CN112739858A - 可生物降解的纺织品、母料和制造可生物降解的纤维的方法 - Google Patents
可生物降解的纺织品、母料和制造可生物降解的纤维的方法 Download PDFInfo
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- CN112739858A CN112739858A CN201980042514.4A CN201980042514A CN112739858A CN 112739858 A CN112739858 A CN 112739858A CN 201980042514 A CN201980042514 A CN 201980042514A CN 112739858 A CN112739858 A CN 112739858A
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Abstract
公开了一种母料和相关方法,以及可生物降解的长丝、纤维、纱线和织物。母料包括0.2至5质量%的CaCO3;脂肪族聚酯,其具有在酯基团之间的链中具有二至六个碳的重复单元,条件是链中的2至6个碳不包括侧链碳;以及载体聚合物,其选自由以下组成的群组:PET、尼龙、其他热塑性聚合物及其组合。
Description
技术领域
本发明涉及适合于纺织品的聚合物组合物,与最常见的聚合物相比,该聚合物组合物在合理有益的短时间跨度内也是可生物降解的。
背景技术
纺织品是人类文化的基础,并且已经由人类制造和使用了数千年。最早的纺织品由并将继续由诸如亚麻、羊毛、丝绸和棉花等天然纤维编织而成。最近,工业上,也已经采用聚合物诸如聚酯、尼龙烯烃、其他热塑性聚合物及其组合来生产纺织品纤维、纱线和织物。许多现代聚合物可以制成几乎无穷无尽的各种形状和产品,这些形状和产品具有吸引力、耐用性和防水性。在许多情况下,这些合成纤维或纱线(取决于所需的技术和最终产品)可以与天然纤维混合,以获得具有天然材料和合成材料的所需特征的最终产品。
虽然耐久性和耐水性是期望的,但这些性能可能导致二次环境问题。由聚合物纤维制成的纺织品不能像天然纤维(诸如棉和羊毛)一样自然地生物降解,并且可能在垃圾填埋场和水(例如,湖泊、海洋)中保留数百年或更长时间。根据美国环境保护署,每天有近4400万磅的合成(聚合物)纺织品运往垃圾填埋场。此外,在衣物洗涤循环期间,从衣服释放的大部分微纤维被废水处理厂的污泥捕获。污泥最终变成生物固体,被送往垃圾填埋场或用作肥料。然后,这些聚合物微纤维在土壤或其他地面环境中堆积,并且甚至可能变成可移动的,最终从陆地环境进入水生环境。根据一些估计,每年约有50万吨因洗涤纺织品而产生的塑料微纤维被释放到海洋中。某些高表面积的微纤维可以吸收大量的毒素负载量,并且类似于微型浮游生物,从而使食物链中积累的生物提高了若干个数量级。反过来,因为人类通常消费顶级捕食物种,这样的微纤维污染可能会对人类健康造成不利影响。
作为附加问题,诸如地毯和室内装潢(住宅和商业)等物品相对于服装而言体积较大,并且通常合并有较大的、较膨松的纱线,因此可能占据大量的填埋空间。
在非织造环境中,现在无处不在的所有类型的“擦拭布”(通常为非织造片材或几层片材)同样占据很大的空间,甚至当被认为是“可冲洗的”时,也可能会堵塞市政污水***,而这对于越来越多地使用的小体积、低流量的马桶来说更是问题。
鉴于这些环境问题,生物可降解的聚合物的产生一直是学术界和工业界十分关注的主题。这些包括以下示例,这些示例是代表性的而非全面性的。
Shah等人在“Microbial degradation of aliphatic and aliphatic-aromaticcopolyesters,”Appl.Microbiol.Biotechnol(2014)98:3437-3447中已经回顾了关于聚酯的降解的文献,并且指出“大多数可生物降解的塑料是具有潜在可水解酯键的聚酯,并且这些易于被解聚酶水解”,并且与芳族酯相比,脂肪族聚酯由于其柔性聚合物链而容易降解。一些聚酯(诸如PET)是不可生物降解的,当该术语用于本文所述的发明中。
许多专利已经描述了可生物降解的聚合物组合物。例如,在Rhodia Poliamida的WO2016/079724中,对聚酰胺组合物进行改性以便生产可生物降解的聚酰胺纤维。在该专利中,生物降解速率是根据ASTMD5511测试标准测量的。在第8-9页,讨论了生物降解的现有技术方法,包括:光降解、降解助剂添加剂诸如过渡金属盐,和快速降解留下具有高界面面积和低结构强度的多孔结构的生物降解聚合物;这些可生物降解的聚合物10列出为包括淀粉基聚合物、聚乳酸、聚己内酯、聚丁二酸丁二醇酯、聚对苯二甲酸丁二醇酯-共-己二酸酯和若干种其他聚合物;然而,该专利申请声明“不幸的是,需要更高的量来使聚合物可生物降解,还需要相容和增塑添加剂”。作为示例性的生物降解剂,该专利参考了Lake等人的美国公开专利申请第2008/010323215号。生物降解剂有利地是包括至少六种添加剂的母料:(1)化学引诱剂或化学趋化性化合物;(2)戊二酸;(3)链长为5-18个碳的羧酸;(4)可生物降解的聚合物;(5)载体树脂;以及(6)溶胀剂。本发明的示例使用2%的市售生物降解剂的母料,通过熔融纺丝来制备聚酰胺纤维。通过ASTMD5511标准测试所得的纤维,发现,在300天后降解了13.9%或15.5%。在相同的ASTMD5511测试下,不含生物降解剂的纤维降解了2.2%和2.3%。
LaPray等人在US 2018/0100060中生产了可生物降解的制品,诸如膜、袋子、瓶子、盖子、片材、盒子或其他容器、板等,其由聚合物与基于碳水化合物的聚合物的共混物制成。生物降解性根据既定的标准诸如ASTM D-5511和ASTM D-6691(模拟海洋条件))进行测试。
Tokiwa等人描述了包含可生物降解的树脂和甘露聚糖(多糖)消化产物的可生物降解树脂组合物。Tokiwa等人列出了可生物降解的甘露聚糖消化产品,包括各种甘露寡糖。
Bastioli等人在美国专利第308,466,237号中描述了一种可生物降解的脂肪族-芳香族共聚酯,其由51至37%的脂肪族酸和49-63%的芳香族羧酸制成,所述脂肪族酸包含至少50%的巴西基酸(1,11-十一碳二羧酸)。可生物降解的聚合物可以通过添加淀粉或聚丁二酸丁二醇酯并与乳酸或聚己内酯共聚来另外改性。
Lake等人在美国专利第9,382,416号中描述了一种用于聚合物材料的可生物降解的添加剂,其包含化学引诱化合物、戊二酸、5羧酸和溶胀剂。呋喃酮化合物被认为是细菌的引诱剂。
Wnuk等人在美国专利第5,939,467号中描述了一种可生物降解的聚羟基烷酸酯聚合物,其含有第二可生物降解的聚合物,诸如聚己内酯,以及流延和吹塑膜的示例。
已知有多种可生物降解的制剂,但通常不属于纺织品领域,不能解决可洗涤性的问题,其中一些可以利用碳酸钙。例如,Yoshikawa等人在美国公开专利申请第2013/0288322号中,Jeong等人在WO2005/017015中,Tashiro等人在美国专利9,617,462中,以及Whitehouse在美国专利申请2007/0259584中。
尽管进行了大量努力,但仍然需要新的方法和材料来提供耐用、防水,且在废水处理厌氧消化器、垃圾填埋条件和海洋环境中降解的合成纺织品。因此,制造合成纺织品将是有益的,所述合成纺织品保持其期望的性能,且在废水处理期间、在厌氧消化器中、在垃圾填埋条件下和在海洋环境中比常规的合成纺织品材料更快速地降解。
发明内容
在一个方面中,本发明提供了一种母料,包含:0.2至5质量%的CaCO3;脂肪族聚酯,其包含在酯基团之间的链中具有二至六个碳的重复单元,其中2至6个碳的链重复单元不包括侧链碳;以及载体聚合物,其包含PET、尼龙、烯烃、其他热塑性聚合物及其组合。链重复单元中的2至6个碳不包括酯(COOR)部分中的碳,并且如果存在侧链碳,则在重复基团中可以存在多于6个碳(加上酯碳)。
在任何本发明方面的一些优选的实施例中,脂肪族聚酯包含在酯基团之间的链中具有三至六个碳或2至4个碳的重复单元。在特别优选的实施例中,脂肪族聚酯包含聚己内酯。在一些优选的实施例中,母料进一步包含聚丁二酸丁二醇酯(PBS)、聚丁二酸丁二醇酯己二酸酯(PBSA)、聚乳酸(PLA)、聚醚砜(PES)、聚羟基丁酸酯(PHB)、聚(3-羟基丁酸酯-共-3-羟基戊酸酯)(PHBV)、聚己二酸丁二醇酯对苯二甲酸酯(PBAT)、聚丁二酸丁二醇酯己二酸酯(PBSA)、聚(丁二酸丁二醇酯-共-对苯二甲酸酯)(PBST)、聚(丁二酸丁二醇酯/对苯二甲酸酯/间苯二甲酸酯)-共-(乳酸酯)PBSTIL及其组合。
优选地,母料(和纺织品)基本上不含糖类。
在另一个方面中,本发明提供了一种熔融的中间体,包含:除PET之外的脂肪族聚酯,其包含在酯基团之间的链中具有二至六个碳的重复单元,其中2至6个碳的链重复单元不包括侧链碳;0.01至0.2质量%的CaCO3;以及至少90质量%的PET、尼龙、烯烃、其他热塑性聚合物及其组合。如本文中所使用的,短语“除PET之外”可以表示为“除聚对苯二甲酸乙二醇酯之外”,或“条件是脂肪族聚酯不是聚对苯二甲酸乙二醇酯”。
在进一步的方面中,本发明提供了一种纤维,包含:除PET之外的脂肪族聚酯,其包含在酯基团之间的链中具有二至六个碳的重复单元,其中2至6个碳的链重复单元不包括侧链碳;0.01至0.2质量%的CaCO3;以及至少90质量%的PET、尼龙、烯烃、其他热塑性聚合物及其组合。
在各种实施例中,纺织品可以具有以下性质中的一种或任意组合:生物降解性,使得当经受ASTMD5511的条件持续266天时,纺织品分解至少40%,或至少50%,或在40%至约80%的范围内,或在40%至约75%的范围内;其中来自ASTM测试的分解产物主要是甲烷和二氧化碳;尺寸稳定性,使得纺织品在经受家庭式洗涤测试AATCC135-2015 1IIAii(80°F机洗,滚筒干燥,五个洗涤循环)的条件时,保持其形状,且收缩小于10%,或小于5%,或小于3%;其中所述纺织品是有色的,并且当经受AATCC 61-20132A(mod 105℉)或AATCC 8-2016或AATCC 16.3-2014(选项3,20AFU)的条件时,具有至少等级3,或至少等级4,或等级5的色牢度;当经受ASTM D3786/D3886M-13的条件时,至少20psi,优选地至少50psi,或至少100psi,或在50至约200psi的范围内,或50至约150psi的胀破强力;以及芯吸能力,使得当经受AATCC 197-2013的条件时,选项B,纺织品在2分钟内将水芯吸出至少10mm或至少20mm的距离,或者在约10mm或约20mm至约150mm的范围内。
在又一个方面中,本发明提供了一种制造纤维、纱线或织物的方法,包含:将本文所述的母料混合到包含PET、尼龙、烯烃、其他热塑性聚合物及其组合的聚合物中,以形成熔融的混合物;挤出混合物以形成长丝;以及冷却长丝。这些长丝可以被纺织和针织(“长丝纱线”),形成为非织造纤维网,或切割成用于织造、非织造和针织织物应用的短纤维。可替代地,熔融的混合物可以被挤出以形成粒料,并且粒料可以随后在挤出混合物以形成纤维的步骤之前被再熔融。在进一步的方面中,本发明提供了一种纺织品,包含:纤维,所述纤维包含CaCO3和至少90质量%的PET、尼龙、烯烃、其他热塑性聚合物及其组合,并且具有生物降解性,使得当经受ASTM D5511的条件持续266天时,纺织品分解至少40%,或至少50%,或在40%至约80%的范围内,或在40%至约75%的范围内;并且其中所述纺织品包含以下性质中的一种或多种:尺寸稳定性,使得当经受家庭式洗涤测试5AATCC 135-2015 1IIAii(80F机洗,滚筒干燥,五个洗涤循环)的条件时,所述纺织品保持其形状并且收缩小于10%,或小于5%,或小于3%;其中所述纺织品是有色的,并且当经受AATCC 61-2013 2A(mod 105F)或AATCC 8-2016或AATCC 16.3-2014(选项3,20AFU)的条件时,具有至少等级3,或至少等级4,或等级5的色牢度;当经受ASTM D3786/D3886M-13的条件时,至少20psi,优选地至少50psi,或至少100psi,或在50至约200psi的范围内,或50至约150psi的胀破强力;以及芯吸能力,使得当经受AATCC 197-2013,选项B的条件时,纺织品在2分钟内芯吸水超过至少10mm或至少20mm的距离,或在约10或约20mm至约150mm的范围内。
在一些优选的实施例中,本发明的优点可以包括每质量%母料的增强的生物降解性;与其他生物降解性处理相比,纤维或纺织品的更高的耐久性;更好地保持纤维或纺织品的性能。
基于以下结合附图的详细描述,本发明的前述和其他目的和优点以及实现这些目的和优点的方式将变得更加清楚。
附图说明
图1-5是本发明的若干个实施例以及纤维素材料和常规聚合物的对照实例的生物降解百分比(%)相对于经过时间(以天表示)的曲线图。
图6是根据本发明的部分消化的纤维的SEM显微照片。
图7是示出了本发明的植物测试的一系列照片。
具体实施方式
词汇表
“脂肪族聚酯”含有重复酯单元,其中烃链包含开放(非芳族)链。这些可以是均聚物、仅含脂肪族基团的共聚物或包含脂肪族基团和芳基基团的共聚物。
“载体聚合物”是母料中的聚合物,它与母料被掺入其中的聚合物相同或相容且可混溶。
旦尼尔(Dpi)是9,000米单独的长丝的克重。可以通过取纱线旦尼尔数且将其除以纱线束中的长丝数来计算。
为了本发明的目的,不可生物降解的聚合物是在根据ASTM D-5511测试266天后降解10%或更少的聚合物。
PET、尼龙和斯潘德克斯弹性纤维(Spandex)具有常规含义。尼龙是聚酰胺;一种优选的尼龙是尼龙6,6。斯潘德克斯弹性纤维是一种聚醚-聚脲共聚物。
聚合物是包含许多重复单元的大分子(分子量超过100道尔顿,通常为数千道尔顿)。
纺织品是一种由天然和/或合成5纤维、长丝或纱线组成的材料,并且可以是针织、机织或非织造形式。
术语“非织造织物”是本领域普通技术人员所熟知的,并且本文中与这种理解一致地使用,包括诸如在Tortora,Phyllis G.,and Robert S.Merkel.Fairchild'sDictionary of Textiles.7th ed.New York,NY:Fairchild Publications,2009,page387中那些的定义。
因此,非织造织物是“通过纤维的粘合或互锁,或两者而产生;通过机械、化学、热或溶剂手段及其组合而实现的纺织品结构”。形成基础纤维网(web)的示例性方法包括梳理纤维、气流成网和湿法成形。这些纤维网可以通过使用粘合剂来固定或粘合,包括散布在纤维网中的低熔点纤维、用于合适的热塑性聚合物的热粘合、针刺、水刺(水力缠结)和纺粘工艺。
本领域技术人员将理解,在纺织品领域中,词语“纺丝”具有两种不同的定义,这两种定义在上下文中都是清楚的。在形成合成长丝时,术语“纺丝”是指将熔融的聚合物挤出成长丝的步骤。
在天然纤维或从变形合成长丝上切割的短纤维的上下文中,术语“纺丝”以其最具历史性的意义(追溯到古代)使用,即将长丝加捻成粘合的纱线结构,从这种纱线结构中可以织造织物。
作为一般参考,Phyllis G.Tortora and Robert S.Merkel,Fairchild'sDictionary of Textiles 7th Edition,New York,Fairchild Publications 2009提供了本领域普通技术人员(技术人员)认可的许多其他定义。
ASTM和AATCC测试协议被认为是行业标准。这些协议通常不会随时间发生显著变化;然而,如果对这些标准的日期(本文未作规定)产生任何疑问,将选择2018年1月生效的标准。
除非有相反的定义,否则术语“百分比”或符号“%”是指质量百分比(“质量%”),其在本说明书中具有与“重量百分数”或“重量百分比”相同的含义。这些用法在上下文中被技术人员很好地理解。
能够实现生物降解的母料制剂通常包含载体聚合物。载体聚合物优选地被配制成与基质(即不可生物降解的聚合物)相匹配。因此,在示例性的实施例中,载体聚合物选自由以下组成的群组:PET、尼龙、烯烃、其他热塑性聚合物及其组合。如示例所示,PET和尼龙与本发明的其他组分结合,已经显示出在可洗涤纺织品中产生优异的生物降解性。
令人惊讶的是,发明人已经发现,在母料中加入碳酸钙显著地提高了所得的纺织品的生物降解性,同时避免了对可洗涤性的负面影响。
尽管本发明不受碳酸钙作用的机理的限制,并且尽管发明人不希望受任何特定理论的束缚,但以下假设似乎是合理的。混合在同质有机聚合物基质中的碳酸钙的微观无机颗粒的存在为生物降解引入了过多的成核点。这种碳酸钙与其他可生物降解的成分同时被定量给料,使得成核点与这些成分非常接近。钙离子可能在细菌增长中起重要作用。细菌中存在的钙结合蛋白有助于信号转导,并且可能有助于其中细菌朝向更高浓度的化学物质移动的积极趋化性的重要过程。
根据这种假设,通过分散的碳酸钙的存在,使得在厌氧细菌的作用下水解酯键将聚合物分解为单体和低聚物的速度加快。二氧化碳(一种代谢副产物)的存在也可以增强聚合物基质中存在的碳酸钙的溶解。
其中细菌中钙和钙结合蛋白可以发挥重要作用的另一机制是群体感应,即一种针对种群增长而优化的细菌的交流手段。单独的细菌努力创造一种水凝胶,其由细菌和细胞外聚合物材料组成,形成协调的功能社区。这种宏观结构放大了细菌的作用,并且有助于导致根据本发明的聚合物的生物降解,特别是可以掺入到这种水凝胶中的高表面积微纤维。
母料制剂嵌入在聚合物基质中。作为假说的进一步的方面,聚合物链上水解侵蚀的化学部分从内部开始。分散在基质中的母料为侵蚀产生成核点,并指数地增加纤维表面积。细菌酶从外部侵蚀并进入体内。细菌(在1微米范围内)最初将从外部作用在纺织纤维上,但随着聚合物基质溶解和分解,暴露出新的表面积。随着水凝胶中协同的细菌群落的形成,大的聚合物链分解成低聚链,并进一步分解成单体,然后消化成CO2和CH4。
因此,可以认为本发明的母料在两个阶段中起作用:在开始时分解成更小的碎片的物理化学作用,和在后半部分中消化25种物质的生物化学作用。
在一些实施例中,纱线或纺织品中的纤维具有在1至50或2至30或高达1,000的每根长丝的旦尼尔数(dpf)。纤维的旦尼尔数被认为对生物降解性并不重要,因为纤维纺织品通常将具有足够的表面积以支持细菌的增长。
在示例性的实施例中,母料包含至少0.5质量%的碳酸钙,在一些实施例中高达10%的碳酸钙,在一些情况下在约0.5%与5%之间的碳酸钙,并且通常约至少1.0%的碳酸钙。本发明的组合物优选地使用细碳酸钙粉末,优选地具有15微米(μm)或更小、10μm或更小、在一些实施例中7μm或更小的质量平均粒径,并且可以在0.1μm与10μm之间,或在1μm与8μm之间,或在5μm与8μm之间的质量平均粒径的范围内。如常规的,可以通过商业光分析设备或其他常规手段来测量粒径。碳酸钙粉末具有至少0.5平方米/克(m2/g)的表面积;在一些情况下至少为1.0m2/g,并且在一些实施例中在0.5与10m2/g之间。如常规的,表面积可以通过诸如用于计算固体的比表面积的ISO 9277标准等的方法来确定,所述方法又基于Brunauer-Emmett-Teller(BET)理论。
在一些优选的实施例中,母料制剂含有下列中的一种或任意组合:聚己内酯(PCL)、聚羟基丁酸酯(PHB)、聚丁二酸丁二醇酯(PBS)、聚乳酸(PLA)和聚(己二酸四亚甲基酯-共-邻苯二甲酸酯)。聚己内酯或包含PCL作为主要脂肪族聚酯组分的共混物似乎是有利的,因为令人惊讶的是,发现,PCL优于聚乳酸(PLA)、PHB和PBS。
因为纺织品需要耐久,所以母料和纺织品组合物应避免不利地影响耐久性的组分。优选地,所述组合物具有低于5质量%,更优选地低于2%,或低于1%的糖类;或者低于呋喃酮的这些量;或者低于这些在洗涤期间滤出的有机(碳基)成分的这些量。在一些实施例中,本发明的组合物缺少任何显著地降低洗涤耐久性的组分。
纺织品优选地具有尺寸稳定性,使得纺织品保持其形状并且收缩小于10%,或小于5%,或小于3%,如通过家用洗涤测试AATCC 135-2015 1IIAii(80F的机器洗涤,滚筒干燥,五个洗涤循环)所测量的。
纺织品或纤维可以是彩色的(诸如红色、蓝色、绿色等)并且优选地具有至少等级3,或至少等级4,或等级5的色牢度,如通过AATCC 61-2013 2A(mod 105F)或AATCC 8-2016、或AATCC 16.3-2014(选项3,20AFU)所测量的。纺织品片(例如,从衬衫或裤子切割的织物样品)优选地具有至少20psi,优选地至少50psi,或至少100psi,或在50至约200psi,或50至约150psi的范围内的胀破强力,其中胀破强力30根据ASTM D3786/D3886M-13测量。
在一些优选的实施例中,织物没有起毛或绒毛(根据ASTM D 3512M-16的等级5)。
在一些实施例中,纺织品芯吸水;这在将汗水从穿着者身上芯吸走的衣服中是特别期望的;在一些优选的实施例中,织物在2分钟内在至少10mm或至少20mm的距离,或在约10mm或约20mm至约150mm的范围内芯吸水;如通过AATCC 197-2013所测量的。根据本发明的一些实施例制造的纺织品的测量值显示在性能测试比较表(即表1-7)中。
在一些情况下,纤维内的精确化学结构可能是未知的,并且上述特性中的一种或组合是表征纺织品的最准确和/或最精确的方法。母料与不可生物降解的聚合物诸如聚对苯二甲酸乙二醇酯、尼龙、烯烃、其他热塑性聚合物及其组合混合。为了本发明的目的,不可生物降解的聚合物是这样的聚合物,即当聚合物不含添加剂时(换句话说,在与母料混合之前),根据ASTM D-5511测试266天后,降解10%或更少(优选地5%或更少,在一些实施例中,3%或更少,并且在一些实施例中,在2%与10%或2%与5%之间。纤维包含至少50质量%,更优选地至少70%,还更优选地至少90%,或至少95%,并且在一些实施例中至少99%的聚合物,所述聚合物选自由以下组成的群组:聚对苯二甲酸乙二醇酯(PET)、尼龙、烯烃、其他热塑性聚合物及其组合。
本发明包括包含这些纤维的纺织品(作为单组分纺织品,或者与其他纤维混合)。许多纺织品包含纤维的混合物(共混物),例如,含有斯潘德克斯弹性纤维的纺织品通常包括棉纤维。在一些实施例中,纺织品包括至少10%,或至少20%,或至少50%,或至少80%,或至少90%,或100%的由聚对苯二甲酸乙二醇酯(PET)、尼龙、烯烃、其他热塑性聚合物及其组合制成的纤维。
由母料生产的纤维通常包含至少90质量%的不可生物降解的聚合物。因为母料优选地以在0.5%至5%之间,优选地至少1%,并且在一些实施例中在1%与5%之间,在一些实施例中在2%与5%之间的量添加,并且因为所有母料都存在于所得组合物中,所以所得纤维将含有相应量的材料。
本发明还包括共混的中间体、纤维、纱线和纺织品。根据本发明的成品的示例包括:针织织物、织造织物、非织造织物、服装、室内装潢、地毯、床上用品诸如床单或枕套、农业或建筑用工业用织物。服装的示例包括:衬衫、裤子、胸罩、内裤、帽子内衣、外套、裙子、连衣裙、紧身衣、弹力裤和围巾。
当然,碳酸钙颗粒被研磨成可用于本发明的尺寸。从功能上来说,研磨的颗粒可以尽可能小,并且非常小的颗粒不呈现缺点。
然而,粒径的上限部分地由旦尼尔数来定义,外行人会用直径来描述。在这些术语中,碳酸钙的平均粒径应不大于挤出长丝的直径的10%,并且最大粒径应不大于挤出长丝的直径的20%,因为大于长丝直径的约10%的粒径在生产和使用的所有阶段导致破裂的可能性更大。
如上所述,下限不那么重要,其中主要考虑的是生产越来越小的颗粒时难度和成本会增加。
因此,作为一个实际示例,一旦(1旦)聚酯纤维具有10微米(μ)的直径,这意味着碳酸钙的粒径不应超过约1μ。技术人员将能够基于这种一般的10%关系选择相关的粒径。
在类似的关系中,母料组合物可以以固体碎片形式生产,用于储存和运输。然后,最终用户可以将碎片研磨成用于其特定最终用途应用的所需尺寸。
在一些实施例中,然后将研磨的母料颗粒与液体混合,接着又将所述液体与所需的最终聚合物混溶。例如(但不限于),聚乙二醇或乙醇适合于聚酯工艺。
作为进一步的考虑,制备的母料可以在生产的替代阶段加入到目标聚合物中。作为一种选项,母料可以在制成聚合物后,但在聚合物保持熔融的状态时,加入到聚合物生产线中。
可替代地,母料可以在目标聚合物的聚合期间加入到连续的聚合物生产线中。在这样的布置中,如果母料与聚合的最后阶段混溶,例如在连续生产线的高聚合釜中,则母料工作良好。
斯潘德克斯弹性纤维.在本发明的上下文中,斯潘德克斯弹性纤维可以是母料工艺的目标聚合物,只要斯潘德克斯弹性纤维是可熔融纺丝的。本领域技术人员认识到斯潘德克斯弹性纤维的变体是溶剂纺丝的而不是熔融纺丝的,并且本发明与熔融纺丝的版本一起使用。
在整个说明书中的示例并不旨在进行限制,但是在各种实施例中,本发明可以由任何选择的特征组合来表征。在一些实施例中,组合物可以部分地由某些组分的缺乏来定义。在一些实施例中,组合物避免包括淀粉或糖类;这样的组分可能是过度地可溶的,并且导致缺乏足够的耐久性的纺织品。添加剂诸如聚丁二酸丁二醇酯优选地不与不可生物降解的聚合物共聚,但在组合物中形成可降解相。
在一些实施例中,本发明的组合物避免脂肪族芳香族聚酯。
本发明的纤维、纱线和织物可以通过它们的物理性能来表征,诸如通过实例中描述的ASTM和/或AATCC测试。例如,纤维、纱线和织物可以根据基于纤维中质量%的生物降解剂的ASTM测试,通过降解程度来定义。前体、中间体和最终产物的分子组成可以通过常规的方法(诸如凝胶渗透色谱法,更优选地聚合物共混物的梯度分析)来确定。
当然,技术人员将理解,一旦母料与主聚合物结合使用,组成数将与添加到主聚合物中的母料的相对量成比例地变化。
本领域技术人员还将理解,当本发明在其实施例中被视为熔融的中间体时,在最常见的纺织品应用中,熔体可以以粒料或长丝的形式挤出。将熔体挤出和骤冷成粒料,提供了在不同的位置(例如,在顾客的位置)储存、运输和再熔融粒料的机会。
当骤冷时,来自组合物的长丝可以使用本领域技术人员熟知的技术进行变形,然后织物可以直接由变形长丝(“长丝纱线”)形成,或者可以将变形长丝切割成短纤维。这样的短纤维又可以纺丝成纱线,最常见的是在开放端***中,但显然环纺丝也是如此。纱线可以进而形成为织物(织造的、针织的、非织造的),或者可以与另一种聚合物(例如,人造纤维)或天然纤维(棉花或羊毛)共混以形成共混的纱线,所述共混的纱线进而可以制成具有共混的纤维的特征的织物。
来自表1的任何配方可以用于本文提及的长丝、粒料、短纤维、变形短纤维、变形长丝或织物中的任何一种。
如本文所使用的,术语“起绒”以及“使起绒”或“有绒毛的”是指对制造的纺织品(例如,Tortora,见上文第378-79页)的众所周知的整理步骤。在这种情况下,本发明也可用于摇粒绒,即通常由聚酯制成的柔软有绒毛的隔热织物。
当形成为合适的长丝时,根据本发明的组合物预期很好地用作隔热服装的填充物。
隔热服装的性质、结构和许多变化对技术人员来说是很好理解的。基本上,隔热材料封装在轻质外壳中,对于这种外壳,低旦尼尔尼龙是典型的,通常包括可以经受至少一些沉淀的防水处理。
根据重量对重量的可压缩性、蓬松度和温暖度与重量的比率,羽绒当然是最好的隔热材料,但是,即使稍微更重且可压缩性稍差,诸如本发明的合成填料成本更低,并且在潮湿时具有更好的隔热性能,。
作为另一个示例,根据本发明的长丝、纤维和纱线预期作为可生物降解的地毯或这种地毯的一部分表现非常好。如本领域技术人员所熟知的,地毯是一种纺织品地板覆盖物,其通常由附着在背衬上的绒头纱线或簇绒纱线形成。在合成材料出现之前,并且目前仍在使用,典型的绒头由羊毛制成,并且背衬由织造的织物制成,纱线可以编织、簇绒或以其他方式附着在织物上。
本领域技术人员通常可互换地使用术语“地毯”和“小地毯”,尽管在一些情况下,“地毯”覆盖整个房间(“铺满整个地板的地毯”),而“小地毯”覆盖小于整个房间的面积。
因为合成材料诸如尼龙、聚丙烯、聚酯以及它们与羊毛的共混物是可用的地毯材料,所以由本发明形成的纤维或纱线对于地毯是完全适合和可用的。本领域技术人员认识到多种背衬材料、背衬结构以及将绒头或簇绒连接到背衬上的手段。重复所有这样的可能性将是多余的,而并非明晰化,并且本领域技术人员可以在任何给定的上下文中并且在无需过度的实验的情况下采用必要的材料和步骤。
实例
制备了具有表1中所示的组合物的各种母料组合物。
这些母料共混到聚对苯二甲酸乙二醇酯中(1%的母料是典型的),并用重力进料器在闭环中进料到装配有双螺杆的熔体挤出机中。添加剂批料在250℃下混合,并通过股模具挤出到水浴或同等骤冷设备中。在分级机去除粒料尺寸分布最末端的颗粒后,将粒料干燥并装袋。
测试中使用的碳酸钙具有6.5微米的质量平均粒径和约1.5平方米/克的表面积。
将制剂以1%的加载速率挤出成PET,并根据ASTM D5511测试与挤出工艺最相容的配方的降解。266天的结果在图1和表2中示出,并且353天的结果在图2和表3中示出。
初始读数在第59天获得;在这个非常早期的读数中,似乎配方13(表1)显示出3.9%的降解,而配方14似乎根本没有开始降解。然而,基于气压事件和数据中的噪声,来自配方13和14的数据似乎是不可靠和不可复制的。此外,如此低的降解读数太接近基线,不可信赖(对于没有添加剂的PET降解3%),因此停止了对这些配方的测试。
以上显示的结果表明优于现有技术。在这些垃圾填埋条件下,PET纤维降解为甲烷和二氧化碳。在266天后,用表中1质量%的母料配方#2、3、6、7和11制备的PET样品分别降解了43.6%、66.1%、56.5%、21.3%和38.3%。在相同条件下,未改性的PET降解了3.2%。最高的降解发生于含有49%的聚己内酯和10%的聚羟基丁酸酯的母料,而最低的降解发生于含有39%的聚己内酯和20%的聚丁二酸丁二醇酯的母料。由49%的聚己内酯和10%的聚羟基丁酸酯制成的材料也比用含有39%的聚己内酯、10%的聚羟基丁酸酯和10%的聚丁二酸丁二醇酯的1%母料改性的PET显著更好地降解。
上述结果可以与WO 2016/079724(“表1-300天后的结果”)中报告的结果进行比较,在WO2016/079724中,聚酰胺纤维是使用2%的市售生物降解剂(https://ecologic-lIc.com/about/eco-one-video-tour;2019年2月11日访问)的母料进行熔融纺丝的。所得纤维通过ASTM D5511标准进行测试,并且发现,在300天后降解了13.9%(“PA6.6”)或15.5%(“PA 5.6”)。在相同的ASTM D5511测试下,不含生物降解剂的WO 2016/079724的纤维降解了2.2%和2.3%。
基于未改性的纤维,并忽略266天与300天之间的差异,常规的PET(本文表2)似乎比WO 2016/079724中的聚酰胺纤维可降解性高3.2/2.25=1.42倍。相比之下,根据本发明的改性的PET比WO 2016/079724中的改性的聚酰胺纤维可降解性高21.3/15.5=1.37倍至66.1/15.5=4.26倍。校正了WO 2016/079724中聚酰胺纤维由两倍多的母料改性的事实(2%相对于1%),根据本发明的PET可降解性在2.74倍与8.52倍之间。校正了未改性的聚酯与聚酰亚胺之间的2.74/1.42的差异,本发明显示出在1.92倍与3.00倍之间的更大的生物降解性。
表4和图3示出了由配方2(表1)和对照聚酯制成的织物的生物降解的改善。
ASTM D5210-在存在污泥的情况下的厌氧降解
将来自两种制剂的成品织物进行石磨滚落以形成微纤维,并且根据ASTM D5210测定微纤维的降解持续55天,其模拟了水处理设施中通常经历的条件。结果在表5和图4中示出。
ASTM D6691-需氧降解模型5a海洋环境
将来自一种制剂的成品织物石磨滚落以形成微纤维,并根据ASTM D6691测试微纤维的降解持续112天。结果在表6和图5汇总。
实例-无毒性
组合物使用ASTM E1963方法进行测试,这是一种使用陆生植物物种(诸如豆类、玉米和豌豆)进行植物毒性测试的方案,以确定测试物质对植物增长和发育的影响。豌豆是很好的指示物,因为它们对土壤条件非常敏感。在该ASTM E 1963测试中,使用了含有来自配方2的ASTM D5511测试的副产物的残留土壤的渗滤液。图7示出了来自ASTM E 1963测试的结果。
检查背景(第1栏)和样品(第3栏)中的植物增长,表明相关副产物样品的渗滤液对植物增长没有抑制作用。
表7-在有母料和没有母料的情况下纺织品性能的实例
经受细菌分解的纤维的显微镜分析
在图6的SEM图像中示出了在ASTM D5511中经受根据本发明的纤维的细菌分解的纤维的电子显微镜成像(SEM IIV:15kv;视野173微米;SEM放大1.5倍;TescanTM Vega 3TM钨热离子发射SEM***(https://www.tescan.com/en-us/technology/sem/vega 3);2019年2月12日访问),并显示在>1年暴露于细菌之后,根据本发明的聚酯纤维的表面上的细菌菌落。
在附图和说明书中,已经阐述了本发明的优选的实施例,并且尽管已经使用了特定的术语,但是它们仅用于一般和描述的意义,而不是用于限制的目的,本发明的范围由权利要求限定。
Claims (14)
1.一种制备纤维的方法,包含:
将基本上由以下组成的母料:
0.2至5质量%的CaCO3;
脂肪族聚酯,其包含在酯基团之间的链中具有二至六个碳的重复单元,条件是所述链中的2至6个碳不包括侧链碳;
以及载体聚合物,其选自由以下组成的群组:PET、尼龙、烯烃、其他热塑性聚合物及其组合,
共混入选自由以下组成的群组中的聚合物:PET、尼龙、烯烃、其他热塑性聚合物及其组合,以形成熔融的混合物;并且随后将所述熔融的混合物挤出成长丝。
2.根据权利要求1所述的制备纤维的方法,包含在制备所述聚合物之后但在所述聚合物保持熔融状态的同时,将所述母料添加到聚合物生产线中。
3.根据权利要求1所述的制备纤维的方法,包含在目标聚合物的聚合过程中,将所述母料添加到连续的聚合物生产线中。
4.根据权利要求1所述的制备纤维的方法,进一步包含将所述挤出的长丝骤冷。
5.根据权利要求4所述的制备纤维的方法,进一步包含使所述长丝变形。
6.根据权利要求5所述的制备纤维的方法,包含将所述变形长丝切割成短纤维。
7.根据权利要求6所述的制备纤维的方法,进一步包含将所述短纤维纺成纱线。
8.根据权利要求7所述的方法,进一步包含将所述纱线机织成织物。
9.根据权利要求7所述的方法,进一步包含将所述纱线编织成织物。
10.根据权利要求6所述的方法,进一步包含由所述短纤维铺设非织造棉胎。
11.根据权利要求1所述的方法,包含将所述熔融的混合物挤出成粒料,并且
随后在挤出所述混合物以形成长丝的步骤之前再熔融所述粒料。
12.根据权利要求1所述的方法,其中待共混的所述母料基本上由以下组成:
在0.9与1.1质量%之间的碳酸钙;并且
其中2-6个碳的脂肪族酯为聚己内酯,量为44-54质量%;
进一步包含聚丁二酸丁二醇酯,量为9-11质量%;并且
其中所述母料的其余部分是作为所述载体聚合物的聚对苯二甲酸乙二醇酯。
13.根据权利要求1所述的方法,其中所述熔融的混合物基本上由以下组成:
0.39-0.48重量%的聚酯;
0.39-0.49重量%的PLC;和
0.01重量%的碳酸钙;以及
至少90质量%的PET。
14.根据权利要求1所述的方法,其中根据权利要求13所述的熔融的混合物进一步包含组合物,所述组合物选自由以下组成的群组:0.05-0.1重量%的PLA、0.05-0.1重量%的PHA、0.05-0.1重量%的PBAT、0.10-0.20重量%的PBS、0.01重量%的二氧化硅以及这些组合物的组合。
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