CN109312099B - 屏障层 - Google Patents
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- CN109312099B CN109312099B CN201780036155.2A CN201780036155A CN109312099B CN 109312099 B CN109312099 B CN 109312099B CN 201780036155 A CN201780036155 A CN 201780036155A CN 109312099 B CN109312099 B CN 109312099B
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Abstract
本发明涉及特殊聚合物层作为屏障,尤其是作为复合材料中的屏障层的用途。所述聚合物层的合适聚合物是乙烯和乙烯醇的或乙烯和一氧化碳的或乙烯和一氧化碳及丙烯的共聚物。这些屏障层相对于不同的气体表现出选择性屏障作用,其中所述屏障作用相对于HFO特别有效。基于这些性能,此类屏障层可以对隔绝和隔离性能产生积极影响,例如在绝热管中。
Description
本发明涉及特殊聚合物作为屏障层,尤其是作为复合材料中的屏障层的用途。这些屏障层相对于不同的气体表现出选择性屏障作用,所述屏障作用相对于HFO特别有效。基于这些性能,此类屏障层可以对保温性能产生积极影响,例如在绝热管中。
用于保温的材料是已知材料。此类泡沫具有许多应用,尤其是用于绝热,因此是许多应用中的重要组成部分。泡沫的保温性能依赖于几个参数,尤其依赖于电解槽气体的组成。
已知类别的泡沫为聚氨酯泡沫(PU),由多元醇和异氰酸酯组成。为了生产这些泡沫,通常还添加了另一种物理发泡剂并且通常搅拌到多元醇组分中,然后在高压搅拌头中与异氰酸酯混合,之后立即对双组分混合物(2C)计量。这种物理发泡剂是PU泡沫中电解槽气体的第一组分。多元醇组分通常含有一定量的水,典型范围为0.5至1.5重量%。这种水引起以下反应:a)与异氰酸酯反应形成氨基甲酸,然而氨基甲酸不稳定并且,在二氧化碳分离时,立即分解形成相应的胺;b)这样生成的胺与另一异氰酸酯分子反应形成相应的脲。
这种反应导致在PU泡沫中形成另外的电解槽气体并因此而有助于发泡过程。生成的脲有利于生成的泡沫的热稳定性。与之有关的详情在Oertel等人(Polyurethane,编辑Günter Oertel,1993年第3版,Hanser Verlag,第13页;第94页)中有描述。
与氯氟烃(HFC)形成鲜明对比,氢氟烯烃(HFO)是因其全球增温潜能(GWP)较低而闻名的已知类别的化合物。因为HFO不易燃,所以将其用作发泡剂,例如正如WO2016/094762中提到的那样。HFO对泡沫的保温性能产生积极影响。
聚合物材料通常对所有类型的渗透物(气态或液态)都具有一定程度的渗透性。然而,聚合物在每种情况下每单位时间特定渗透物迁移通过给定材料的量上显著不同。聚合物材料作为空气中的气体,尤其是氮气(N2)、氧气(O2)、二氧化碳(CO2)和水(H2O)的用途本身是已知的。因此,EP 1355103描述了一种基于EVOH或PVDC的屏障,其减少了CO2、N2和O2气体的扩散,但同时水可渗透。EP2340929描述了相对于O2和CO2作为屏障的EVOH层。WO92/13716描述了相对于HFC作为屏障的EVOH层。如上所述,与HFO相比,HFC原则上具有不同的性质。
鉴于此,似乎希望提供具有改进保温性能的泡沫。
似乎还希望提供具有屏障性能的材料,尤其是具有选择性屏障性能的材料。
根据独立权利要求达到了以上所列目的。从属权利要求构成有利实施方案。在说明书和附图中可以找到其它有利实施方案。结合本发明给出的任何一般、优选和特别优选的实施方案、范围等可以彼此组合。同样,各个定义、实施方案等均可省略或者可以不相关。
下面详细描述本发明。不言而喻,可以组合下面公开和描述的各个实施方案、优先选择和范围中的任何一个。另外,根据实施方案,可以不使用特定定义、优先选择和范围。此外,术语“包含”包括“含有”和“由......组成”的含义。
本发明中使用的术语以通常意义使用,本领域技术人员熟悉这些意义。如果直接连接没有其它含义,则以下术语尤其具有本文给出的含义/定义。
还通过附图说明了本发明;除了以下描述之外,还可以在这些图中找到本发明的其它实施方案。
图1是泡沫保温套(20)上根据本发明的复合材料(10)的结构的横截面示意图。该图中,保温套(20)和(21)的聚合物(22)是保温套(20)的含HFO的电解槽气体。屏障(1)的各种实施方案显示为:
(a)自支撑结构元件(1);
(b)具有外屏障(1)、附着力促进剂(2)和热塑性塑料(3)的复合材料(10);
(c)具有内屏障(1)、附着力促进剂(2、2’)和热塑性塑料(3、3’)的复合材料(10)。
因此,本发明涉及聚合物层作为气体屏障(1)的用途,聚合物层的聚合物包含由乙烯和乙烯醇组成的共聚物或由乙烯和一氧化碳组成的共聚物或由乙烯和一氧化碳及丙烯组成的共聚物;并且所述气体选自氢氟烯烃类。
已经发现,氢氟烯烃HFO,尤其作为泡沫(22)中的电解槽气体(21),被所述聚合物层(1)非常有效地阻挡。因此,例如泡沫中这些电解槽气体的流失时间可以减到最少,以便长时间保持该泡沫的绝热效果。
还发现,本文所述的聚合物层(1)对二氧化碳具有相对较高程度的渗透性。因此,例如,当形成聚氨酯泡沫(PU)时产生的二氧化碳可以随时间推移通过扩散离开聚合物层(1)。
还发现,本文所述的供使用的生产方法可以以简单且成本有效的方式实施,并且可以整合在连续过程中。
这种用途和各个特征应在下面进行解释。
屏障(1):在几个技术领域中,例如在导管/管道系统领域中已知扩散屏障。
根据本发明,屏障(1)呈分层形式。根据本发明,屏障可以作为单层或单独的几层提供。
聚合物材料的渗透性值在很宽的范围内变化;大于因数105。对于不同的渗透物而言,与屏障作用的存在有关的标准是不同的。
O2、N2和CO2的测量值(根据ISO 15105-1测定)通常以cm3/m2*天*巴给出。如果值小于20,则屏障作用良好并且认为所述聚合物不可渗透。如果值大于100,则不再提供屏障作用并且认为所述聚合物可渗透。对于介于之间的值,认为所述聚合物是半渗透的。
HFO(根据ISO 15105-1:2007-10测定)、Cp(根据ISO 15105-2:2003-02测定)和水(根据ISO 15105-3:2003-01测定)的测量值通常以ml/m2*天给出。如果值小于3,则屏障作用良好并且认为所述聚合物不可渗透。如果值大于20,则不再存在屏障作用并且认为所述聚合物可渗透。对于介于之间的值,认为所述聚合物是半渗透的。
本发明还涉及聚合物层作为气体选择性屏障(1)的用途,所述聚合物层的聚合物包含如本文所述由乙烯和乙烯醇组成的共聚物或由乙烯和一氧化碳组成的共聚物或由乙烯和一氧化碳及丙烯组成的共聚物;并且所述屏障优选为
·对来自HFO类的气体不可渗透;
·对水和水蒸汽可渗透;
·对二氧化碳半渗透;并且
·对来自周围区域的气体,尤其是氮气和氧气及空气不可渗透;或
所述屏障优选为
·对来自HFO类的气体不可渗透;
·对水和水蒸汽半渗透;
·对二氧化碳不可渗透;并且
·对来自周围区域的气体,尤其是氮气和氧气及空气不可渗透。
已经发现,本文所述的屏障(1)非常好地满足这些要求。
聚合物层(1)有利地具有以下扩散系数:
·HFO小于3ml/m2*天
·H2O(气体)大于3ml/m2*天
·CO2大于20cm3/m2*天*巴
·O2小于20cm3/m2*天*巴
·N2小于20cm3/m2*天*巴
这些值尤其可通过选择聚合物和/或层厚来实现。已经证明此类值对许多应用有利,尤其是在保温套领域中,例如用于导管。
对于HFO的屏障作用:由于其低度导热性,HFO在保温套中是有利的电解槽气体。因此有利的是将所述气体阻止在保温材料中。本文所述的层允许HFO通过层(1)的扩散减少。该性能很重要,例如以便长期确保导管/管道系统的保温能力。
对于水蒸汽的屏障作用:对所述水蒸汽扩散的阻碍不应太强,因为这样否则会产生所述水蒸汽积聚在保温套中并因此损害导热性的风险。
另外,保温套中水分的积聚也有损坏所述保温套的风险。在一个有利的实施方案中,本文所述的层还允许水从保温套中扩散出来。这种性能对于导管/管道系统特别重要,导管/管道系统的介质管由塑料材料制成。如果在此类导管/管道系统中输送水性介质,则水可以从介质,通过导管转移到保温套中,因此可以降低保温能力并损坏泡沫保温套。
对于二氧化碳的屏障作用:在一个有利的实施方案中,本文所述的层还对CO2提供一定程度的渗透性。特别合适的CO2渗透率值在0.5至100cm3/m2*天*巴的范围内。
对氧气的屏障作用:O2会导致保温材料氧化性损坏,特别是在高使用温度下,如在塑料套管(PJP)中。因此,电解槽气体不应含有O2并且应避免其扩散到保温套中。
对于氮气的屏障作用:首先,预计N2不会对PU泡沫产生不利影响,但N2的导热性程度为26mW/m*K明显高于其它电解槽气体。因此,其在PU泡沫中的存在也会增加其导性程度,这是不希望的。
因此屏障层可以适应所需要求概要。为了生产具有尽可能低的导热性程度并且还长时间保持这种低导热性程度的泡沫,所述屏障层旨在防止氧气和氮气扩散到泡沫中,允许CO2从泡沫中扩散出来,并防止HFO从泡沫中扩散出来。这越有效,泡沫的性能越好。
来自HFO类的电解槽气体(21)与本文所述的根据式(II)、(III)和(IV)的屏障层(1)的组合在绝热导管中产生特别良好的超加性保温性能。这些组成部分之间的此类积极相互作用令人惊讶。不受任何理论束缚,这种超加性作用可归因于根据式(II)、(III)和(IV)的材料的屏障性能。
聚合物:如图所示,屏障包含由乙烯与一氧化碳(所谓的聚酮)或乙烯醇(所谓的乙烯-乙烯醇)组成的共聚物。
聚酮(PK):在一个有利的实施方案中,屏障包含含有聚酮或由聚酮组成的聚合物。因此,聚合物层包含聚酮和聚酮共混物。聚酮是本身已知的材料,其特征在于聚合物链中的酮基(C=O)。
在这个实施方案中,聚合物有利地包含多达50至100重量%,优选多达80至100重量%的式(II)或式(III)的结构单元。
其中
o表示1或2,优选1,
p表示1或2,优选1,
q表示1至20,并且
r表示1至20。
在一个实施方案中,所述聚合物含有90至100重量%的式(II)的结构单元,其中o和p表示1。
在一个实施方案中,所述聚合物含有90至100重量%的式(III)的结构单元,其中q和r彼此独立地表示1至20。
在一个实施方案中,式(II)的聚合物的分子量Mw大于20,000,尤其为50,000至500,000。在一个实施方案中,式(III)的聚合物的分子量Mw大于20,000,尤其为50,000至500,000。
在一个实施方案中,式(II)或式(III)的聚合物的熔融温度高于200℃(DSC期间测量,根据ISO 11357-1/3为10K/分钟)。
在一个实施方案中,根据DIN EN ISO 62:2008-05测量,式(II)或式(III)的聚合物具有较低程度的吸水性,优选低于3%(在23℃水中的饱和度)。
聚酮可通过一氧化碳与相应烯烃如丙烯和/或乙烯的催化转化获得。此类聚酮也称为脂族聚酮。这些聚合物可商购获得,例如来自Hyosung的聚酮共聚物(式II)或聚酮三元共聚物(式III)。此类聚酮也可以商品名PK商购获得。
与EVOH(IV)相比,PK(II、III)对于O2和N2的屏障性能较差,并且对于H2O和CO2的屏障性能较差。因此,根据计划的用途,这些屏障材料中的一种可能是有利的。例如,如果使用由塑料材料制成的介质管,则更重要的是允许水分迁移以防止其在PU泡沫中积聚。如果使用由金属制成的介质管,则输送的温水迁移到泡沫中的效果不明显。在这种情况下,由于在输送能量并且必须最小化损失的经典区域供热中优选使用通常使用的KMR管,因此可能更为重要的是长时间保持泡沫的导热性程度尽可能低。
乙烯-乙烯醇(EVOH):在另一个有利的实施方案中,屏障包含含有乙烯-乙烯醇或由乙烯-乙烯醇组成的聚合物。
在这个实施方案中,所述聚合物包含50至100重量%,优选80至100重量%的式(IV)的结构单元,
其中
m表示1至10,并且
n表示2至20。
合适的EVOH尤其为统计共聚物,其中m/n比率为30/100至50/100。
合适的EVOH尤其分子量Mw大于20,000,尤其为50,000至500,000。
EVOH可商购获得,例如作为来自Kuraray的EVAL FP系列或EP系列。这些的特征在于良好的可加工性,尤其是它们很容易与通常通过共挤出使用的夹套材料聚乙烯(PE)一起加工,因为其溶体粘度和熔融温度在相似的范围内。
与PK(II、III)相比,EVOH(IV)对于O2和N2显示出更好的屏障性能,并且对于H2O和CO2显示出更好的屏障作用。因此,在存在少量H2O和/或CO2时这些材料特别适合使用。连同PK呈现的考虑因素在此适用。
气体:如上所述,气体选自氢氟烷烃(HFO)类。这种气体可以是泡沫,尤其是例如泡沫保温套(20)的电解槽气体(21)。这种气体可由HFO组成或含有HFO。气体的典型附加组分尤其是(环)烷烃、CO2、N2、O2和H2O。
氢烯烃:HFO是已知的并且可商购获得或者可使用已知方法生成。该术语既包括仅含碳、氢和氟的化合物,也包括还含氯的化合物(也称为HFCO),并且每种化合物在分子中含有至少一个不饱和键。HFO可以是不同组分的混合物或纯组分。HFO也可以是异构体混合物,尤其是E-异构体/Z-异构体,或异构纯化合物。
在本发明的上下文中,特别合适的HFO的沸点高于0℃。
在本发明的上下文中,特别合适的HFO选自包含式(I)化合物的类别,
其中R5表示H、F、Cl、CF3,优选Cl、Cf3,并且R6表示H、F、Cl、CF3,优选H。
特别合适的HFO为1233zd(例如来自Honeywell的Solstice LBA)和1336mzz(例如来自DuPont的Formacel 1100)。
令人惊讶地发现,当保温套(20)的电解槽气体(21)含有至少10体积%,优选至少30体积%,特别优选50体积%的HFO时,并且当该保温套被如本文所述的屏障(1)包围时,绝热导管具有改善的保温特性。
(环)烷烃:这些称为绝热管中保温套的电解槽气体。所述烷烃或环烷烃有利地选自丙烷、丁烷、戊烷、环戊烷、己烷和环己烷。通过将(环)烷烃与HFO组合,可以精细调节产品性能和/或可以提高可生产性和/或可以降低成本以及合理的质量损失。所述(环)烷烃可以是纯化合物或混合物;脂族烷烃可以是异构纯的化合物或异构体混合物。特别合适的(环)烷烃为环戊烷(Cp)。
二氧化碳(CO2):这称为绝热管中保温套的电解槽气体。它可以作为生产过程的副产物形成,或者可以按特定量添加。电解槽气体的CO2含量通常低于50体积%。
氮气(N2)、氧气(O2):生产过程可以使来自大气/环境空气的组分进入电解槽气体。这些基本上为N2和/或O2,例如空气。电解槽气体含量在生产时通常低于5体积%。
水(H2O):这可以呈气体或液体的形式。H2O通常借助于冷凝从周围区域进入保温套电解槽气体中,或者借助于渗透从载有介质的元件进入保温套电解槽气体中。
因此,在一个实施方案中,本发明涉及本文所述的用途,其中电解槽气体(21)是包含10至100体积%的HFO和0至50体积%的(环)烷烃和0至50体积%的CO2的混合物。
泡沫:如上所述,气体可以是泡沫,尤其是泡沫保温套(20)的电解槽气体(21)。
此类泡沫本身是已知的。满足以下标准的泡沫:DIN EN 253:2015-12(尤其对于PJP而言)和EN15632-1:2009/A1:2014、EN15632-2:2010/A1:2014和EN15632-3:2010/A1:2014(尤其对于PMP而言)特别合适。该术语包括硬泡沫和软泡沫。泡沫可为闭孔型或开孔型,优选为闭孔型,尤其是例如标准DINEN 253:2015-12中所示。此类泡沫优选选自聚氨酯(PU)、聚异氰酸酯(PIR)、热塑性聚酯(尤其是PET)和热塑性聚烯烃(尤其是PE和PP)。
因此本发明还涉及如本文所述的聚合物层作为气体屏障(1)的用途,所述气体为泡沫的电解槽气体,其特征在于所述泡沫(聚合物(22)和电解槽气体(21))满足以下标准:
-PU含有50至100体积%的1233zd和0至50体积%的Cp;
-PU含有50至100体积%的1336mzz和0至50体积%的Cp;
-PIR含有50至100体积%的1233zd和0至50体积%的Cp;
-PIR含有50至100体积%的1336mzz和0至50体积%的Cp;
-PET含有50至100体积%的1233zd和0至50体积%的Cp;
-PET含有50至100体积%的1336mzz和0至50体积%的Cp;
-PE含有50至100体积%的1233zd和0至50体积%的Cp;和/或
-PE含有50至100体积%的1336mzz和0至50体积%的Cp。
在一个实施方案中,所述电解槽气体相互补充达到100体积%。在另一个实施方案中,这些电解槽气体与CO2和空气互补达到100%。
本发明还涉及本文所述的用途,其中所述聚合物层(1)为自支撑结构元件。因此聚合物层(1)可为薄膜或模制体。
本发明还涉及本文所述的用途,其中所述聚合物层(1)为复合材料(10)的一部分。此类复合材料本身是已知的。对于本文所述的用途,所述复合材料(10)可具有以下分层结构:热塑性聚合物(3)、任选附着力促进剂(2)、如本文所述作为屏障(1)的聚合物层、任选附着力促进剂(2')、任选热塑性聚合物(3')。组分(2)和(3)是本领域技术人员已知的可商购产品。
热塑性聚合物(3):可以使用各种热塑性塑料;这些通常比层(1)具有更小的屏障作用。有利地使用选自商用类型的PE的热塑性聚合物(3、3'),如高密度PE(HDPE)、低密度PE(LDPE)、线性低密度PE(LLDPE)。
附着力促进剂(2、2'):可以使用各种附着力促进剂;这些通常比层(1)具有更小的屏障作用。附着力促进剂(2、2')有利地选自PE接枝共聚物,其具有至少一种其它组分,例如马来酸酐。此类物质可以商品名例如AmplifyTM从Dow或以AdmerTM从Mitsui商购获得。
所述各层的厚度可以在很宽的范围内变化,并且取决于对于各渗透物的所需屏障作用,取决于材料,并且最后尤其取决于生产和成本因素。已经证明以下值是合适的:聚合物层(1)的层厚有利地在0.01至1mm的范围内,优选地在0.03至0.5mm的范围内,特别优选在0.05至0.3mm的范围内。在每种情况下附着力促进剂层(2、2')的层厚有利地在0.01至1mm的范围内,优选在0.05至0.5mm的范围内,特别优选在0.1至0.3mm的范围内。在每种情况下热塑性聚合物(3、3')的层厚有利地在0.01至1mm的范围内,优选在0.05至0.5mm的范围内,特别优选在0.1至0.3mm的范围内。
本发明还涉及在许多技术领域中如本文所述的作为屏障(1)的聚合物层或复合材料(10)对于气体的用途。根据本发明的用途不限于单一用途;相反,可以用于对HFO的屏障作用是有用的或合乎需要的所有领域中。
本发明相应地涉及如本文所述的聚合物层(1)或如本文所述的复合材料(10)的用途
·其作为保温套的屏障材料,尤其是冷却装置,用于局部或区域供热的管道系统,用于冷却建筑物的管道系统,用于输送冷却介质的管道系统,工业应用中的管道系统,用于输送气体、液体或固体的管道系统的屏障材料;和/或
·其作为用于包装,尤其是用于医药品、食品和电子元件的屏障材料;和/或
·其作为容器和储罐的屏障材料。
保温套:该术语尤其包括来自塑料介质管道系统(PMP)和塑料夹套式管道系统(PJP)类的绝热管道系统。这些用于输送加热或冷却的介质,尤其是水或水溶液。但是,它们也可用于输送其它物质和化学品。
基于以下非限制性实施例更详细地解释本发明。
在来自聚氨酯类的泡沫中,在生产过程结束时存在许多电解槽气体。表中示出了可能的电解槽气体及其基本属性的汇总。作为实例给出的泡沫类型的规定量与尚未老化的新生产泡沫的值有关。
实施例1:通过聚合物薄膜的扩散
已经以指定标准中描述的方式通过实验测定了O2、N2、CO2、HFO1233zd、Cp和H2O通过不同聚合物薄膜的扩散。结果汇总在表中。
Cp:环戊烷;PK,脂族聚通;EVOH:由乙烯和乙烯醇组成的共聚物;PAN:聚丙烯酰胺;LDPE:低密度聚乙烯。
根据上述定义,对于观察的所有渗透物而言EVOH是良好屏障。LDPE几乎没有屏障作用,而仅对于水具有部分屏障作用。脂族PK和PAN对于O2、N2、HFO和Cp具有良好的屏障作用,并且对于CO2和H2O具有部分屏障作用。
关于实际应用,PAN难以加工,易碎且商业上可用性差的事实是不利的。EVOH和PK可以容易地加工并且可以商购获得。
实施例2:在不同环境条件下老化之后测量泡沫的电解槽气体
焊接宽度为20至30cm的薄膜网以形成具有约8升体积的袋子。为这些袋子填充含有环戊烷作为发泡剂的PU泡沫。一旦发泡过程结束,就在上端焊接袋子。
然后先切割每个袋子并测定电解槽气体的组成(第0天)。其它样品在两个老化试验箱中老化;其中一个老化试验箱的温度为70℃,空气相对湿度(RH)为10%,而另一个老化试验箱的温度为70℃,相对湿度(RH)为90%。
表中列出了各气体按体积%计的值。
可以清楚地看出,对于材料EVOH和PAN而言,屏障作用很大程度上取决于周围区域的湿度。
由实施例1的结果,预计HFO和Cp的结果类似。因此,对于这些气体而言,EVOH和PK是合理的屏蔽层。
虽然本申请描述了本发明的优选实施方案,但应该指出的是,本发明不限于这些实施方案,并且还可以具有在以下权利要求范围内的不同设计。
Claims (13)
4.根据权利要求1所述的用途,其特征在于式(I)的氢氟烯烃选自1233zd和1336mzz。
5.根据权利要求1所述的用途,其特征在于式(I)的氢氟烯烃选自如权利要求4中所定义的沸点高于0℃的氢氟烯烃。
6.根据权利要求1所述的用途,其特征在于所述气体为泡沫的电解槽气体(21)。
7.根据权利要求6所述的用途,其特征在于所述电解槽气体(21)为包含10至100体积%的式(I)的氢氟烯烃和0至50体积%的烷烃或环烷烃和0至50体积%CO2的混合物。
8.根据权利要求6所述的用途,其特征在于所述泡沫为选自以下的聚合物(22):聚氨酯(PU)、聚异氰脲酯(PIR)、热塑性聚酯(PET)和热塑性聚烯烃。
9.根据权利要求6或8所述的用途,其特征在于所述聚合物(22)或电解槽气体(21)的泡沫满足以下标准:
-PU含有50至100体积%的1233zd和0至50体积%的环戊烷;
-PU含有50至100体积%的1336mzz和0至50体积%的环戊烷;
-PIR含有50至100体积%的1233zd和0至50体积%的环戊烷;
-PIR含有50至100体积%的1336mzz和0至50体积%的环戊烷;
-PET含有50至100体积%的1233zd和0至50体积%的环戊烷;
-PET含有50至100体积%的1336mzz和0至50体积%的环戊烷;
-PE含有50至100体积%的1233zd和0至50体积%的环戊烷;和/或
-PE含有50至100体积%的1336mzz和0至50体积%的环戊烷。
10.根据权利要求1所述的用途,其特征在于所述聚合物层具有以下扩散系数:
-式(I)的氢氟烯烃小于5cm3/m2*天*巴;
-O2小于20cm3/m2*天*巴;
-N2小于5cm3/m2*天*巴;
-CO2大于0.5cm3/m2*天*巴;及
-气体H2O大于0.4cm3/m2*天*巴。
11.根据权利要求1所述的用途,其特征在于所述聚合物层(1)为复合物材料(10)的一部分或为自支撑结构元件。
12.根据权利要求11所述的用途,其特征在于所述复合物材料(10)具有以下分层结构:热塑性聚合物(3)、任选的附着力促进剂(2)、根据权利要求1作为屏障材料(1)的聚合物层、任选的附着力促进剂(2’)、任选的热塑性聚合物(3’)。
13.根据权利要求12所述的用途,其特征在于
所述热塑性聚合物(3、3’)选自高密度PE(HDPE)、低密度PE(LDPE)、线性低密度PE(LLDPE)并且层厚为0.01至1mm;和/或
所述附着力促进剂(2、2’)选自具有至少一种其它组分的PE接枝共聚物,并且层厚为0.01至1mm。
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- 2017-07-11 UA UAA201900529A patent/UA123456C2/uk unknown
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CH712779A1 (de) | 2018-01-31 |
KR102179314B1 (ko) | 2020-11-18 |
CN109312099A (zh) | 2019-02-05 |
CA3031240A1 (en) | 2018-01-25 |
EP3387052B1 (de) | 2019-05-15 |
UA123456C2 (uk) | 2021-04-07 |
JP2019524477A (ja) | 2019-09-05 |
CA3031240C (en) | 2020-11-17 |
EP3387052A1 (de) | 2018-10-17 |
DK3387052T5 (da) | 2020-09-14 |
WO2018015215A1 (de) | 2018-01-25 |
EA201990066A1 (ru) | 2019-05-31 |
JP6802293B2 (ja) | 2020-12-16 |
DK3387052T3 (da) | 2019-08-12 |
KR20190032360A (ko) | 2019-03-27 |
US20190338088A1 (en) | 2019-11-07 |
EA035521B9 (ru) | 2020-07-10 |
PL3387052T3 (pl) | 2019-11-29 |
EA035521B1 (ru) | 2020-06-29 |
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