CN103339315B - 经稳定的超高分子量聚烯烃纤维 - Google Patents
经稳定的超高分子量聚烯烃纤维 Download PDFInfo
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Abstract
本发明涉及一种涂有涂料组合物的超高分子量聚烯烃纤维,其中所述涂料组合物包含UV稳定剂,特征在于,基于固体计算相对于涂料组合物的总重,所述UV稳定剂的量为2wt%到80wt%。UV吸收剂可以选自由羟基二苯甲酮类、羟基苯基苯并三唑类、N,N′-二苯基乙二酰胺类、苯基酯类、苯并恶嗪酮类、氰基丙烯酸酯类、甲脒类、丙二酸亚苄酯类和羟基苯基三嗪类及其组合组成的组。所述纤维特别适用于绳索和渔网。
Description
本发明涉及一种高强度纤维,特别是具有改善的UV稳定性的超高分子量聚烯烃纤维,涉及高强度纤维的用途,例如绳索和渔网。
暴露于UV时,虽然一般认为高强度纤维,特别是超高分子量聚烯烃纤维,例如高性能聚乙烯(HPPE)纤维是相对稳定的,但在某些情况下,作为风化作用(weathering)的结果所述纤维可能会显示出韧度损失,这进而又可能导致使用寿命减少。当所述纤维用于绳索或钓鱼线或渔网时,特别可能发生这些状况。
在US5246988中,描述如何制备热稳定和氧化稳定的制品,其中含氮的抗氧化剂包含在载体(是一种润滑剂)中。这种热稳定和氧化稳定的涂层并不总是适合于改善稳定性或抗UV辐射性。此外,需要改进其中所用的涂料组合物。
US2010/007119描述了一种由氧化的聚丙烯腈构成的织物或纱线,其至少部分地涂有固化的硅聚合物树脂。所述硅聚合物树脂可以以硅聚合物重量的0.3-10份的量与UV稳定剂(例如二苯甲酮)共混。硅聚合物可以以原纱线或织物的约5wt%到200wt%的量涂覆到纱线或织物上。JP3249289还提供了对由超高分子量聚烯烃纤维制成且涂有热固性或热塑性树脂(可以含有UV吸收剂)的绳索的一般性公开。然而,据观察,US2010/007119或JP3249289的产品对UV辐照的稳定性仍可以优化。
改善聚合物纱线的UV稳定性的另一种方法是使用包含具有UV稳定性能的填料的纤维来代替使用涂有含UV稳定剂的涂料的纤维。例如JP5287680A中描述了这样的方法,其中公开了一种由包含与UV稳定剂共混的聚合物的组合物来纺制纤维的方法。然而,值得注意的是,通过该方法得到的纱线的UV稳定性仍可以进一步优化。
在第一个实施方式中,本发明提供了一种涂有涂料组合物的超高分子量聚烯烃纤维,其中所述涂料组合物包含UV稳定剂,特征在于,基于固体计算相对于涂料组合物的总重,UV稳定剂的量为2wt%到80wt%。优选地,UV稳定剂的所述量为至少5wt%,更优选至少10wt%,甚至更优选至少20wt%,最优选至少30wt%。优选地,UV稳定剂的所述量为至多75wt%,更优选至多70wt%,甚至更优选至多65wt%,最优选至多60wt.%。测量纤维被涂布之前和被涂布之后(如果必要的话,之后干燥)的重量,以计算优选干燥的涂料组合物的量或重量。优选地,相对于超高分子量聚烯烃纤维的总重、基于固体计算,涂料组合物的量为至少1wt%,更优选至少4wt%,最优选至少8wt%。优选地,涂料组合物的所述量为至多20wt%,更优选至多17wt%,最优选至多15wt%。在一个优选的实施方式中,提供了一种包含超高分子量聚烯烃纤维的绳索,其中相对于绳索的总重、基于固体计算,涂料组合物的量为1wt%到30wt%,更优选2wt%到15wt%。在进一步优选的实施方式中,提供了一种绳索,所述绳索包含本发明的被涂的超高分子量聚烯烃纤维,其中相对于绳索的总重、基于固体计算,涂料组合物的量为1wt%到30wt%,更优选2wt%到15wt%。
在第二个实施方式中,本发明提供了一种涂有涂料组合物的高强度纤维,其中所述涂料组合物包含UV吸收剂,特征在于,基于固体计算相对于涂料组合物的总重,UV吸收剂的量为至少10wt%。优选地,UV吸收剂的所述量为至少20wt%,最优选至少30wt%。优选地,UV吸收剂的所述量为至多80wt%,更优选至多70wt%,最优选至多60wt.%。优选地,相对于高强度纤维的总重、基于固体计算,涂料组合物的量为至少1wt%,更优选至少4wt%,最优选至少8wt%。优选地,涂料组合物的所述量为至多20wt%,更优选至多17wt%,最优选至多15wt%。在一个优选的实施方式中,提供了一种包含高强度纤维的绳索,其中相对于绳索的总重、基于固体计算,涂料组合物的量为1wt%到30wt%,更优选2wt%到15wt%。在一个优选的实施方式中,提供了一种包含高强度纤维的绳索,其中相对于绳索的总重、基于固体计算,涂料组合物的量为1wt%到30wt%,更优选2wt%到15wt%。在一个进一步优选的实施方式中,提供了一种绳索,所述绳索包含本发明的高强度纤维,其中相对于绳索的总重、基于固体计算,涂料组合物的量为1wt%到30wt%,更优选2wt%到15wt%。在一个优选的实施方式中,提供了一种包含高强度纤维的绳索,其中相对于绳索的总重、基于固体计算,涂料组合物的量为1wt%到30wt%,更优选2wt%到15wt%。
在纤维的涂层中使用UV吸收剂的好处在于,该稳定剂保护纤维免受UV光的影响,而对纤维的机械性能没有影响。最重要的是,观察到,本发明的纤维可以显示出对其机械性能(特别是其韧度)改善的保持。此外,所述吸收剂的使用没有以任何方式对纤维的制造工艺产生影响。对于本发明来说,术语“UV稳定剂”和“UV吸收剂”可互换使用。
在本发明的实施方式中,优选地,基于固体计算相对于涂料组合物(即,干燥的涂料组合物)的总重,UV稳定剂以2wt%到80wt.%的量存在。优选地,所述量为5wt%到60wt.%的稳定剂。
根据本发明所用的优选的UV稳定剂是这样的化合物,其能吸收UV辐射从而使UV辐射较少地影响制造纤维所用的聚合物。优选的稳定剂能吸收290到400nm范围内的UV。根据本发明的稳定剂可以是有机或无机吸收剂。
无机稳定剂的实例为炭黑、二氧化钛(TiO2)、ZnO和CeO2。
有机稳定剂的实例是落入羟基二苯甲酮类、羟基苯基苯并三唑类、N,N′-二苯基乙二酰胺(oxalanilide,草酰苯胺)类、苯基酯类、苯并恶嗪酮(benzooxazinone)类、氰基丙烯酸酯类、甲脒类、丙二酸亚苄酯类和羟基苯基三嗪类的那些。
例如在EP0697481A2、WO2006/082145、WO2009/060043和WO2007/08814中描述了适用于本发明的UV稳定剂的实例。
羟基二苯甲酮类化合物的更多实例为2-羟基-4-正辛氧基二苯甲酮;2-羟基-4-甲氧基二苯甲酮;2-羟基-4-正十二烷氧基二苯甲酮;2,4-二羟基二苯甲酮;2-丙烯酸2-(4-苯甲酰基-3-羟基苯氧基)乙酯;[2-羟基-4-(苯基甲氧基)苯基]甲酮;2,2′-二羟基-4-甲氧基二苯甲酮;2,2′,4,4′-四羟基二苯甲酮;2,2′-二羟基-4,4′-二甲氧基二苯甲酮;聚-4-(2-丙烯酰氧基乙氧基)-2-羟基二苯甲酮;双-(2-甲氧基-4-羟基-5-苯甲酰基-苯基)甲烷;[3-(2,4-二羟基苯甲酰基)苯基][2-羟基-4-(2-丙烯基氧基)苯基]甲酮;2,2-二羟基-4,4’-二甲氧基-二苯甲酮-5,5’-双-(磺酸钠);2-羟基-4-甲氧基-二苯甲酮-5-磺酸;[2-羟基-4-(2-羟基乙氧基)苯基]苯基甲酮;2,2’,4,4’-四羟基二苯甲酮与2,2’-二羟基-4,4’-二甲氧基二苯甲酮的混合物;1,4-双(4-苯甲酰基-3-羟基苯氧基)丁烷;2-丁烯酸2-(4-苯甲酰基-3-羟基苯氧基)-1-[(4-苯甲酰基-3-羟基苯氧基)甲基]乙酯。
羟基苯基苯并三唑类化合物的更多实例为2-(2’-羟基-3’,5’-二叔丁基-苯基)苯并三唑;2-(2′-羟基-3′-叔丁基-5′-甲基苯基)-5-氯苯并三唑;2-(5-氯-2H-苯并三唑-2-基)-4,6-双(1,1-二甲基乙基)苯酚;2-(2′-羟基-3,5′-二叔戊基苯基)苯并三唑;2-(2H-苯并三唑-2-基)-4-甲基苯酚;2-(2H-苯并三唑-2-基)-4-(1,1-二甲基乙基)苯酚;2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚;苯丙酸3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基-1,6-己二醇酯;双[2-羟基-5-叔辛基-3-(苯并三唑-2-基)苯基]甲烷;2-[2-羟基-3,5-二(1,1-二甲基苄基)苯基]2H-苯并三唑;2-[2-羟基-3-(3,4,5,6-四氢邻苯二甲酰亚氨甲基)-5-甲基苯基]苯并三唑;双[2-羟基-5-甲基-3-(苯并三唑-2-基)苯基]甲烷;2(2’-羟基-5-甲基丙烯酰氧基乙基苯基)2H-苯并三唑;2-(2H-苯并三唑-2-基)-4-(1,1-二甲基乙基)-6-(2-甲基丙基)苯酚;2-(2H-苯并三唑-2-基)对甲酚与十二烷烷基化的异构体混合物;α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基-4-羟基苯基]-1-氧代丙基]-ω-羟基聚(氧-1,2-亚乙基);α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基苯基1]-1-氧代丙基]-ω-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基苯基]-1-氧代丙基]]聚(氧-1,2-亚乙基);苯丙酸3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基-C7-9-支化和线性的烷基酯;2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)4-(1,1,3,3-四甲基丁基)苯酚;2-(2’-羟基-5’-(2-羟基乙基))-苯并三唑;2-(2-羟基-4-辛基氧基苯基)-2H-苯并三唑;苯并三唑基丁苯酚磺酸钠;3-[3-叔丁基-4-羟基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸辛酯;3-[3-叔丁基-4-羟基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸2-乙基己基酯;2-(2H-苯并三唑-2-基)-6-[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]甲基]-4-(1,1,3,3-四甲基丁基)苯酚。
N,N′-二苯基乙二酰胺类化合物的更多实例为2-乙氧基-5-叔丁基-2’-乙基-N,N′-二苯基乙二酰胺;2-乙基-2′-乙氧基-N,N′-二苯基乙二酰胺;N-(2-乙氧基-苯基)-N’-(4-异十二烷基-苯基)-N,N′-二苯基乙二酰胺。
苯基酯类化合物的更多实例为4-叔丁基-苯基水杨酸酯;3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯;苯甲酸2-羟基苯基酯。
苯并恶嗪酮类化合物的更多实例为2.2′-(1,4-亚苯基)双[4H-3,1-苯并恶嗪-4-酮。
氰基丙烯酸酯类化合物的更多实例为2-氰基-3,3-二苯基丙烯酸乙酯;2-氰基-3,3-二苯基丙烯酸2-乙基己酯;1,3-双[2’-氰基-3’,3-二苯基丙烯酰基)氧]-2,2-双{[2-氰基-3’,3’-二苯基丙烯酰基)氧]甲基}丙烷。
更多的实例包括N-(对-乙氧基-羰基苯基)-N’-甲基-N’-苯基甲脒;N-(对-乙氧基-羰基苯基)-N′-乙基-N′-苯基甲脒和2-丙烯酸3-(4-甲氧基苯基)-2-乙基己酯;丙二酸[(4-甲氧基苯基)-亚甲基]-二甲酯;2,2’-(1,4-亚苯基-二亚甲基)-双丙二酸四乙酯。
羟基苯基三嗪类化合物的实例为2-[4,6-二苯基-1,3,5-三嗪-2-基]-5-(己基)氧-苯酚;丙酸2-[4-[4,6-双([1,1′-二苯基]-4-基)-1,3,5-三嗪-2-基]-3-羟基苯氧基]异辛酯;2-[4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛基氧)-苯酚;2-[4-[(2-羟基-3-(2’-乙基)己基)氧]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;2-[4-[(2-羟基-3-十二烷基氧基丙基)氧]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;2-[4-[(2-羟基-3-十三烷基氧基丙基)氧]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪;2,4-双[2-羟基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三嗪;5,5′-双(2-乙基己基氧)-2,2′-[6-(4-甲氧基苯基)-1,3,5-三嗪-2,4-二基]二苯酚;丙酸2,2′,2″-[1,3,5-三嗪-2,4,6-三基三[(3-羟基-4,1-亚苯基)氧]]三-1,1′,1″-三辛酯。
最优选的化合物式具有下面所示结构的那些:
根据本发明一个优选的方面,含有UV吸收剂的涂料组合物还包含载体。
载体可以是用于超高分子量聚烯烃纤维或高强度纤维的任何已知的涂层,例如蜡、聚丙烯酸酯涂层、聚氨酯涂层或硅酮涂层。
优选地,根据本发明所用的涂料组合物包含硅聚合物(更优选交联的硅酮聚合物)作为UV稳定剂的载体。
特别地,本发明提供了一种如上所述的超高分子量聚烯烃纤维或高强度纤维,其中所述涂层包含交联的硅酮聚合物作为UV稳定剂的载体。
例如在未公开的专利申请PCT/EP2010/060813(通过引用结合到本文)描述了所述涂层。
在本发明中,超高分子量聚烯烃纤维或高强度纤维上的涂层优选地通过涂布包含可交联硅酮聚合物的涂料组合物获得。将涂料组合物涂覆到纤维上之后,涂料组合物可以通过例如加热使可交联的硅酮聚合物交联而固化。交联也可以通过本领域技术人员已知的任意合适的方法引发。用于固化涂料组合物的温度为20到200℃,优选为50到170℃,更优选为120到150℃。为了有效固化,固化温度不应过低。固化温度也不应过高,否则使超高分子量聚烯烃纤维或高强度纤维存在强度劣化并损失强度的风险。
测量纤维被在涂布之前和涂布固化之后的重量,以计算交联涂层的重量。对于纤维来说,基于纤维的总重,交联涂层的重量优选占1到20wt.%,优选占1到10wt.%。对于绳索来说,优选地,基于绳索和涂层的总重,交联涂层的重量占1到30wt.%,优选占2到15wt.%。
可以控制交联度。交联度可以通过例如温度或加热的时间来控制。如果以其他方式进行交联,可以通过本领域技术人员已知的方法来控制交联度。可以按照下列方法进行交联度的测量:
将(至少部分)具有交联涂层的纤维浸入溶剂中。选择溶剂,使得聚合物中未交联的可提取基团(主要是单体)溶解而交联网络不溶解。优选的溶剂是己烷。通过称量浸入所述溶液之后绳索或纤维的重量,可以确定未交联部分的重量,并且可以计算交联硅酮与可提取物的比例。
优选地,交联度为至少30%。即,基于涂层的总重,用溶剂提取之后至少30%的涂层留在纤维或绳索上。更优选地,交联度为至少50%。最大的交联度为约100%。
优选地,可交联的硅酮聚合物包括具有反应性端基的硅酮聚合物。已发现,在硅酮聚合物端基的交联产生良好的抗弯曲性。在端基交联而不是在重复单元的分支上交联的硅酮聚合物产生刚性较小的涂层。不想受限于此,本发明人将绳索改善的性能归功于涂层的刚性较小的结构。
优选地,可交联的端基是烯化端基,更优选C2-C6烯化端基。特别地,所述端基是乙烯基或己烯基,乙烯基是优选的。
优选地,可交联的硅酮聚合物具有下式:
CH2=CH-(Si(CH3)2-O)n-CH=CH2 (1)
其中,n为2到200的数,优选10到100,更优选20到50。
优选地,涂料组合物还包含交联剂。该交联剂优选地具有下式:
Si(CH3)3-O-(SiCH3H-O)m-Si(CH3)3 (2)
其中,m为2到200的数,优选10到100,更优选20到50。
优选地,涂料组合物还包含用于使可交联的硅酮聚合物交联的金属催化剂,所述金属催化剂优选铂、钯或铑,更优选为铂金属络合物催化剂。这些催化剂是本领域技术人员已知的。
优选地,涂料组合物是多组分硅酮体系,其包含:含有可交联硅酮聚合物和交联剂的第一乳液、以及含有可交联硅酮聚合物和金属催化剂的第二乳液。
优选地,第一乳液与第二乳液的重量比为约100∶1到约100∶30,优选100∶5到100∶20,更优选100∶7到100∶15。
上述涂料组合物是本领域已知的。它们通常被称之为加成固化的硅酮涂料或涂料乳液。当乙烯基端基与交联剂的SiH基团反应时,发生交联或固化。
这样的涂料的实例为来自Wacker Silicones的430(交联剂)和440(催化剂);来自Bluestar Silicones的Emulsion 催化剂913;以及来自Dow Coming的7950Emulsion Coating和7922Catalyst Emulsion。
本发明的UV稳定剂可以在交联之前包含在载体组合物中。
在本发明的上下文中,“纤维”被理解为长度不确定的细长体,它们的长度尺寸远远大于宽度和厚度。在一个实施方式中,术语“纤维”包括选自由下列物体组成的组中的物体:单丝、多丝纱线、丝带、条带或带。纤维可以具有规则或不规则的横截面。术语“纤维”还包括上述任意一种的多个或组合。
因此,根据本发明的涂料可以涂覆到单根纤维或纱线上,也可以涂覆到不止一根纤维的束(亦被称为纱线)上。
具有单丝形式的纤维或带状纤维可以具有不同纤度,但纤度通常在10到几千dtex的范围内,优选在100到2500dtex的范围内,更优选在200-2000dtex的范围内。多丝纱线包含多根纤度通常在0.2-25dtex范围内的丝,优选约0.5-20dtex线。多丝纱线的纤度也可以差别很大,例如50到几千dtex,但优选在约200-4000dtex的范围内,更优选在300-3000dtex的范围内。
用于本发明的高强度纤维表示韧度为至少1.5N/tex,更优选至少2.0N/tex、甚至更优选至少2.5N/tex、最优选至少3.0N/tex的纤维。在超高分子量聚烯烃纤维的情况下,所述纤维的韧度优选地为至少2.0N/tex,更优选至少2.5N/tex,最优选至少3.0N/tex。通过基于ASTM D2256-97的已知方法来测定丝线的拉伸强度(亦简称为“强度”)或韧度。通常,所述高强度聚合物丝线或超高分子量聚烯烃纤维也具有高拉伸模量,例如至少50N/tex,优选至少75、100或甚至至少125N/tex。
高强度纤维的实例是由聚芳酰胺制成的纤维,诸如聚(对亚苯基对苯二甲酰胺)(例如聚(四氟乙烯)(PTFE);芳族共聚酰胺(对苯二胺/3,4’-二苯醚撑对苯二甲酰共聚物(亦称为聚{2,6-二咪唑并-[4,5b-4’,5’e]吡啶-1,4(2,5-二羟基)苯撑}(亦称为M5);聚(对-苯撑-2,6-苯并二噁唑)(PBO)(亦称为热致液晶聚合物(LCP),如从例如US4384016中已知的;还有聚烯烃,例如聚乙烯或聚丙烯,如聚乙烯或聚丙烯的均聚物和共聚物。由上述聚合物制成的纤维的组合也可以用在本发明的绳索中。优选的高强度纤维是是聚乙烯、聚芳酰胺或LCP的纤维。
超高分子量聚烯烃纤维的优选的实例是超高分子量聚乙烯纤维。
最优选的纤维是高性能聚乙烯(HPPE)纤维。HPPE纤维在本文中被理解为由超高摩尔质量聚乙烯(亦被称为超高分子量聚乙烯;UHMWPE)制成的纤维,韧度为至少1.5N/tex,优选至少2.0N/tex,更优选至少2.5N/tex或甚至至少3.0N/tex。HPPE纤维的韧度不必设上限,原因是韧度为约5或6N/tex的HPPE纤维也是可用的。HPPE纤维还具有高拉伸模量,例如至少75N/tex,优选至少100N/tex或至少125N/tex。HPPE纤维也被称为高模量聚乙烯纤维。
在一个优选的实施方式中,本发明中的HPPE纤维是一根或多根多丝纱线。
HPPE纤维、丝线或多丝纱线可以通过下列方法制备:将UHMWPE在适当溶剂中的溶液纺成凝胶纤维,并在部分或完全除去溶剂之前、期间和/或之后拉伸所述纤维;即,通过所谓的凝胶纺丝工艺。UHMWPE溶液的凝胶纺丝是本领域技术人员熟知的,在多个出版物中有所描述,包括EP0205960A、EP0213208A1、US4413110、GP2042414A、EP0200547B1、EP0472114B1、WO01/73173A1和“Advanced Fibre SpinningTechnology”,Ed.T.Nakajima,Woodhead Publ.Ltd(1994),ISBN1-855-73182-7,以及它们所引用的参考文献,所有这些通过引用结合于本文。
HPPE纤维、丝线或多丝纱线也可以通过UHMWPE的熔融纺丝来制备,尽管与通过凝胶纺丝工艺制备的HPPE纤维相比,机械性能(例如韧度)更有限。可以熔融纺丝的UHMWPE的分子量的上限低于通过凝胶纺丝的UHMWPE的分子量的上限。熔融纺丝工艺在本领域是众所周知的,包括下列步骤:加热PE组合物以形成PE熔体,挤出PE熔体,冷却所挤出的熔体得到固化的PE,拉伸所述固化的PE至少一次。该工艺在例如EP0344860A1和EP173659A1中提到,它们都通过引用结合于本文。
UHMWPE被理解为特性粘度(IV,在135℃下在十氢化萘溶液中测量)为至少5dl/g、优选为约8到40dl/g的聚乙烯。特性粘度是摩尔质量(也称为分子量)的量度,它比例如Mn和Mw的实际摩尔质量参数更易确定。IV和Mw之间存在一些经验关系,但这些关系高度依赖于摩尔质量的分布。基于方程Mw=5.37*104[IV]1.37(参见EP0504954A1),8的IV相当于约930Kg/mol的Mw。优选地,UHMWPE是每100个C原子具有小于1个侧链、更优选每300个C原子具有小于1个侧链的线性聚乙烯;分支或侧链或链分支通常包含至少10个碳原子。线性聚乙烯也可以进一步包含至多5mol%的一种或更多种共聚单体,如烯烃,例如丙烯、丁烯、戊烯、4-甲基戊烯或辛烯。
在一个实施方式中,UHMWPE包含少量(优选每1000个碳原子至少0.2或至少0.3个)相对小的基团作为悬挂的侧基,优选C1-C4烷基。这样的纤维显示出高强度和抗蠕变性的有利组合。然而,侧基过大或侧基数量过多,将对制备纤维的过程产生不利的影响。为此,UHMWPE优选地包含甲基或乙基侧基,更优选甲基侧基。优选地,侧基的量为每1000个碳原子至多20个、更优选至多10个、5个或至多3个。
根据本发明的HPPE可以进一步包含少量(通常小于5质量%,优选小于3质量%)的常用添加剂,例如抗氧化剂、热稳定剂、着色剂、流动促进剂等。UHMWPE可以是单的聚合物等级,但也可以是两种或更多种聚乙烯等级的混合物,例如IV或摩尔质量分布不同,和/或类型及共聚单体的数量或侧基不同。
本发明的超高分子量聚烯烃纤维或高强度纤维可以在通常应用所述纤维的任意领域使用。特别地,本发明的纤维可以用于绳索、钓鱼线和渔网。
尽管本发明中描述了具有涂层的纤维,根据另一个实施方式,涂层也可以涂覆到含有所述纤维的制品上,例如绳索或渔网。因此,本发明还涉及一种涂有涂料组合物的制品,优选绳索或渔网,其中所述涂料组合物包含UV吸收剂。UV吸收剂和涂料组合物的优选的实施方式如上所述。
制备绳索或渔网的方法是本领域技术人员已知的。
通过下面的实施例进一步说明本发明。
分析方法
耐候性
根据ISO4982-2在最长120天的时间内针对其未经处理的参比纱线对样品进行UV测试。测定直到韧度降低50%的时间。
机械性能
根据ASTM D2256在Zwick1435上测定拉伸性能。
实施例
用包含与交联剂预先配制的反应性硅酮聚合物的第一乳液和包含硅酮聚合物与金属催化剂的第二乳液制备涂料组合物。第一乳液是来自DowComing的乳液7950Emulsion Coating),其包含30.0-60.0wt%的二甲基乙烯基封端的二甲基硅氧烷和1.0-5.0wt%的二甲基,甲基氢硅氧烷。第二乳液是来自Dow Coming的乳液7922CatalystEmulsion),其包含30.0-60.0wt%的二甲基乙烯基封端的二甲基硅氧烷和铂催化剂。第一乳液和第二乳液以8.3∶1的重量比混合。
第三溶液由水和UV稳定剂制成,或者如果UV稳定剂本身是水基溶液,其可以原样使用。用第三溶液将第一乳液和第二乳液的混合物稀释至预定的固含量(参加表1)。通过调整第三溶液的加入量可以确定UV稳定剂的量。
在室温下,将购自荷兰DSM的HPPE纤维(1760dtex)浸入涂料组合物中。在温度为120℃的烘箱中加热纤维,从而发生交联。
表1
*从Ciba Inc.得到
从上面的实施例中可以看出,稳定剂的加入显著改善纤维暴露于UV辐射时韧度降低的时间。
Claims (14)
1.一种涂有涂料组合物的超高分子量聚烯烃纤维,其中所述涂料组合物包含紫外稳定剂,特征在于,基于固体计算相对于涂料组合物的总重,所述紫外稳定剂的量为2wt%到80wt%,并且其中所述涂料组合物包含交联的硅酮聚合物作为所述紫外稳定剂的载体。
2.根据权利要求1的纤维,其中,所述紫外稳定剂能吸收290到400nm范围内的紫外辐射。
3.根据权利要求1的纤维,其中,所述紫外稳定剂选自由羟基二苯甲酮类、羟基苯基苯并三唑类、N,N'-二苯基乙二酰胺类、苯基酯类、苯并恶嗪酮类、氰基丙烯酸酯类、甲脒类、丙二酸亚苄酯类和羟基苯基三嗪类或其组合组成的组。
4.根据权利要求3的纤维,其中,所述紫外稳定剂是具有下式的化合物:
5.根据权利要求1的纤维,其由超高分子量聚乙烯(UHMWPE)制成,其在135℃下在十氢化萘中测定的特性粘度为至少5dl/g。
6.根据权利要求1的纤维,其中,所述交联硅酮聚合物的交联度为至少20%。
7.根据权利要求1的纤维,其中,包含所述交联硅酮聚合物的涂层通过下列步骤得到:将包含可交联的硅酮聚合物的涂料组合物涂覆到所述纤维;并且使所述可交联的硅酮聚合物交联。
8.根据权利要求7的纤维,其中,所述可交联的硅酮聚合物包括具有可交联端基的硅酮聚合物。
9.根据权利要求8的纤维,其中所述可交联的硅酮聚合物具有下式:
CH2=CH-(Si(CH3)2-O)n-CH=CH2 (1)
其中,n为2到200的数。
10.根据权利要求7的纤维,其中所述涂料组合物还包含具有下式的交联剂:
Si(CH3)3-O-(SiCH3H-O)m-Si(CH3)3 (2)
其中,m为2到200的数。
11.根据权利要求7的纤维,其中,所述涂料组合物还包含铂催化剂。
12.根据权利要求1至11中任意一项的纤维用于制备绳索或渔网的用途。
13.一种包含权利要求1至11中任意一项的纤维的制品。
14.根据权利要求13的制品,其中所述制品为绳索或渔网。
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EP11152724A EP2481847A1 (en) | 2011-01-31 | 2011-01-31 | UV-Stabilized high strength fiber |
EP11152724.8 | 2011-01-31 | ||
PCT/EP2012/051560 WO2012104302A1 (en) | 2011-01-31 | 2012-01-31 | Stabilized ultra high molecular weight polyolefin fiber |
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US (1) | US20140023863A1 (zh) |
EP (2) | EP2481847A1 (zh) |
KR (1) | KR101925790B1 (zh) |
CN (1) | CN103339315B (zh) |
AU (1) | AU2012213480B2 (zh) |
BR (1) | BR112013019527A2 (zh) |
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CA2865228A1 (en) * | 2012-03-20 | 2013-09-26 | Dsm Ip Assets B.V. | Polyolefin fiber |
ES2699984T3 (es) * | 2013-05-23 | 2019-02-13 | Dsm Ip Assets Bv | Fibra de UHMWPE |
NO20141103A1 (no) * | 2014-09-12 | 2016-03-14 | Offshore & Trawl Supply As | Strømlinjebekledning i beskyttelseskappe for et langstrakt, lastbærende legeme |
NO337236B1 (en) * | 2015-01-15 | 2016-02-22 | Calorflex As | A mooring member |
EP3259388A1 (en) * | 2015-02-20 | 2017-12-27 | Dow Global Technologies LLC | Carbon fibers obtained from silicon treated polyolefin precursor fibers |
KR20180067569A (ko) * | 2015-10-09 | 2018-06-20 | 디에스엠 아이피 어셋츠 비.브이. | 복합성 긴 몸체 |
JP6256669B1 (ja) | 2016-03-18 | 2018-01-10 | 株式会社村田製作所 | 金属製多孔膜、それを用いた分級方法、および分級装置 |
US20180037726A1 (en) * | 2016-08-04 | 2018-02-08 | Veerag Mehta | Ultra highmolecular weight polyethylene compositions |
CN108914595A (zh) * | 2018-04-11 | 2018-11-30 | 巢湖市瀚海渔具有限公司 | 一种高强度复合渔网丝的制备方法 |
TWI754918B (zh) * | 2020-04-20 | 2022-02-11 | 財團法人紡織產業綜合研究所 | 光變色聚丙烯纖維及其製備方法 |
CN112941935A (zh) * | 2021-02-05 | 2021-06-11 | 常州科旭纺织有限公司 | 一种带颜色的含hppe纤维的纱线及其染色方法 |
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- 2012-01-31 US US13/981,434 patent/US20140023863A1/en not_active Abandoned
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WO2012104302A1 (en) | 2012-08-09 |
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