引起生产效率的不同,需要配合配方调整生产温度、速度等工艺参数。
因此,研发一种无需改变沥青涂盖料、即可改变沥青热老化性能的沥青防水卷材成为当下之需。
发明内容
本发明旨在克服上述现有技术的至少一种缺陷(不足),提供一种阻氧膜,替代普通的膜层,无需改变沥青涂盖料即可提升沥青防水卷材的热老化性能。
本发明的另一目的,在于提供一种阻氧膜的制备方法。
本发明的又一目的,在于提供包含该阻氧膜的沥青防水卷材。
本发明采取的技术方案是,一种阻氧膜,其特征在于,包括由上往下依次布置的第一PE膜层、第一PVA层、粘合剂层、第二PVA层、第二PE膜层。
沥青防水卷材生产后,由于长时间的放置,防水卷材中的沥青会与空气中的氧发生反应,生成氢过氧化物中间体(R-O-O-H)。一方面,氢过氧化物中间体容易自我分解产生羰基;另一方面,它也可以作为氧化剂,使沥青中的硫醚、硫醇被氧化成亚砜官能团。经过氧化反应历程,沥青中羰基与亚砜基官能团的含量增加,致使热老化性能下降。如果涂盖料沥青的配方进行改善,容易引起其它性能的变化且生产线的实验成本巨大,调整切换涂盖料配方需至少十几个小时,大大增加生产成本的消耗。
本发明的阻氧膜一般是作为沥青防水卷材的底膜或直接与沥青涂盖料层接触的膜层;本发明的阻氧膜的PVA层中,聚乙烯醇(PVA)具有良好的阻氧效果,通过将聚乙烯醇水溶液涂布在PE膜上,再复合,形成双层的PVA层,可以很好地阻挡氧气进入沥青涂盖料层,确保沥青防水卷材长时间放置后仍能具有优异的耐老化性能;本发明仅仅通过改变沥青防水卷材中的膜层,无需改变沥青涂盖料的配方,即可提升沥青防水卷材热老化后的低温柔性与剥离强度。
进一步地,所述第一PE膜层与所述第二PE膜层为不同取向的PE膜层。
所述第一PE膜层与所述第二PE膜层采用不同取向的PE膜层,有利于提高阻氧膜的强度。
更进一步地,所述第一PE膜层为45°取向PE膜层,所述第二PE膜层为-45°取向PE膜层。
45°取向的PE膜层与-45°取向的PE膜层能够获得更好地的力学性能,当然,其它角度的取向也有利于力学性能的提升。
进一步地,所述第一PE膜层、第一PVA层、粘合剂层、第二PVA层、第二PE膜层的厚度分别为30~70μm、1~5μm、1~10μm、1~5μm、30~70μm。
一种如上述的阻氧膜的制备方法,其特征在于,包括如下具体步骤:
S1:制备PE管状薄膜;
S2:45°取向的片状薄膜的制备:将步骤S1得到的PE管状薄膜充气、进行斜向45°螺旋切割、收卷,得到分子链取向与纵向成斜向45°夹角的片状薄膜;
S3:PVA涂布液的制备;
S4:将步骤S3制得的PVA涂布液涂刷在S2制得的45°取向的片状薄膜的一侧;
S5:取S4涂布有PVA的45°取向的片状薄膜两张,PVA涂布层在内,取向方向彼此交叉,通过无溶剂复合或淋膜进行交叉复合,得到阻氧膜。
所述无溶剂复合采用双组份聚氨酯胶粘剂;所述淋膜采用改性线性低密度聚乙烯(改性LLDPE)或聚乙烯-马来酸酐接枝共聚物(PE-g-MAH),或改性LLDPE与PE-g-MAH混合物。
在本发明中,制得PE管状薄膜后,进行斜向45°螺旋切割,通过在最终复合时,使方向彼此交叉,即得到所述的第一PE膜层和第二PE膜层;所述第一PVA层、第二PVA层是由PVA涂布液分别涂布在第一PE膜层、第二PE膜层表面形成的;将涂布有PVA的第一PE膜层和第二PE膜层复合时,通过无溶剂复合或淋膜的方式在所述第一PVA层和所述第二PVA层之间形成粘合剂层。
进一步地,在步骤S1中,所述PE管状薄膜包括如下组分:
高密度聚乙烯100重量份;
Figure BDA0003231047650000031
进一步地,在步骤S1中,PE管状薄膜的具体制备步骤如下:
将高密度聚乙烯、抗氧剂、光稳定剂、色母粒、碳酸钙放入搅拌器中,充分搅拌得到均匀的混合物;将混合物放入挤出机进料斗,通过挤出机内熔融、圆形口模挤出、吹胀、冷却成型后,得到管状薄膜;管状薄膜经过取向拉伸,吹胀倍率为2~5倍,拉伸后进行退火、放气、收卷;得到分子链取向与薄膜收卷方向平行的PE管状薄膜,薄膜上下表面均需进行电晕处理,保证电晕值不小于38达因。
优选地,所述抗氧剂为抗氧剂1010和/或抗氧剂168。
进一步地,所述涂布液包括如下组分按重量份数配制:
聚乙烯醇水溶液 60~80份;
异丙醇 5~35份;
硅烷偶联剂 0.1~2份;
所述聚乙烯醇水溶液的质量浓度为5~40%。
聚乙烯醇具有良好的阻氧效果,但是,聚乙烯醇是极性材料,聚乙烯膜为非极性材料,当两种不同极性的材料相接触,涂布液会产生缩孔,无法铺展在聚乙烯薄膜上;因此,加入异丙醇,可以调节涂布液的润湿效果,使其能够良好的铺展于底膜层上;硅烷偶联剂的加入,一方面能够促进纳米二氧化硅在聚乙烯醇涂层中的分散,另一方面提高涂布膜层与PE膜层、粘合剂层、纳米二氧化硅颗粒的粘接性能。
优选地,所述聚乙烯醇水溶液的质量浓度为10%。聚乙烯醇水溶液浓度过低,阻氧效果差;浓度过高,溶液不稳定,易析出沉淀,涂布至PE膜时容易涂布不均匀,最终导致得到的阻氧膜阻氧效果不稳定。
进一步地,所述硅烷偶联剂包括γ-缩水甘油醚氧丙基三甲氧基硅烷、γ―氨丙基三乙氧基硅烷、γ―甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、正辛基三乙氧基硅烷、乙烯基三异丙氧基硅烷中的一种或多种。
优选地,所述硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷。
进一步地,所述涂布液还包括5~35重量份的正硅酸乙酯和0.1~2重量份的二元酸。
本发明的涂布液包含了聚乙烯醇水溶液、异丙醇、硅烷偶联剂、正硅酸乙酯及丁二酸。在涂布液中,丁二酸作为聚乙烯醇的交联剂,促使聚乙烯醇交联,使线型的聚乙烯醇分子形成空间网状结构,提高了聚乙烯醇的耐水性能。另一方面,丁二酸在水中释放出氢离子,可以作为溶胶-凝胶反应的催化剂。在涂布液中,正硅酸乙酯水解释放出硅溶胶,丁二酸为溶胶-凝胶反应所需的酸催化剂,促使线型的硅溶胶逐步交联形成空间立体网状结构的纳米二氧化硅粒子,提高聚乙烯醇涂层的强度、刚度、粘接性能及耐水性能;原位生成空间立体网状结构的纳米二氧化硅粒子与交联的聚乙烯醇在局部形成互穿网络结构,使得聚乙烯醇只能在水中溶胀而无法溶解,提高了聚乙烯醇涂层的耐水性,互穿网络结构也有效降低纳米二氧化硅的团聚,利于纳米二氧化硅的分散,进一步提高聚乙烯醇涂层的强度、刚度,粘接性能及耐水性能。硅烷偶联剂一方面能够促进纳米二氧化硅在聚乙烯醇涂层中的分散,另一方面提高涂布膜层与PE膜层、粘合剂层、纳米二氧化硅颗粒的粘接性能。
进一步地,在步骤S3中,涂布液的具体制备步骤如下:
称取聚乙烯醇放入水中,搅拌均匀得到聚乙烯醇水溶液,加入异丙醇和正硅酸乙酯,搅拌均匀后,静置24~48小时,再加入二元酸、硅烷偶联剂,搅拌均匀,静置10~20min,得到涂布液。
一种沥青防水卷材,包含上述的阻氧膜。
进一步地,所述阻氧膜上依次布置有沥青涂盖料层、PET隔离膜。
进一步地,所述阻氧膜、沥青涂盖料层、PET隔离膜的厚度为70~160μm、0.8~2.0mm、25~40μm。
本发明所制得的沥青防水卷材的氧气渗透率为0~60cc/m2·day。
与现有技术相比,本发明的有益效果为:
(1)不改变原有沥青涂盖料配方,明显提升沥青防水卷材热老化后的低温柔性与剥离强度;
(2)不改变原有沥青防水卷材的生产工艺参数,切换顺畅,不影响正常生产,生产效率大大提高;
(3)在制备PE交叉膜的过程中,在PE交叉膜内侧涂布PVA涂布液,有效降低成型材料聚乙烯薄膜的氧气渗透率,延长沥青防水卷材的保质期。
附图说明
图1为本发明的沥青防水卷材的层次结构图。
图2为本发明的阻氧膜的层次结构图。
附图中标记为:PET隔离膜-100;沥青涂盖料层-200;阻氧膜-300;45°取向PE膜层-310,第一PVA层-320,粘结层-330,第二PVA层-340,-45°取向PE膜层-350。
具体实施方式
本发明实施例仅用于示例性说明,不能理解为对本发明的限制。
实施例1
一种阻氧膜的制备方法,具体步骤如下:
S1将高密度聚乙烯100重量份、抗氧剂1010 0.5重量份、抗氧剂168 0.5重量份、光稳定剂2020 0.5重量份、色母粒2.0重量份、碳酸钙20重量份放入搅拌器中,充分搅拌得到均匀的混合物;将混合物放入挤出机进料斗,通过挤出机内熔融、圆形口模挤出、吹胀、冷却成型后,得到管状薄膜;管状薄膜经过取向拉伸,吹胀倍率为4倍,拉伸后进行退火、放气、收卷;得到分子链取向与薄膜收卷方向平行的PE管状薄膜,薄膜上下表面均需进行电晕处理,得到PE管状薄膜;
S2将步骤S1得到的PE管状薄膜充气、进行斜向45°螺旋切割、收卷,得到分子链取向与纵向成斜向45°夹角的片状薄膜;
S3称取一定量的聚乙烯醇,配制成10%的聚乙烯醇水溶液,取聚乙烯醇水溶液60重量份,加入异丙醇10重量份和正硅酸乙酯30重量份,搅拌均匀后,静置24小时,再加入丁二酸1重量份、γ-缩水甘油醚氧丙基三甲氧基硅烷1重量份,搅拌均匀,静置20min,得到涂布液;
S4将步骤S3制得的PVA涂布液涂刷在S2制得的45°取向的片状薄膜的一侧;
S5取S4涂布有PVA的45°取向的片状薄膜两张,PVA涂布层在内,取向方向彼此交叉,通过淋膜(聚乙烯-马来酸酐接枝共聚物)进行交叉复合,得到阻氧膜。
实施例2
一种阻氧膜的制备方法,具体步骤如下:
S1将高密度聚乙烯100重量份、抗氧剂1010 0.5重量份、抗氧剂168 0.5重量份、光稳定剂2020 0.5重量份、色母粒2.0重量份、碳酸钙20重量份放入搅拌器中,充分搅拌得到均匀的混合物;将混合物放入挤出机进料斗,通过挤出机内熔融、圆形口模挤出、吹胀、冷却成型后,得到管状薄膜;管状薄膜经过取向拉伸,吹胀倍率为4倍,拉伸后进行退火、放气、收卷;得到分子链取向与薄膜收卷方向平行的PE管状薄膜,薄膜上下表面均需进行电晕处理,得到PE管状薄膜;
S2将步骤S1得到的PE管状薄膜充气、进行斜向45°螺旋切割、收卷,得到分子链取向与纵向成斜向45°夹角的片状薄膜;
S3称取一定量的聚乙烯醇,配制成10%的聚乙烯醇水溶液,取聚乙烯醇水溶液70重量份,加入异丙醇10重量份和正硅酸乙酯20重量份,搅拌均匀后,静置24小时,再加入丁二酸1份、γ-缩水甘油醚氧丙基三甲氧基硅烷1份,搅拌均匀,静置20min,得到涂布液;
S4将步骤S3制得的PVA涂布液涂刷在S2制得的45°取向的片状薄膜的一侧;
S5取S4涂布有PVA的45°取向的片状薄膜两张,PVA涂布层在内,取向方向彼此交叉,通过淋膜(聚乙烯-马来酸酐接枝共聚物)进行交叉复合,得到阻氧膜。
实施例3
一种阻氧膜的制备方法,具体步骤如下:
S1将高密度聚乙烯100重量份、抗氧剂1010 0.5重量份、抗氧剂168 0.5重量份、光稳定剂2020 0.5重量份、色母粒2.0重量份、碳酸钙20重量份放入搅拌器中,充分搅拌得到均匀的混合物;将混合物放入挤出机进料斗,通过挤出机内熔融、圆形口模挤出、吹胀、冷却成型后,得到管状薄膜;管状薄膜经过取向拉伸,吹胀倍率为4倍,拉伸后进行退火、放气、收卷;得到分子链取向与薄膜收卷方向平行的PE管状薄膜,薄膜上下表面均需进行电晕处理,得到PE管状薄膜;
S2将步骤S1得到的PE管状薄膜充气、进行斜向45°螺旋切割、收卷,得到分子链取向与纵向成斜向45°夹角的片状薄膜;
S3称取一定量的聚乙烯醇,配制成10%的聚乙烯醇水溶液,取聚乙烯醇水溶液80重量份,加入异丙醇10重量份和正硅酸乙酯10重量份,搅拌均匀后,静置24小时,再加入丁二酸1重量份、γ-缩水甘油醚氧丙基三甲氧基硅烷1重量份,搅拌均匀,静置20min,得到涂布液;
S4将步骤S3制得的PVA涂布液涂刷在S2制得的45°取向的片状薄膜的一侧;
S5取S4涂布有PVA的45°取向的片状薄膜两张,PVA涂布层在内,取向方向彼此交叉,通过淋膜(聚乙烯-马来酸酐接枝共聚物)进行交叉复合,得到阻氧膜。
实施例4
一种阻氧膜的制备方法,具体步骤如下:
S1将高密度聚乙烯100重量份、抗氧剂1010 0.5重量份、抗氧剂168 0.5重量份、光稳定剂2020 0.5重量份、色母粒2.0重量份、碳酸钙20重量份放入搅拌器中,充分搅拌得到均匀的混合物;将混合物放入挤出机进料斗,通过挤出机内熔融、圆形口模挤出、吹胀、冷却成型后,得到管状薄膜;管状薄膜经过取向拉伸,吹胀倍率为4倍,拉伸后进行退火、放气、收卷;得到分子链取向与薄膜收卷方向平行的PE管状薄膜,薄膜上下表面均需进行电晕处理,得到PE管状薄膜;
S2将步骤S1得到的PE管状薄膜充气、进行斜向45°螺旋切割、收卷,得到分子链取向与纵向成斜向45°夹角的片状薄膜;
S3称取一定量的聚乙烯醇,配制成10%的聚乙烯醇水溶液,取聚乙烯醇水溶液80重量份,加入异丙醇10重量份,搅拌均匀后,静置24小时,再加入γ-缩水甘油醚氧丙基三甲氧基硅烷1重量份,搅拌均匀,静置20min,得到涂布液;
S4将步骤S3制得的PVA涂布液涂刷在S2制得的45°取向的片状薄膜的一侧;
S5取S4涂布有PVA的45°取向的片状薄膜两张,PVA涂布层在内,取向方向彼此交叉,通过淋膜(聚乙烯-马来酸酐接枝共聚物)进行交叉复合,得到阻氧膜。
对比例1
本对比例与实施例1的区别在于,本对比例的45°夹角的片状薄膜不进行PVA涂布即进行交叉复合,得到PE交叉膜。
沥青防水卷材的制备:
采用双辊挤压的方式,将实施例1~4制得的阻氧膜及对比例1制得的PE交叉膜,分别与沥青涂盖料层、PET隔离膜层挤压成型,经过冷却、切割、收卷、包装,得到成品。
如图1所示,实施例1~4所制的沥青防水卷材,包括由上往下依次布置的PET隔离膜层、沥青涂盖料层、阻氧膜;所述PET隔离膜层、沥青涂盖料层、阻氧膜的厚度分别为35μm、1.5mm、100μm。
如图2所示,实施例1~4所制的阻氧膜包括由上往下依次布置的45°取向PE膜层、第一PVA层、粘合剂层、第二PVA层、-45°取向PE膜层;所述粘合剂层为聚乙烯-马来酸酐接枝共聚物层;所述45°取向PE膜层、第一PVA层、粘合剂层、第二PVA层、-45°取向PE膜层的厚度分别为45μm、2μm、10μm、2μm、45μm。
将实施例1~4及对比例1制得的沥青防水卷材进行性能测试,结果如表1所示:
表1实施例1~4及对比例1制得的沥青防水卷材性能测试表
Figure BDA0003231047650000081
Figure BDA0003231047650000091
由上述实验结果可知,实施例1~4的沥青防水卷材具有优异的阻氧效果,并且,在热处理后,仍具有较好的低温柔性及剥离强度。从实施例3、4中可得到,正硅酸乙酯和丁二酸虽然对PVA涂布液的阻氧性能有一定影响,但是能够提高沥青防水卷材老化后的剥离强度。
显然,本发明的上述实施例仅仅是为清楚地说明本发明技术方案所作的举例,而并非是对本发明的具体实施方式的限定。凡在本发明权利要求书的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。

Claims (10)

1.一种阻氧膜,其特征在于,包括由上往下依次布置的第一PE膜层、第一PVA层、粘合剂层、第二PVA层、第二PE膜层。
2.根据权利要求1所述的一种阻氧膜,其特征在于,所述第一PE膜层为45°取向PE膜层,所述第二PE膜层为-45°取向PE膜层。
3.根据权利要求1或2所述的一种阻氧膜,其特征在于,所述第一PE膜层、第一PVA层、粘合剂层、第二PVA层、第二PE膜层的厚度分别为30~70μm、1~5μm、1~10μm、1~5μm、30~70μm。
4.一种如权利要求2或3所述的阻氧膜的制备方法,其特征在于,包括如下具体步骤:
S1:制备PE管状薄膜;
S2:45°取向的片状薄膜的制备:将步骤S1得到的PE管状薄膜充气、进行斜向45°螺旋切割、收卷,得到分子链取向与纵向成斜向45°夹角的片状薄膜;
S3:PVA涂布液的制备;
S4:将步骤S3制得的PVA涂布液涂刷在S2制得的45°取向的片状薄膜的一侧;
S5:取S4涂布有PVA的45°取向的片状薄膜两张,PVA涂布层在内,取向方向彼此交叉,通过无溶剂复合或淋膜进行交叉复合,得到阻氧膜。
5.根据权利要求4所述的阻氧膜的制备方法,其特征在于,在步骤S1中,所述PE管状薄膜包括如下组分:
高密度聚乙烯100重量份;
Figure FDA0003231047640000011
6.根据权利要求5所述的阻氧膜的制备方法,其特征在于,在步骤S1中,PE管状薄膜的具体制备步骤如下:
将高密度聚乙烯、抗氧剂、光稳定剂、色母粒、碳酸钙放入搅拌器中,充分搅拌得到均匀的混合物;将混合物放入挤出机进料斗,通过挤出机内熔融、圆形口模挤出、吹胀、冷却成型后,得到管状薄膜;管状薄膜经过取向拉伸,吹胀倍率为2~5倍,拉伸后进行退火、放气、收卷;得到分子链取向与薄膜收卷方向平行的PE管状薄膜,薄膜上下表面均需进行电晕处理,保证电晕值不小于38达因。
7.根据权利要求4所述的阻氧膜的制备方法,其特征在于,所述涂布液包括如下组分按重量份数配制:
聚乙烯醇水溶液 60~80份;
异丙醇 5~35份;
硅烷偶联剂 0.1~2份;
所述聚乙烯醇水溶液的质量浓度为5~40%。
8.根据权利要求7所述的阻氧膜的制备方法,其特征在于,所述涂布液还包括5~35重量份的正硅酸乙酯和0.1~2重量份的二元酸。
9.根据权利要求8所述的阻氧膜的制备方法,其特征在于,在步骤S3中,涂布液的具体制备步骤如下:
称取聚乙烯醇放入水中,搅拌均匀得到聚乙烯醇水溶液,加入异丙醇和正硅酸乙酯,搅拌均匀后,静置24~48小时,再加入二元酸、硅烷偶联剂,搅拌均匀,静置10~20min,得到涂布液。
10.一种沥青防水卷材,其特征在于,包含如权利要求1~3任一所述的阻氧膜,或根据权利要求4~9任一项所述的制备方法制得的阻氧膜。
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