CN101442965A - 包括衍生自可再生资源的合成聚合物的吸收制品及生产所述制品的方法 - Google Patents
包括衍生自可再生资源的合成聚合物的吸收制品及生产所述制品的方法 Download PDFInfo
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- CN101442965A CN101442965A CNA2007800177141A CN200780017714A CN101442965A CN 101442965 A CN101442965 A CN 101442965A CN A2007800177141 A CNA2007800177141 A CN A2007800177141A CN 200780017714 A CN200780017714 A CN 200780017714A CN 101442965 A CN101442965 A CN 101442965A
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Classifications
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Abstract
本发明公开了一种吸收制品,所述吸收制品包括顶片、与顶片接合的底片、设置在顶片和底片之间的吸收芯、以及通过至少一种中间化合物衍生自第一可再生资源的合成超吸收聚合物,其中所述超吸收聚合物表现出指定的盐水流动传导率值和耐压吸收性值。作为另外一种选择,本发明公开了一种吸收制品,所述吸收制品含有通过至少一种中间化合物衍生自第一可再生资源的合成聚烯烃。所述合成聚烯烃表现出指定的性能特征,使得聚烯烃尤其可用于吸收制品的某些组件中。本发明还公开了制备上述吸收制品的方法。
Description
发明领域
本发明涉及包括衍生自可再生资源的合成聚合物材料的吸收制品,其中所述材料具有使其尤其适用于吸收制品中的特定性能特征。
发明背景
一次性尿布、成人失禁衬垫和短内裤、以及经期用品如卫生巾之类的吸收制品的开发引起广泛的商业关注。存在大量的涉及吸收制品的设计、制造此类制品的方法、以及用于其构造中的材料的技术。具体地讲,人们付出了很大的努力来开发显示具有用于吸收制品的最佳性能特征的材料。此类材料包括薄膜、纤维、非织造材料、层压体、超吸收聚合物、泡沫、弹性体、粘合剂等。
用于目前的商业吸收制品的大多数材料衍生自不可再生资源,尤其是石油。通常,顶片、底片和腿箍之类的组件由诸如聚乙烯和聚丙烯的聚烯烃制成。这些聚合物衍生自诸如乙烯和丙烯的烯属单体,其通过裂解和精制方法直接获自于石油。衍生自石油的丙烯还用于通过催化氧化方法制备丙烯酸。衍生自石油的丙烯酸为用于最新超吸收聚合物制造中的主要给料,所述聚合物在目前的商业吸收制品的吸收芯中被利用。
因此,石油给料的价格和可获得性最终会对利用衍生自石油的材料的吸收制品的价格具有显著影响。由于全球石油价格攀升,因此吸收制品的价格也不断上升。
此外,许多消费者表现出对衍生自石化产品的产品的厌恶。在某些情况下,消费者对购买由有限的不可再生资源如石油和煤炭制成的产品犹豫不决。其它消费者可能会对衍生自石油产品的产品具有负面印象,认为其是“非天然的”或对环境不友好的。
已公开了用于吸收制品中的衍生自非石化产品或可再生资源的某些可供选择的材料。例如,授予Chao的美国专利5,889,072描述了一种制备交联聚天冬氨酸超吸收材料的方法。均授予Huppe等人的美国专利6713460和6,444,653描述了一种包括玻璃状多糖的超吸收材料。此外,已公开了具有不同生物降解度的尿布。授予Ehret等人的美国专利5,783,504描述了一种适合用于尿布中的复合结构,该复合结构包括由衍生自乳酸的聚合物制造的非织造材料和由可生物降解的脂族聚酯聚合物制造的薄膜。PCT专利申请WO 99/33420公开了一种包括可再生和/或可生物降解原料的超吸收材料。然而,这些尿布和材料趋于具有比衍生自石化产品的材料显著降低的性能和/或更高的成本。例如,公开于WO 99/33420中的超吸收材料显示出低的加载吸收容量和低的凝胶强度。具有低凝胶强度的超吸收材料趋于在溶胀时变形并降低超吸收颗粒之间的空隙空间。这种现象称为凝胶阻塞。一旦发生凝胶阻塞,则进一步的液体摄入或分配将通过极慢的扩散过程进行。实际上,凝胶阻塞使得吸收制品更易于渗漏。
因此,期望提供一种包括衍生自可再生资源的聚合物的吸收制品,其中所述聚合物具有使得该聚合物尤其适合用于吸收制品中的特定性能特征。理想的是,期望提供一种包括多个吸收制品的消费品,所述吸收制品包括衍生自可再生资源的所述聚合物以及相关的环境信息的传达。
发明概述
本发明涉及一种具有相对的纵向边缘的吸收制品,所述吸收制品包括顶片、与顶片接合的底片、设置在顶片和底片之间的吸收芯、以及通过至少一种单体中间化合物衍生自第一可再生资源的合成聚合物。将所述聚合物设置在或结合到吸收制品的一个或多个元件中。所述元件选自由吸收芯、顶片、底片和阻挡腿箍组成的组。
本发明还涉及一种具有面向身体的表面和面向衣服的表面的吸收制品。所述制品包括顶片、与顶片接合的底片、设置在顶片和底片之间的吸收芯、一对阻碍箍、以及合成聚烯烃。合成聚烯烃通过至少一种中间化合物衍生自第一可再生资源。合成聚烯烃为聚丙烯或聚乙烯。顶片、底片或箍基底包括聚烯烃。
本发明还涉及一种制备吸收制品的方法,所述方法包括以下步骤:提供可再生资源、由可再生资源来衍生中间单体化合物、聚合单体化合物以形成合成聚合物、以及将聚合物设置在或结合到吸收制品的一个或多个元件中。所述元件选自由吸收芯、顶片、底片和阻挡腿箍组成的组。
附图概述
图1A为处于平展未收缩状态的尿布形式的示例性吸收制品的平面图。
图1B为图1A中尿布沿横向中心线截取的剖面图。
图2A至2B为包括吸收制品的包装的透视图。
图3A至3F为传达减弱的石化依赖和/或环境友好的几种适当的图标实施方案的图例。
图4为用于进行盐水流动传导率测试的适当渗透性测量体系的局部横截面侧视图。
图5为用于进行盐水流动传导率测试的活塞/滚筒组合件的横截面侧视图。
图6为适用于图5中所示的活塞/滚筒组合件中的活塞头的顶视图。
图7为放置在用于溶胀相的烧结盘上的图5中活塞/滚筒组合件的横截面侧视图。
发明详述
本发明涉及包括衍生自可再生资源的合成聚合物的吸收制品,其中所述聚合物具有特定性能特征。当衍生自可再生资源的合成聚合物为超吸收聚合物形式时,其表现出至少约15.0g盐水每克聚合物的耐压吸收性(AAP)值和/或至少约30×10-7cm3·秒/g的盐水流动传导率(SFC)。当聚合物为适于用作顶片的聚烯烃非织造材料时,其可表现出小于约4秒的液体透湿值。当聚合物为适于用作阻挡腿箍的聚烯烃非织造材料时,其可表现出至少约5mbar的水头。当聚合物为适于用作底片的可透气的聚烯烃薄膜时,其可表现出至少约2000g/m2/24小时的湿气透过率。当聚合物为适于用作底片的聚烯烃薄膜时,其可具有至少约0.5N/cm的纵向拉伸强度。
在另一方面,吸收制品包括衍生自可再生资源的合成聚合物,其中所述聚合物具有约1.0×10-14或更大的14C/C比。
本发明还涉及包括至少一个吸收制品和保护所述吸收制品的外包裹物的包装,所述吸收制品包括衍生自可再生资源的合成聚合物。所述吸收制品包括衍生自可再生资源的合成聚合物。所述包装还可包括相关的环境信息的传达。
本发明还涉及一种制备包括衍生自可再生资源的合成聚合物的吸收制品的方法。所述方法包括以下步骤:提供可再生资源;由所述可再生资源衍生至少一种中间化合物,其中所述中间化合物包括单体化合物;聚合单体化合物以形成至少一种聚合物,其中所述至少一种聚合物表现出用于吸收制品中的必需性能;以及将所述至少一种聚合物结合到吸收制品中。如本文所述,可将另外的步骤结合到该方法中。任选地,所述至少一种聚合物可在聚合步骤之后被改性。
I.定义
如本文所用,下列术语应当具有下文明确规定的意义:
“一次性的”是指旨在经有限次使用(通常单次使用)后丢弃的物品(即,最初的吸收制品原则上不打算洗涤或作为吸收制品再利用,尽管该吸收制品的某些材料或部分可回收、再利用或堆肥处理)。例如,某些一次性吸收制品可暂时复原以通过可移除/可替换组件的使用基本履行其功能,但仍然认为该制品为一次性的,因为整个制品旨在经有限次使用后丢弃。
“吸收制品”是指吸收和容纳身体流出物的装置,更具体地讲是指紧贴或邻近穿用者的身体放置以吸收和容纳各种由身体排放的流出物的装置。示例性吸收制品包括尿布、训练裤、套穿裤型尿布(即,如美国专利6,120,487所示具有预成形的腰部开口和腿部开口的尿布)、可重复扣紧的尿布或裤型尿布、失禁贴身短内裤和内衣、尿布固定器和衬里、妇女卫生内衣如紧身短裤衬里(例如美国专利4,425,130、4,687,478、5,267,992和5,733,274中所公开的)、吸收插件等。吸收制品可为一次性的或者可包含可再使用或复原的部分。
“近侧”和“远侧”分别是指元件的位置相对靠近或远离结构的纵向或横向中心线(例如,纵向延伸元件的近侧边缘距纵向中心线的位置,比同一元件的远侧边缘相对于同一纵向中心线的位置更近)。
“面向身体”和“面向衣服”分别指某个元件的相对位置、或某个元件或一组元件的表面。“面向身体”是指在穿着期间元件或表面与某个其它元件或表面相比更靠近穿着者。“面向衣服”是指在穿着期间元件或表面与某个其它元件或表面相比更远离穿着者(即,元件或表面邻近可贴穿在吸收制品外面的穿着者的衣服)。
“超吸收制品”是指在25℃时能够吸收其干重的至少十倍的0.9%盐水溶液的材料。超吸收聚合物通过渗透机理吸收液体以形成凝胶,其通常称作术语“水凝胶”,并与该术语互换使用。
“纵向”是指从制品的一个腰部边缘向相对的腰部边缘基本垂直延伸并且通常平行于制品的最大线性尺寸的方向。在纵向45度内的方向被认为是“纵向”。
“横向”是指从制品的一个纵向边缘向相对的纵向边缘延伸并且通常与纵向成直角的方向。在横向45度内的方向被认为是“横向”。
“设置”是指元件被定位在特定的部位或位置。
“接合”是指这样一些构型,其中将一个元件直接连接到另一个元件上从而使该元件直接固定到另一个元件上;也指这样一些构型,其中将一个元件连接到中间构件上,继而再把中间构件固定到另一个元件上,从而使该元件间接固定到另一个元件上。
“薄膜”是指一种片状材料,其中材料的长度和宽度远远超过材料的厚度。典型地,薄膜具有约0.5mm或更小的厚度。
“不可渗透的”通常是指在0.14lb/in2或更小的压力下流体不能渗透过制品的整个Z方向上的厚度的制品和/或元件。优选地,不可渗透的制品或元件在0.5lb/in2或更小的压力下不被流体所渗透。更优选地,不可渗透的制品或元件在1.0lb/in2或更小的压力下不被流体所渗透。用于测定渗透性的测试方法遵照Edana 120.1-18或INDA IST 80.6。
“可延伸性”和“可延展的”是指松弛状态下的组件的宽度或长度在受到张力时可延伸或增加至少约10%而不断裂或破裂。
“弹性的”、“弹性体”和“弹性体的”是指这样一种材料,所述材料通常能够延伸至至少50%的应变而不断裂或破裂,并且在变形力被移除之后能够基本恢复至其原有尺寸。
“弹性体材料”为显示弹性性能的材料。弹性体材料可包括弹性体薄膜、稀松布、非织造材料、以及其它片状结构体。
“外侧”和“内侧”分别指元件的位置,即该元件相对于第二元件、相对远离或靠近尿布的纵向中心线设置。例如,如果元件A是元件B的外侧,则元件A比元件B更远离纵向中心线。
“裤”是指具有预成形的腰部开口和腿部开口的吸收制品。可通过将穿着者的双腿伸入腿部开口并将裤提拉到围绕穿着者下体的适当位置来穿用裤。裤通常也称为“闭合尿布”、“预紧固尿布”、“套穿尿布”、“训练裤”和“尿布裤”。
“石化产品”是指衍生自石油、天然气或煤炭的有机化合物。
“石油”是指原油及其石蜡烃、环烷烃和芳族烃的组分。原油可获自沥青砂、沥青田和油页岩。
“可再生资源”是指在100年的期限内可再补充的天然资源。所述资源可天然或者通过农业技术再补充。可再生资源包括植物、动物、鱼类、细菌、真菌、以及林产品。它们可为天然存在的、杂交的、或遗传工程的生物体。诸如原油、煤炭和泥炭的天然资源由于需要比100年更长的时间来形成,因此不被认为是可再生资源。
“农产品”是指得自土地耕种(如农作物)或动物(包括鱼类)饲养的可再生资源。
“单体化合物”是指可聚合生成聚合物的中间化合物。
“聚合物”是指包括重复单元的高分子,其中所述高分子具有至少1000道尔顿的分子量。聚合物可为均聚物、共聚物、三聚物等。聚合物可借助自由基聚合、缩合聚合、阴离子聚合、阳离子聚合、齐格勒-纳塔聚合、茂金属聚合、或开环机理生成。聚合物可为直链、支链和/或交联的。
“合成聚合物”是指由至少一种单体通过化学方法产生的聚合物。合成聚合物不直接由活生物体产生。
“聚乙烯”和“聚丙烯”是指分别由乙烯和丙烯制备的聚合物。聚合物可为均聚物,或者可包含最多约10%摩尔的来自共聚单体的重复单元。
“传达”是指传递信息、教导或讯息的媒介或手段。
“相关的环境信息”是指传达包括衍生自可再生资源的聚合物的吸收制品的有益效果或优点的信息。此类有益效果包括更环境友好地、具有降低的石油依赖性、衍生自可再生资源等。
除非另外指明,本文所有百分数均按重量计。
II.衍生自可再生资源的聚合物
许多可再生资源包含适用于吸收制品中的聚合物(即,聚合物获自于可再生资源而无需中间体)。适当的提取和/或纯化步骤可能是必要的,但是不需要中间化合物。此类聚合物直接衍生自包括以下成分的可再生资源:纤维素(如纸浆纤维)、淀粉、甲壳质、多肽、聚(乳酸)、聚羟基链烷酸酯等。可对这些聚合物随后进行化学改性以改善最终使用特性(例如,将纤维素转换得到羧酸纤维素或者将甲壳质转换得到脱乙酰壳多糖)。然而,在此类情况下,所得聚合物为原料聚合物的结构类似物。直接衍生自可再生资源(即,无中间化合物)的聚合物以及它们的衍生物为人们所了解,并且这些材料不在本发明的范围内。
本发明的合成聚合物通过涉及一种或多种中间化合物的间接路线衍生自可再生资源。衍生自可再生资源的适当的中间化合物包括糖。适当的糖包括单糖、二糖、三糖和低聚糖。诸如蔗糖、葡萄糖、果糖、麦芽糖的糖可易于由诸如甘蔗和糖用甜菜的可再生资源生产。糖也可衍生自(例如,通过酶解)诸如淀粉或纤维素的农业产品。例如,葡萄糖可通过玉米淀粉的酶水解大规模制备。尽管玉米为北美洲的可再生资源,但是其它常见的农作物也可用作转换成葡萄糖的基础淀粉。小麦、荞麦、秘鲁胡萝卜、马铃薯、大麦、野葛、木薯、高粱、甘薯、山药、竹芋、西米、以及其它类似含淀粉的水果、种子或块茎也可用于葡萄糖的制备。
衍生自可再生资源的其它适当的中间化合物包括诸如甲醇或乙醇的单官能醇以及诸如甘油的多官能醇。乙醇可衍生自许多与葡萄糖相同的可再生资源。例如,可将玉米淀粉酶水解以得到葡萄糖和/或其它糖。所得糖可通过发酵转化成乙醇。与葡萄糖生产一样,玉米为北美洲理想的可再生资源;然而也可用其它作物代替。甲醇可由生物质的发酵来生产。甘油通常由存在于天然脂肪或油类中的甘油三酯的水解得到,所述天然脂肪或油类可获自诸如动物或植物的可再生资源。
衍生自可再生资源的其它中间化合物包括有机酸(例如,柠檬酸、乳酸、藻酸、氨基酸等),醛(例如,乙醛)、以及酯(例如,棕榈酸鲸蜡酯、硬脂酸甲酯、油酸甲酯等)。
诸如甲烷和一氧化碳的另外中间化合物也可通过发酵和/或氧化方法衍生自可再生资源。
可将衍生自可再生资源的中间化合物转化成聚合物(例如,甘油转化成聚甘油)或者可在反应路线中将它们转化成其它中间化合物,最终得到可用于吸收制品中的聚合物。中间化合物能够生产一种以上的次要中间化合物。类似地,取决于所利用的反应路线,具体的中间化合物可衍生自许多不同的前体。
尤其理想的中间体包括(甲基)丙烯酸及其酯和盐;以及烯烃。在特定实施方案中,中间化合物可为丙烯酸、乙烯或丙烯。
例如,丙烯酸为可通过许多适当的路线衍生自可再生资源的单体化合物。此类路线的实例提供如下。
可根据两步法将衍生自可再生资源的甘油(例如,通过大豆油和其它甘油三酯油的水解)转换成丙烯酸。在第一步中,甘油可被脱水以得到丙烯醛。尤其适当的转换方法涉及使气态甘油暴露于氧化铝载体上的酸性固体催化剂如H3PO4(其常常称作固体磷酸)以得到丙烯醛。有关甘油脱水以得到丙烯醛的细节公开于例如美国专利2,042,224和5,387,720中。在第二步中,丙烯醛被氧化以生成丙烯酸。尤其适当的方法涉及丙烯醛与氧在金属氧化物催化剂存在下进行气相相互作用。也可采用钼和钒氧化物催化剂。有关氧化丙烯醛以得到丙烯酸的细节公开于例如美国专利4,092,354中。
可根据两步法将衍生自可再生资源的葡萄糖(例如,通过玉米淀粉的酶水解)转换成丙烯酸,其中乳酸作为中间产物。在第一步中,葡萄糖可被生物发酵以得到乳酸。可利用能够对葡萄糖发酵以得到乳酸的任何适当的微生物,所述微生物包括乳酸菌属的成员(例如L乳酸乳杆菌)以及美国专利5,464,760和5,252,473中确认的那些。在第二步中,可通过利用酸性脱水催化剂使乳酸脱水生成丙烯酸,所述催化剂如已浸渍磷酸盐的惰性金属氧化物载体。这种酸性脱水催化方法更详细地描述于美国专利4,729,978中。在可供选择的适当的第二步中,乳酸可通过与包括固体磷酸铝的催化剂反应转化成丙烯酸。这种催化脱水方法更详细地描述于美国专利4,786,756中。
用于将葡萄糖转化成丙烯酸的另一种适当的反应路线涉及其中3-羟基丙酸作为中间化合物的两步法。在第一步中,葡萄糖可被生物发酵以得到3-羟基丙酸。能够对葡萄糖发酵以得到3-羟基丙酸的微生物已被遗传工程化,以表达用于转化的必需酶。例如,表达源自肺炎克雷伯菌的dhaB基因和用于醛脱氢酶的基因的重组微生物已示出能够将葡萄糖转化成3-羟基丙酸。关于重组生物体的生产的细节存在于美国专利6,852,517中。在第二步中,3-羟基丙酸可被脱水以生产丙烯酸。
可通过多步反应路线将衍生自可再生资源的葡萄糖(例如,通过由玉米可再生资源获得的玉米淀粉的酶水解)转化成丙烯酸。葡萄糖可被发酵以得到乙醇。乙醇可被脱水以得到乙烯。在这种情况下,乙烯可被聚合以生成聚乙烯。然而,乙烯可在诸如八羰基钴或铑络合物的催化剂存在下利用一氧化碳和氢通过乙烯的加氢醛化而转化成丙醛。在诸如硼氢化钠和氢化锂铝的催化剂存在下可通过丙醛的催化加氢生成正丙醇。正丙醇可在酸性催化反应中脱水得到丙烯。在这种情况下,丙烯可被聚合以生成聚丙烯。然而,丙烯可通过汽相催化氧化转化成丙烯醛。丙烯醛随后可在钼-钒催化剂存在下被催化氧化以生成丙烯酸。
尽管以上反应路线可得到丙烯酸,但技术人员将会知道丙烯酸可易于转化成酯(例如,丙烯酸甲酯、丙烯酸乙酯等)或盐。
诸如乙烯和丙烯的烯烃也可衍生自可再生资源。例如,衍生自生物质发酵的甲醇可转化成乙烯或丙烯,两者均为适当的单体化合物,如美国专利4,296,266和4,083,889中所述。衍生自可再生资源发酵的乙醇可通过脱水转化成乙烯单体化合物,如美国专利4,423,270中所述。类似地,衍生自可再生资源的丙醇或异丙醇可脱水得到丙烯单体化合物,如美国专利5,475,183中所示例的。丙醇为杂醇油的主要组分,所述杂醇油为马铃薯或谷物发酵生成乙醇时由某些氨基酸生成的副产物。
衍生自生物质的木炭可用于产生合成气(即,CO+H2),诸如乙烷和丙烷的烃类可由其制备(费托方法)。乙烷和丙烷可脱氢得到乙烯和丙烯的单体化合物。
III.示例性合成聚合物
A.超吸收聚合物-衍生自可再生资源的某些化合物可被聚合以得到适当的合成超吸收聚合物。例如,通过上述甘油/丙烯醛路线衍生自大豆油的丙烯酸可在适当的条件下被聚合以得到包含聚(丙烯酸)的超吸收聚合物。可用于本发明中的吸收性聚合物可通过能够实现期望性能的任何聚合和/或交联技术形成。生产这些聚合物的典型方法描述于授予Brandt等人的再颁发美国专利32,649;美国专利4,666,983、4,625,001、5,408,019;以及授予Dahmen的公布的德国专利申请4,020,780中。加工(即,干燥、研磨、筛分等)所得超吸收聚合物以得到有用形式为本领域所熟知。
聚合物可以中和的、部分中和的、或未中和的形式制备。在某些实施方案中,吸收性聚合物可由约50%摩尔至约95%摩尔被中和的丙烯酸形成。吸收性聚合物可利用均相溶液聚合方法制备,或者通过多相聚合技术如反相乳液聚合或悬浮聚合方法制备。聚合反应一般将在相对少量的双官能或多官能单体(例如N,N′-亚甲基双丙烯酰胺、三羟甲基丙烷三丙烯酸酯、乙二醇二(甲基)丙烯酸酯、三烯丙基胺、以及上述丙烯酸酯的甲基丙烯酸酯类似物)存在下发生。双官能或多官能单体化合物用于轻度交联聚合物链,从而使得它们为水不溶性的但水可溶胀的。
在某些实施方案中,包含衍生自可再生资源的丙烯酸的合成超吸收聚合物可形成于淀粉-丙烯酸接枝共聚物、部分中和的淀粉-丙烯酸接枝共聚物、聚丙烯酸的交联聚合物、以及部分中和的聚丙烯酸的交联聚合物。这些材料的制备公开于美国专利3,661,875、4,076,663、4,093,776、4,666,983和4,734,478中。
合成超吸收聚合物颗粒可在聚合反应之后通过与适当的反应交联剂反应进行表面交联。如下所述,衍生自可再生资源的初始形成的超吸收聚合物颗粒的表面交联提供了在溶胀状态下具有相对高的吸收容量和相对高的流体渗透性的超吸收聚合物。本领域中公开了许多引入表面交联的方法。用于表面交联的适当方法公开于美国专利4,541,871、4,824,901、4,789,861、4,587,308、4,734,478和5,164,459;公布的PCT申请WO92/16565、WO90/08789和WO93/05080;授予Dahmen的公布德国专利申请4,020,780;以及授予Gartner的公布欧洲专利申请509,708中。适当的交联剂包括双官能或多官能交联剂,例如双/多卤代烷、双/多环氧化物、双/多酰基氯、双/多甲苯磺酰基烷烃、双/多醛、二元/多元醇等。
本发明的合成超吸收聚合物的一个重要特征为用体液溶胀时聚合物颗粒区域或层的渗透性或流动传导性。本文根据超吸收聚合物的盐水流动传导率(SFC)值来定义此渗透性或流动传导性。盐水流动传导率测定溶胀水凝胶区域或层在使用压力下传送或分布体液的能力。据信当超吸收聚合物在吸收构件中以高浓度存在并随后在使用压力下溶胀形成水凝胶时,水凝胶的边界进行接触,并且在这种高浓度区域中的空隙空间一般由水凝胶限定。当其发生时,据信该区域的渗透性或流动传导性通常反映了由单独的超吸收聚合物形成的水凝胶区域或层的渗透性或流动传导性。还据信增加这些溶胀的高浓度区的渗透性至接近或者甚至超过常规的采集/分配材料(如木浆绒毛)的程度可为吸收构件和吸收芯提供卓越的流体处理性能,因此降低了渗漏的可能,尤其是在高流体载荷下。较高的盐水流动传导率值还反映了形成的水凝胶在正常使用条件下采集体液的能力。
可用于本发明的衍生自可再生资源的合成超吸收聚合物的盐水流动传导率值为至少约30×10-7cm3·秒/g。在其它实施方案中,可用于本发明中的超吸收聚合物的盐水流动传导率值为至少约50×10-7cm3·秒/g。在其它实施方案中,可用于本发明中的超吸收聚合物的盐水流动传导率值为至少约100×10-7cm3·秒/g。通常,这些盐水流动传导率值在约30×10-7至约1000×10-7cm3·秒/g的范围内。然而,盐水流动传导率值的范围可为约50×10-7至约500×10-7cm3·秒/g或者约50×10-7至约350×10-7cm3·秒/g。测定超吸收聚合物的盐水流动传导率值的方法提供于下文测试方法部分中。
本发明的超吸收聚合物的另一个重要特性为它们的耐载荷溶胀能力。这种相对载荷的容量依据超吸收聚合物的耐压吸收性(AAP)能力来定义。当超吸收聚合物以高浓度结合到吸收构件中时,聚合物必须能够在使用压力下于合理的时间段内吸收大量体液。施加在吸收制品内所用的超吸收聚合物上的使用压力既包括机械压力(例如,由穿着者的重量和运动所施加的、包装力等),也包括毛细管压力(例如,源于吸收芯中的采集组件,其在超吸收聚合物吸收流体之前暂时性保持流体)。
可用于本发明的吸收聚合物的耐压吸收容量一般为至少约15g/g。在某些实施方案中,吸收制品的耐压吸收容量一般为至少约20g/g。通常,耐压吸收值的范围为约15g/g至约25g/g。然而,耐压吸收值的范围也可为约17g/g至约23g/g或者约20g/g至约23g/g。测定这些吸收聚合物的耐压吸收容量值的方法提供于下文测试方法部分中。
B.聚烯烃-可将衍生自可再生资源的烯烃聚合以得到聚烯烃。衍生自可再生资源的乙烯可在适当条件下聚合以制备具有理想特性的聚乙烯,用于吸收制品的特定组件中或所述制品的包装中。聚乙烯可为高密度、中密度、低密度、或线性低密度。可借助自由基聚合技术,或者通过利用齐格勒-纳塔催化或茂金属催化剂生产聚乙烯和/或聚丙烯。
可依据本领域已知的方法将聚烯烃加工成适用于聚合物最终用途的形式。聚烯烃的适当形式包括薄膜、开孔薄膜、微孔薄膜、纤维、长丝、非织造材料、或层压体。适当的非织造形式包括纺粘纤维网、熔喷纤维网、以及它们的组合(例如,纺粘-熔喷纤维网(SM)、纺粘-熔喷-纺粘纤维网(SMS)等)。聚烯烃可包括与其它聚合物(例如衍生自石化产品的聚烯烃)的混合物或共混物。取决于最终用途和形式,聚烯烃可包括其它化合物,例如无机化合物、填充剂、颜料、染料、抗氧化剂、紫外稳定剂、粘合剂、表面活性剂、润湿剂等。例如,聚烯烃薄膜可浸渍有无机化合物,例如碳酸钙、二氧化钛、粘土、二氧化硅、沸石、高岭土、云母、碳、以及它们的混合物。此类化合物可用作成孔剂,其可在拉紧薄膜时改善薄膜的透气性。这种方法进一步描述于美国专利6,605,172中。粘合剂可用于聚烯烃纤维、长丝、或非织造纤维网。适当的粘合剂为苯乙烯-丁二烯胶乳粘合剂,以商品名GENFLOTM 3 160得自OMNOVA Solutions Inc.;Akron,Ohio。所得粘合剂/聚烯烃纤维网可用作采集层,所述采集层可与吸收芯相连。聚烯烃材料(尤其是聚烯烃纤维、长丝和非织造纤维网)可用表面活性剂或润湿剂处理,例如得自Ciba Specialty Chemicals,Tarrytown,NY的IrgasurfTM。
用于吸收制品中的聚烯烃非织造材料可具有约1g/m2至约50g/m2或约5g/m2至约30g/m2的基重,如依据以下提供的基重测试所测量的。适于用作顶片的聚烯烃非织造材料可具有小于约4秒的平均液体透湿时间,如依据以下提供的液体透湿试验所测量的。在其它实施方案中,聚烯烃非织造材料可具有小于约3秒或小于约2秒的平均透湿时间。
用作阻挡腿箍的聚烯烃非织造材料可具有大于约5mbar或约6mbar且小于约10mbar或约8mbar的水头,如依据以下提供的水头测试所测量的。
适于用作底片的聚烯烃薄膜可具有大于约0.5N/cm或约1N/cm且小于约6N/cm或约5N/cm的纵向拉伸强度,如依据以下提供的拉伸测试所测量的。对于适于用作底片的可透气聚烯烃薄膜,该薄膜具有至少约2000g/m2/小时,优选地大于约2400g/m2/小时,甚至更优选地大于约3000g/m2/小时的湿气透过率(MVTR),如通过以下提供的湿气透过率测试所测量的。应认识到也用于尿布中的不可透气底片将表现出约0g/m2/小时的湿气透过率值。
C.其它聚合物-应当认识到任何上述合成聚合物可通过利用衍生自可再生资源的单体与衍生自不可再生资源(如石油)的单体的组合生成。例如,聚(丙烯酸)超吸收聚合物可由衍生自可再生资源的丙烯酸与衍生自不可再生资源的丙烯酸的组合进行聚合。衍生自可再生资源的单体可构成按重量计至少约5%[可再生资源单体的重量/所得聚合物的重量×100],按重量计至少约10%,按重量计至少约20%,按重量计至少约30%,按重量计至少约40%,或者按重量计至少约50%的超吸收聚合物。
IV.包括衍生自可再生资源的合成聚合物的吸收制品
本发明涉及包括衍生自可再生资源的合成聚合物的吸收制品。
所述聚合物具有特殊的性能特征。衍生自可再生资源的聚合物可为任何适当形式如薄膜、非织造材料、超吸收体等。
图1A为处于平展未收缩状态(即,没有弹性引起的收缩)的尿布20形式的吸收制品的示例性、非限制性实施方案的平面图。尿布20的面向衣服的表面120面向观察者,而面向身体的表面130与观察者相对。尿布20包括纵向中心线100和横向中心线110。图1B为图1A中尿布20沿横向中心线110截取的剖面图。尿布20可包括底座22。尿布20和底座22显示具有前腰区36、与前腰区36相对的后腰区38和定位在前腰区36和后腰区38之间的裆区37。腰区36和38通常包括尿布20在被穿用时环绕穿着者腰部的那些部分。腰区36和38可包括弹性元件,使得它们聚集在穿着者的腰部周围以改善贴合性和密封性。裆区37是当穿用尿布20时,尿布20通常位于穿着者两腿之间的那一部分。
尿布20和/或底座22的外周边由纵向边缘12和横向边缘14所限定。底座22可具有大致平行于纵向中心线100取向的相对的纵向边缘12。然而,为了增加贴合性,纵向边缘12可弯曲或成角度以产生例如当以平面图观察时“沙漏形”形状的尿布。底座22可具有大致平行于横向中心线110取向的相对的横向边缘14。
底座22可包括液体可透过的顶片24、底片26、以及位于顶片24和底片26之间的吸收芯28。吸收芯28可具有面向身体的表面和面向衣服的表面。顶片24可接合到芯28和/或底片26上。底片26可接合到芯28和/或顶片24上。应当认识到,其它结构体、元件或基底也可定位在芯28和顶片24和/或底片26之间。在某些实施例中,底座22包括尿布20的主结构,并且可添加其它组件而形成复合尿布结构。顶片24、底片26和吸收芯28可以多种熟知的构型组装,所述构型一般描述于美国专利3,860,003、5,151,092、5,221,274、5,554,145、5,569,234、5,580,411和6,004,306中。
吸收芯28可包括衍生自本发明的可再生资源的超吸收聚合物以及通常用于尿布和其它吸收制品中的多种其它液体吸收材料。适当的吸收材料的实例包括:通常称为透气毡的粉碎木浆,化学硬化、改性或交联的纤维素纤维,超吸收聚合物或吸收胶凝材料,包括共成形的可生物分解的微纤维在内的熔喷聚合物,包括薄纸包装材料和薄纸层压材料在内的薄纸,吸收泡沫,吸收海绵,或任何其它已知的吸收材料或材料的组合。用作吸收芯28的示例性吸收结构描述于美国专利4,610,678、4,673,402、4,834,735、4,888,231、5,137,537、5,147,345、5,342,338、5,260,345、5,387,207、5,397,316、5,625,222和6,932,800中。进一步的示例性吸收结构可包括不可移除的吸收芯组件和可移除的吸收芯组件。此类结构描述于美国专利公布2004/0039361A1、2004/0024379A1、2004/0030314A1、2003/0199844A1和2005/0228356A1中。理想的是,吸收芯28可完全由衍生自可再生资源的材料组成。然而,吸收芯28也可包括衍生自不可再生资源的材料。
吸收芯28可包括流体采集组件、流体分配组件和流体存储组件。包括采集层、分配层和存储层的适当的吸收芯28描述于美国专利6,590,136中。
其中可采用本发明的超吸收聚合物的另一种适当的吸收芯构造描述于授予Busam等人的美国专利公布2004/0167486中。上述专利公布中,吸收芯在芯内不使用或在备选方案中使用最小量的吸收性纤维材料。一般来讲,吸收芯可包括不超过约20%重量的吸收性纤维材料(即,[纤维材料的重量/吸收芯的总重量]×100)。
顶片24一般为尿布20的一部分,该部分可设置成至少部分地接触或紧邻穿着者。适当的顶片24可由多种材料制成,例如天然纤维(例如,木纤维或棉纤维)、合成纤维(例如,聚酯纤维或聚丙烯纤维)或者天然纤维与合成纤维组合的机织纤维网或非织造纤维网,开孔塑料薄膜,多孔泡沫或蜂窝状泡沫。顶片24通常为柔顺的、感觉柔软的、并且对穿着者的皮肤无刺激性。一般来讲,顶片24的至少一部分为液体可透过的,从而允许液体轻易地穿过顶片24的厚度。适当地,顶片24包括衍生自可再生资源的聚合物(例如聚乙烯)。作为另外一种选择,适当的顶片24以供应商代码055SLPV09U得自BBA Fiberweb,Brentwood,TN。
可将顶片24的任何部分涂上本领域已知的洗剂。适当的洗剂的实例包括描述于美国专利5,607,760、5,609,587、5,635,191和5,643,588中的那些。顶片24可全部地或部分地弹性化或者可被缩短,以便在顶片24和芯28之间提供空隙空间。包括弹性化的或缩短的顶片的示例性结构更详细地描述于美国专利4,892,536、4,990,147、5,037,416和5,269,775中。
底片26一般定位成使得其可成为尿布20的面向衣服表面120的至少一部分。底片26可设计成防止被吸收芯28所吸收并容纳在尿布20内的渗出物脏污可能接触尿布20的制品,例如床单和内衣。在某些实施方案中,底片26为基本上水不可透过的。然而,底片26可制成可透气的以便允许蒸汽逸出同时防止液体渗出物逸出。聚乙烯薄膜可通过内含无机颗粒材料以及随后张紧薄膜来制成可透气的。可透气底片可包括诸如机织纤维网、非织造纤维网、复合材料(如膜包衣的非织造纤维网和微孔薄膜)之类的材料。适当地,底片26包括衍生自如上所述的可再生资源的聚合物(例如聚乙烯)。衍生自不可再生资源的可供选择的底片26包括由Tredegar IndustriesInc.,Terre Haute,IN制造并以商品名X15306、X10962和X10964销售的薄膜;以及诸如由Mitsui Toatsu Co.,Japan以命名ESPOIR NO制造和由EXXON Chemical Co.,Bay City,TX以命名EXXAIRE制造的微孔薄膜。其它可供选择的可透气底片26描述于美国专利5,865,823、5,571,096和6,107,537中。
底片26也可由多于一个的层组成。例如,底片26可包括外覆盖件和内层,或者可包括两个外层和设置在它们之间的内层。外覆盖件可具有纵向边缘,并且内层可具有纵向边缘。外覆盖件可由柔软的非织造材料制成。内层可由基本上水不渗透性薄膜制成。外覆盖件和内层可通过粘合剂或任何其它适当的材料或方法接合在一起。适当地,非织造材料外覆盖件和水不渗透性薄膜包括可衍生自可再生资源的聚合物(例如,聚乙烯)。作为另外一种选择,衍生自不可再生资源的适当外覆盖件和内层分别按供应商代码A18AH0得自Corovin GmbH,Peine,Germany和按供应商代码PGBR4WPR得自RKW Gronau GmbH,Gronau,Germany。尽管本文设想了多种底片构型,但对于本领域的技术人员显而易见的是,在不背离本发明的精神和保护范围的情况下可作出许多其它的改变和变型。
尿布20也可包括扣紧系统50。当扣紧时,扣紧系统50互连前腰区36和后腰区38。当扣紧时,尿布20包括一个限制性腰部开口和两个限制性腿部开口。扣紧系统50可包括接合构件52和接纳构件54。接合构件52可包括吊钩、套环、粘合剂、胶粘剂、插片、或其它扣紧机构。接纳构件54可包括吊钩、套环、狭槽、粘合剂、胶粘剂、或其它可接纳接合构件52的扣紧机构。适当的接合构件52和接纳构件54的组合为本领域所熟知,并且包括但不限于吊钩/套环、吊钩/吊钩、粘合剂/聚合物薄膜、胶粘剂/胶粘剂、粘合剂/粘合剂、插片/狭槽和纽扣/扣孔。适当地,扣紧系统50可包括衍生自可再生资源的聚合物(例如,聚乙烯薄膜或聚乙烯非织造材料)。
尿布20可包括前耳片(未示出)和/或后耳片42。前耳片和/或后耳片42可为尿布20的一体元件(即,它们不是固定到尿布20上的独立操纵的元件,而是由尿布的一个或多个不同的层形成并且是其伸出部)。在某些实施方案中,前耳片和/或后耳片42可为接合到底座22上的离散元件,如图1A所示。离散的前耳片和/或后耳片42可通过本领域已知的任何粘结方法例如粘合剂粘结、压力粘结、热粘结等接合到底座22上。在其它实施方案中,前耳片和/或后耳片42可包括接合到底座22上的离散元件,其中底座22具有延伸超过前耳片和/或后耳片42的层、元件或基底。前耳片和后耳片42可为可延展的、不可延展的、弹性的或非弹性的。前耳片和后耳片42可由下列材料形成:非织造纤维网、机织纤维网、针织织物、聚合物膜和弹性体薄膜、开孔薄膜、海绵、泡沫、稀松布、以及它们的组合和层压体。在某些实施方案中,前耳片和后耳片42可由包括第一非织造材料42a、弹性体材料42b、以及任选地第二非织造材料42c的拉伸层压体或其它类似层压体形成。第一与第二非织造材料42a、42c可包括衍生自可再生资源的合成聚合物(例如聚乙烯)。适当的弹性体材料42b可包括诸如天然橡胶的天然弹性体或者可包括诸如弹性体薄膜的合成弹性体,所述弹性体薄膜以供应商代码X25007得自Tredegar Corp,Richmond,VA。可供选择的拉伸层压体可由设置在两个非织造层(以供应商代码FPN332得自BBA Fiberweb,Brentwood,TN)之间的Tredegar X25007弹性体形成。
尿布20还可包括腿箍32a、32b,其提供改进的液体和其它身体渗出物密封性。腿箍32a、32b也可称作衬圈箍、外腿箍、腿围、侧翼、弹性箍、阻挡箍、第二箍、内腿箍或“直立”弹性侧翼。美国专利3,860,003描述了提供可收缩腿部开口的一次性尿布,所述腿部开口具有侧翼和一个或多个弹性构件以提供弹性化腿箍(即衬圈箍)。美国专利4,808,178和4,909,803描述了具有可改善腿区容纳性的“直立”弹性侧翼(即阻挡箍)的一次性尿布。美国专利4,695,278和4,795,454描述了具有双箍(包括衬圈箍和阻挡箍)的一次性尿布。
图1A至1B示出了具有双箍(衬圈箍32a和阻挡箍32b)的尿布20。阻挡箍32b可包括一个或多个阻挡弹性构件33b。阻挡弹性构件33b可接合到阻挡箍基底34上。阻挡箍基底34可包括衍生自可再生资源的聚合物。在某些实施例中,阻挡箍基底34可为聚合物薄膜或非织造材料。阻挡箍32b可设置在底座22的面向身体的表面上。阻挡箍基底34可由底座22的纵向边缘12横向延伸至纵向边缘122内侧的一点。阻挡箍32b一般纵向延伸至少穿过裆区37。阻挡弹性构件33b使得阻挡箍32b的一部分与尿布20的面向身体的表面间隔开。
衬圈箍32a可包括一个或多个衬圈弹性构件33a。衬圈弹性构件33a可接合到尿布20的一个或多个现有元件或基底(例如顶片24、底片26、阻挡箍基底34等)上。在一些实施方案中,可期望用疏水表面涂层处理全部或部分腿箍32,如美国专利申请2005/0177123A1所述。适当的衬圈和阻挡弹性构件33a、33b包括天然橡胶、合成橡胶、以及其它弹性体。
在其它适当的实施方案中,尿布20可由制造商预成形以形成裤。裤可通过任何适当的技术来预成形,所述技术包括但不限于使用可重复扣紧的和/或不可重复扣紧的粘合件(例如,接缝、焊接、粘合剂、胶粘剂粘结、扣件等)将制品的各部分接合在一起。例如,图1A中的尿布20可被制造具有接合的扣紧系统50(即,接合构件52接合到接纳构件54上)。作为附加实例,图1A中的尿布20可制造成前耳片40通过粘结接合到后耳片42上,所述粘结例如粘合剂粘结、机械粘结、或本领域已知的某种其它粘结技术。适当的裤公开于美国专利5,246,433、5,569,234、6,120,487、6,120,489、4,940,464、5,092,861、5,897,545和5,957,908中。
V.向消费者提供吸收制品
一个或多个吸收制品(例如,尿布)220可作为包装200提供,如图2A至2B所示。通常,包装200使得一定量的吸收制品220被递送至消费者并被消费者购买,同时节省空间并简化运输和存储。包装200包括至少一个由外包裹物250保护的吸收制品220。外包裹物250可部分或全部覆盖吸收制品,所述吸收制品可压缩或未压缩。图2A描绘了完全覆盖并装入多个吸收制品220的外包裹物250。外包裹物250可包括多种材料,包括但不限于热塑性薄膜、非织造材料、机织材料、箔、织物、纸张、纸板、弹性部件、绳索、带子、以及它们的组合。其它适当的包装结构及外包裹物描述于美国专利4,846,587、4,934,535、4,966,286、5,036,978、5,050,742和5,054,619中。在某些实施方案中,外包裹物250包括衍生自可再生资源的合成聚合物(如聚烯烃)。尽管包装200的形状不受限制,但期望包装200具有平行六面体形状或基本上类似于平行六面体形状(例如,至少一个基本平底面和四个平侧面的固体)。此类形状对于包装、堆码和运输是理想的。包装200的尺寸不受限制;然而,在某些实施方案中,包装200的尺寸应不大于包含吸收制品220所需的尺寸。
包装200可具有柄部240。在某些实施方案中,柄部240可为离散元件,例如固定到外包裹物250上的带子。在图2A至2B所示的实施方案中,柄部240与外包裹物250成一整体。对于该实施方案,柄部240可包括来自外包裹物250的伸出部252。伸出部252可具有穿过其的小孔254。小孔254的理想尺寸容许成人手部的一个或多个手指通过。
开启装置260可提供在外包裹物250中。例如,在由纸张、纸板或薄膜制成的外包裹物250中,开启装置260可包括弱线262(如穿孔)。开启装置260容许侧翼256的部分或全部移除,所述侧翼为外包裹物250的一部分。侧翼256的部分或全部移除可使得更好地接近吸收制品220。开启装置260和侧翼256以封闭构型示于图2A中,并以开口构型示于图2B中。示例性开启装置260存在于美国专利申请5,036,978中。
包装200可包含多个外包裹物250。例如,多个吸收制品可用诸如热塑性薄膜的第一外包裹物保护,然后多个薄膜包裹的吸收制品可安放在诸如纸板盒或另一种热塑性薄膜的第二外包裹物内。
VI.向消费者传达相关的环境信息
本发明还可包括相关的环境信息或者还可包括向消费者传达相关的环境信息的步骤。相关的环境信息可传达包括衍生自可再生资源的聚合物的吸收制品的有益效果或优点。相关的环境信息可确定吸收制品为:环境友好或地球友好:具有降低的石油(或油类)依赖性或含量;具有降低的国外石油(或油类)依赖性或含量;具有降低的石化产品或者具有不含石化产品的组件;和/或由可再生资源制成或者具有由可再生资源制成的组件。这种传达对以下消费者很重要:可能讨厌石化产品使用的消费者(例如,关心天然资源耗竭的消费者或认为基于石化的产品不天然或不环境友好的消费者),以及有环境意识的消费者。若没有此类传达,本发明的有益效果可能对一些消费者不起作用。
传达可以多种传达形式实现。合适的传达形式包括商店展示、招贴、告示、计算机程序、小册子、包装印刷、货架信息、视频、广告、因特网址、象形图、图解、或任何其它适当的传达形式。所述信息可在商店里、电视上、可利用计算机的形式中、广告中、或任何其它适当的场合中被利用。理想的是,可采用多种传达形式来散布相关的环境信息。
传达可为书面的、口头的,或者借助一种或多种图画、图形或图标来表达。例如,基于电视或因特网的广告可具有相关的环境信息的叙述、画外音或其它可听到的传达。同样,相关的环境信息可以书面形式利用以上列举的任何适当的传达形式来传达。在某些实施方案中,可期望与目前可商购获得的吸收制品相比,量化本发明吸收制品石化产品用量的减少。
在其它实施方案中,传达形式可为一个或多个图标。图3A至3F描画了几种以图标310形式传达的适当的实施方案。一种或多种图标310可用于传达减少的石化产品用量的相关的环境信息。传达减少的石油用量的相关的环境信息的适当图标310示于图3A至3B中。传达环境友好或利用可再生资源的相关的环境信息的图标示于图3C至3F中。在某些实施方案中,图标310可位于包含吸收制品的包装200上(如图2A至2B所示)、吸收制品上、邻接包装或制品的插件上、或与以上列举的任何其它形式的传达组合。
相关的环境信息也可包括石化产品等价性的信息。如在背景技术中所介绍的,已公开了许多可再生的、天然存在的、或非石油衍生的聚合物。然而,这些聚合物经常缺乏在用于吸收制品中时消费者已期望的性能特征。因此,为了让消费者清楚如上所述衍生自可再生资源的聚合物表现出与衍生自石油的聚合物相比等价或更优的性能特征,石油等价性的信息可能是必要的。适当的石化产品等价性信息可包括与不含有衍生自可再生资源的聚合物的吸收制品的比较。例如,适当的组合信息可为“具有环境友好吸收材料的商标A尿布如商标B尿布一样能吸收”。这种信息同时传达相关的环境信息和石化产品等价性信息。
VII.制备含有衍生自可再生资源的聚合物的吸收制品的方法
本发明还涉及制备包括衍生自可再生资源的超吸收聚合物的吸收制品的方法。所述方法包括以下步骤:提供可再生资源;由所述可再生资源衍生单体;聚合所述单体以形成合成超吸收聚合物,所述聚合物具有至少约30×10-7cm3·s/g的盐水流动传导率值和至少约15g/g的耐压吸收值;并将所述超吸收聚合物结合到吸收制品中。本发明还涉及向消费者提供一个或多个吸收制品并向消费者传达降低的石化产品用量信息。衍生自可再生资源的聚合物可在结合到吸收制品中之前经历另外的工序。此类工序包括干燥、筛分、表面交联等。
本发明还涉及制备包括衍生自可再生资源的合成聚烯烃的吸收制品的方法。所述方法包括以下步骤:提供可再生资源;由所述可再生资源衍生烯烃单体;聚合所述单体以生成具有约1.0×10-14或更大的14C/C比的合成聚烯烃;以及将所述聚烯烃结合到吸收制品中。合成聚烯烃表现出一种或多种以上参考的性能特征。本发明还涉及向消费者提供一个或多个吸收制品并向消费者传达降低的石化产品用量信息。衍生自可再生资源的聚合物可在结合到吸收制品中之前经历另外的工序。此类工序包括成膜、纤维形成、环轧制等。
VIII.衍生自可再生资源的聚合物的验证
一种适当的验证技术是通过14C分析。碳-14年代测定中常见的分析技术为测量样本内14C与总碳的比率(14C/C)。研究表明化石燃料与石化产品一般具有小于约1×10-15的14C/C比。然而,完全衍生自可再生资源的聚合物通常具有约1.2×10-12的14C/C比。当比较时,衍生自可再生资源的聚合物具有的14C/C比可比衍生自石化产品的聚合物的14C/C比高三个数量级(103=1,000)。可用于本发明的聚合物具有约1.0×10-14或更大的14C/C比。在其它实施方案中,本发明的石化产品等价聚合物可具有约1.0×10-13或更大的14C/C比或1.0×10-12或更大的14C/C比。用于14C分析的合适技术为本领域所已知并包括加速器质谱法、液体闪烁计数法、以及同位素质谱法。这些技术描述于美国专利3,885155、4,427,884、4,973,841、5,438,194和5,661,299中。
IX.测试方法
盐水流动传导率
测定溶胀水凝胶层718渗透性的方法为“盐水流动传导率”,也被称作“凝胶层渗透性”,并描述于多个参考文献中,包括提交于1993年12月1日的EP A 640 330,提交于2004年2月3日的USSN 11/349,696,提交于2006年2月3日的USSN 11/347,406,提交于1982年9月30日的USSN06/682,483,以及提交于1982年10月14日的USPN 4,469,710。用于该方法的设备描述如下。
渗透性测量体系
图4示出了渗透性测量体系400,其配备有恒静压头贮存器414、准许空气进入的开口端管410、用于再填充的塞口412、实验架416、传输管418、活塞420、环形支撑架422、接受容器424、天平426与活塞/滚筒组合件428。
图5示出了包括金属砝码512、活塞轴514、活塞头518、封盖516、以及滚筒520的活塞/滚筒组合件428。滚筒520由透明的聚碳酸酯(如)制成并具有6.00cm(面积=28.27cm2)的内径p,其中内滚筒壁550为光滑的。滚筒520的底部548覆盖有美国标准400目不锈钢网布(未示出),其在连接到滚筒520的底部548上之前双向拉伸至绷紧状态。活塞轴514由透明的聚碳酸酯(如)制成并具有大约127mm的总长度q。活塞轴514的中部526具有21.15mm的直径r。活塞轴514的上部528具有15.8mm的直径s,形成轴肩524。活塞轴514的下部546具有大约5/8英寸的直径t,并具有螺纹以紧紧地拧到活塞头518的中心孔618中(参见图6)。活塞头518被穿孔,其由透明的聚碳酸酯(如)制成,并且也装有拉伸的美国标准400目不锈钢网布(未示出)。砝码512为不锈钢,具有中心孔530,滑动至活塞轴514的上部528并停留在轴肩524上。活塞头518、活塞轴514与砝码512的组合重量为596g(±6g),其对应滚筒520面积上的0.30磅/英寸2。可通过沿着活塞轴514的中心轴线532向下钻盲孔以移除材料和/或提供腔体以增加砝码来调整组合重量。滚筒封盖516在其中心具有第一封盖开口534用于垂直对准活塞轴514,且靠近边缘538具有第二封盖开口536用于将流体由恒静压头贮存器414引入滚筒520。
沿着砝码512的上表面552径向划出第一线性指示标记(未示出),所述第一线性指示标记横向于活塞轴514的中心轴线532。沿着活塞轴514的顶部表面560径向划出相应的第二线性指示标记(未示出),所述第二线性指示标记横向于活塞轴514的中心轴线532。沿着活塞轴514中部526划出相应的第三线性指示标记(未示出),所述第三线性指示标记平行于活塞轴514的中心轴线532。沿着滚筒封盖516的上表面540径向划出相应的第四线性指示标记(未示出),所述第四线性指示标记横向于活塞轴514的中心轴线532。此外,沿着滚筒封盖516的唇缘554划出相应的第五线性指示标记(未示出),所述第五线性指示标记平行于活塞轴514的中心轴线532。沿着外滚筒壁542划出相应的第六线性指示标记(未示出),所述第六线性指示标记平行于活塞轴514的中心轴线532。对齐第一、第二、第三、第四、第五和第六线性指示标记使得砝码512、活塞轴514、滚筒封盖516以及滚筒520在每次测量时用相对于彼此相同的取向重新定位。
滚筒520规格细节为:
滚筒520的外径u:70.35mm
滚筒520的内径p:60.0mm
滚筒520的高度v:60.5mm
滚筒封盖516规格细节为:
滚筒封盖516的外径w:76.05mm
滚筒封盖516的内径x:70.5mm
包括唇缘554的滚筒封盖516的厚度:12.7mm
不含唇缘的滚筒封盖516的厚度:6.35mm
第一封盖开口534的直径:22.25mm
第二封盖开口536的直径b:12.7mm
第一封盖开口534与第二封盖开口536中心之间的距离:23.5mm
砝码512规格细节为:
外径c:50.0mm
中心孔530的直径d:16.0mm
高度e:39.0mm
活塞头518规格细节为:
直径f:59.7mm
高度g:16.5mm
外孔614(总共14个)具有9.65mm的直径h,外孔614等距间隔开,其中心距中心孔618的中心47.8mm
内孔616(总共7个)具有9.65mm的直径i,内孔616等距间隔开,其中心距中心孔618的中心26.7mm
中心孔618具有5/8英寸的直径j,并被拧以容纳活塞轴514的下部546。
使用之前,应检查活塞头518和滚筒520的不锈钢筛网(未示出)是否堵塞、有洞或过度拉伸,在必要时可置换。具有损坏筛网的盐水流动传导率设备可给出错误的盐水流动传导率结果,并且在筛网已替换之前一定不要使用。
在滚筒520上于连接到滚筒520的底部548上的筛网(未示出)之上5.00cm(±0.05cm)的高度k处划出5.00cm标记556。这标志分析期间要保持的流体含量。保持正确且恒定的流体含量(静水压)对于测量准确度很关键。
恒静压头贮存器414用于传输盐溶液432至滚筒520,并保持盐溶液432的含量在连接到滚筒520的底部548上的筛网(未示出)之上5.00cm(±0.05cm)的高度k处。定位进气管410的底部434,以便在测量期间保持滚筒520内的盐溶液432的含量在所需的5.00cm高度k处,即当滚筒520位于接受容器424之上的环架440上的支撑筛网(未示出)上时,进气管410的底部434与滚筒520上的5.00cm标记556位于大致同一平面438内。进气管410与滚筒520上的5.00cm标记556的适当高度对齐对于分析很关键。适当的贮存器414由广口瓶430组成,其包含:用于流体传输的水平取向的L型传输管418、用于使得空气处于恒静压头贮存器414内的固定高度处的垂直取向的末端开口管410、以及用于再填充恒静压头贮存器414的塞口412。管410具有xx mm的内径。接近恒静压头贮存器414的底部442定位的传输管418包含用于开始/停止盐溶液432传输的活塞420。定制传输管418的出口444的尺寸以穿过滚筒封盖516上的第二封盖开口536,其末端定位在滚筒520的盐溶液432的表面之下(在盐溶液432在滚筒520内达到5.00cm高度之后)。用O形环定位套(未示出)将进气管410保持在适当位置。可将恒静压头贮存器414定位在实验室起重机416上,以便相对于滚筒520的高度调整其高度。定制恒静压头贮存器414的组件尺寸以便快速填充滚筒520至所需高度(即,静压头)并在测量期间保持该高度。恒静压头贮存器414必须能够以至少3g/s的流量传输盐溶液432至少10分钟。
将活塞/滚筒组合件428定位在16目刚性不锈钢支撑筛网(未示出)(或等同物)上,所述支撑筛网支撑在环架440或适当的可供选择的刚性架上。该支撑筛网(未示出)可充分渗透以便不会阻止盐溶液432流动,并且具有足够刚性以支撑不锈钢网布(未示出)不被拉伸。支撑筛网(未示出)应平坦且水平的以避免测试期间活塞/滚筒组合件428倾斜。将通过支撑筛网(未示出)的盐溶液432收集在接受容器424内,所述容器定位在支撑筛网(未示出)之下(但是未支撑)。将接受容器424置于精确至至少0.01g的天平426上。将天平426的数字输出连接到计算机处理的数据采集系统(未示出)上。
试剂的制备(未示出)
Jayco合成尿(JSU)712(参见图7)用作溶胀相(参见以下盐水流动传导率步骤),而0.118M的氯化钠(NaCl)溶液用作流动相(参见参见以下盐水流动传导率步骤)。以下制备是参照标准的1升体积。若制备不同于1升的体积,所有的量因此按比例称量。
JSU:用蒸馏水填充1L的容量瓶至其体积的80%,并将磁力搅拌棒置于容量瓶中。利用分析天平用称量纸或烧杯分别称量以下干燥成分的量(精确至±0.01g),并将它们以下面所列出的相同顺序定量加入到容量瓶中。在适当的搅拌盘上搅拌溶液直至所有固体溶解,取出搅拌棒,并用蒸馏水稀释溶液至1L的体积。再次放入搅拌棒,并在搅拌棒上另外搅拌溶液几分钟。
制备1升Jayco合成尿的盐用量:
氯化钾(KCl)2.00g
硫酸钠(Na2SO4)2.00g
磷酸二氢铵(NH4H2PO4)0.85g
磷酸氢二铵((NH4)2HPO4)0.15g
氯化钙(CaCl2)0.19g-[或水合氯化钙(CaCl2·2H2O)0.25g]
氯化镁(MgCl2)0.23g-[或水合氯化镁(MgCl2·6H2O)0.50g]
为了使制备更迅速,每种盐在加入下一种之前要完全溶解。Jayco合成尿可在干净的玻璃容器中储存2周。如果溶液变浑浊,则该溶液不应再使用。在干净的塑料容器中的储藏期限为10天。
0.118M的氯化钠(NaCl)溶液:0.118M的氯化钠用作盐溶液432。利用称量纸或烧杯将6.90(±0.01g)氯化钠称量并定量转移到1L的容量瓶中;用蒸馏水填充容量瓶至体积。加入搅拌棒并在搅拌盘上搅拌溶液直至所有固体溶解。
测试准备
利用实心参考圆柱型砝码(未示出)(40mm直径;140mm高度),调整内卡规(未示出)(例如Mitotoyo Digimatic Height Gage)以读零。该操作可在光滑且水平的工作台446上方便进行。将不含超吸收体活塞/滚筒组合件428置于内卡规(未示出)之下并记录读数L1,精确至0.01mm。
用盐溶液432填充恒静压头贮存器414。定位进气管410的底部434,以便在测量期间保持滚筒520中液体弯月面(未示出)的顶部(未示出)在5.00cm标记556处。进气管410在滚筒520上的5.00cm标记556处的适当高度对齐对于分析很关键。
将接受容器424置于天平426上,并将天平426的数字输出连接到计算机处理的数据采集系统(未示出)上。将带有16目刚性不锈钢支撑筛网(未示出)的环架440置于接受容器424之上。该16目筛网(未示出)应具有足够的刚性以在测量期间支撑活塞/滚筒组合件428。支撑筛网(未示出)必须平坦且水平。
盐水流动传导率步骤
利用分析天平将0.9g(±0.05g)超吸收体称量到适当的称量纸上。利用分析天平将0.9g(±0.05g)超吸收体称量到适当的称量纸上。超吸收体的含水量依据Edana含水量测试方法430.1-99(“Superabsorbent materials-Polyacrylatesuperabsorbent powders-MOISTURE CONTENT-WEIGHT LOSS UPONHEATING”(99年2月))进行测量。如果聚合物的含水量大于5%,则聚合物重量应对水分进行校正(即,添加的聚合物应基于干重为0.9g)。
将空的滚筒520放置在水平的工作台446上,并将超吸收体定量转移到滚筒520中。通过轻轻摇晃、旋转和/或轻拍滚筒520而使超吸收颗粒均匀分散在连接到滚筒520的底部548上的筛网(未示出)上。颗粒在连接到滚筒520的底部548上的筛网(未示出)上的均匀分布很重要,以获得最高的精度结果。在超吸收体已均匀分布在连接到滚筒520的底部548上的筛网(未示出)上之后,颗粒一定不能粘附到内滚筒壁550上。插入活塞轴514通过第一封盖开口534,其中封盖516的唇缘554面向活塞头518。将活塞头518小心地插入到滚筒520中至几厘米的深度。然后将封盖516放置到滚筒520的上部边缘544上,同时小心地保持活塞头518远离超吸收体。然后小心旋转封盖516和活塞轴526,以便排列第三、第四、第五和第六线性指示标记,随后将它们对齐。然后轻轻降低活塞头518(通过活塞轴514)以停留在干燥的超吸收体上。将砝码512放置在活塞轴514的上部528上,以便其停靠在轴肩524上,使得第一与第二线性指示标记对齐。封盖516的适当位置防止水凝胶层718上砝码的粘合并确保均匀分配。
溶胀相:8cm直径的烧结盘(7mm厚;如Chemglass Inc.# CG 201-51,粗孔隙)710如下达到饱和:将过量的JSU 712添加到烧结盘710上直至烧结盘710饱和。将饱和的烧结盘710置于宽的平底培养皿714中,并添加JSU 712直至其达到烧结盘710的顶部表面716。JSU的高度一定不要超过烧结盘710的高度。
连接到滚筒520的底部548上的筛网(未示出)易于拉伸。为防止拉伸,仅仅在封盖516之上用食指将侧压施加在活塞轴514上,同时抓住活塞/滚筒组合件428的滚筒520。这样就将活塞轴514对着封盖516“锁定”在适当位置,以便活塞/滚筒组合件428可被升起而不会将过度的力施加在筛网(未示出)上。
将整个活塞/滚筒组合件428以这种方式升起并置于培养皿714内的烧结盘710上。来自于培养皿714的JSU 712通过烧结盘710,并被超吸收聚合物(未示出)吸收以形成水凝胶层718。培养皿714中的JSU 712应足够用于所有的溶胀相。如果需要,可在水合期间将更多的JSU 712添加到培养皿714中,以保持JSU 712与烧结盘710的顶部表面716齐平。60分钟过后,将活塞/滚筒组合件428从烧结盘710上移除,注意如上所述对着封盖516锁定活塞轴514,并确保水凝胶层718在该步骤中不损失JSU 712或吸入空气。将活塞/滚筒组合件428置于内卡规(未示出)之下并记录读数L2,精确至0.01mm。如果读数随时间变化,则只记录初始值。由L2-L1决定水凝胶层718的厚度L0,精确至0.1mm。
将整个活塞/滚筒组合件428以上述这种方式升起并置于连接到环架440的支撑筛网(未示出)上。应注意使得水凝胶层718在该步骤中不损失JSU712或吸入空气。培养皿714中的JSU 712应足够用于所有的溶胀相。如果需要,可在水合期间将更多的JSU 712添加到培养皿714中,以保持JSU 712与5.00cm的标记556齐平。60分钟过后,将活塞/滚筒组合件428移除,注意如上所述对着封盖516锁定活塞轴514。将活塞/滚筒组合件428置于内卡规(未示出)之下,并测量厚度(未示出)为L2,精确至0.01mm。由L2-L1决定水凝胶层718的厚度L0,精确至0.1mm。如果读数随时间变化,则只记录初始值。
将活塞/滚筒组合件428转移到与环形支撑架440连接的支撑筛网(未示出)上,注意将活塞轴514对着封盖516锁定在适当位置。放置恒静压头贮存器414,使得传输管418通过第二封盖开口536。以下面的顺序开始测量:
a)打开恒静压头贮存器410的活塞420以容许盐溶液432达到滚筒520上的5.00cm标记556。该盐溶液432含量应在打开活塞420的10秒内获得。
b)一旦获得5.00cm的盐溶液432,启动数据采集程序。
借助连接到天平426上的计算机(未示出),每间隔20秒记录通过水凝胶层718的盐溶液432的质量,时间为10分钟。10分钟后,关闭恒静压头贮存器410上的活塞420。立即移除活塞/滚筒组合件428,置于内卡规(未示出)之下并记录读数L3,精确至0.01mm。如上所述,由L3-L1决定水凝胶层718的最终厚度Lf,精确至0.1mm。由(Lf/L0)×100决定水凝胶层718的厚度改变百分比。水凝胶层718厚度的改变一般在约±10%之内。
在盐水流动传导率计算中采用60秒至实验结束的数据。60秒之前采集的数据不包括在计算中。流量Fs(单位为g/s)为由60秒至600秒收集的盐溶液432的重量(单位为克)作为时间(单位为秒)函数的图的线性最小平方拟合的斜率。
在单独测量中,通过渗透性测量体系400的流量(Fa)如上所述进行测量,不同的是不存在水凝胶层718。如果Fa远远大于水凝胶层718存在时通过渗透性测量体系400的流量Fs,则不必对渗透性测量体系400(包括活塞/滚筒组合件428)的流动阻力进行校正。在该限度内,Fg=Fs,其中Fg为水凝胶层718对渗透性测量体系400的流量的贡献。然而,如果这种要求不令人满意,则以下校正用于由Fs和Fa的值计算Fg值:
Fg=(Fa×Fs)/(Fa-Fs)
水凝胶层718的盐水流动传导率(K)由下式计算:
K=[Fg(t=0)×L0]/[ρ×A×ΔP],
其中Fg为由流量结果的回归分析和由于渗透性测量体系400的流动阻力的任何校正确定的流量,单位为g/秒,L0为水凝胶层718的初始厚度,单位为cm,ρ为盐溶液432的密度,单位为gm/cm3。A(上式中)为水凝胶层718的面积,单位为cm2,ΔP为流体静压力,单位为dyne/cm2,且盐水流动传导率K的单位为cm3·秒/gm。应记录三次测定的平均值。
对于其中流量基本上恒定的水凝胶层718,可利用下式由盐水流动传导率计算渗透系数(κ):
κ=Kη
其中η为盐溶液432的粘度,单位为泊,且渗透系数κ的单位为cm2。
一般来讲,流量不必为常数。通过用流过渗透性测量体系400的盐溶液432的重量增量(单位为克)除以时间增量(单位为秒)确定通过体系的时间相关流量FS(t),单位为g/秒。仅仅在60秒和10分钟之间收集的数据用于流量计算。60秒和10分钟之间的流量结果用于计算Fs(t=0)值,即通过水凝胶层718的初始流量。通过将Fs(t)对时间的最小平方拟合结果外推至t=0计算FS(t=0)。
耐压吸收性
该测试测量超吸收聚合物所吸收的0.90%盐溶液的量,所述聚合物在围压下横向限制在活塞/滚筒组合件内一小时。利用题目为“Absorption UnderPressure”的European Disposables and Nonwovens Association(EDANA)测试方法442.2-02。
基重
该测试测量基底的每单位面积的质量。利用题目为“Mass Per Unit Area”的European Disposables and Nonwovens Association(EDANA)测试方法40.3-90。
液体透湿
该测试测量施用到基底表面上的已知体积的液体通过基底到达下面的吸收垫所用时间。利用题目为“Liquid Strike-Through Time”的EuropeanDisposables and Nonwovens Association(EDANA)测试方法150.4-99。
拉伸测试
该测试测量基底表现出的峰值载荷。进行该测试的一个优选设备是张力检验器,例如MTS Synergie100或MTS Alliance,装有计算机界面和Testworks 4软件,得自MTS Systems Corporation 14000 Technology Drive,Eden Prairie,MN,USA。该仪器测量恒定拉伸速率和力,其中牵拉钳以均匀速率移动,随着力的增加测量装置移动微乎其微的距离(小于0.13mm)。选择测力传感器使得所测样本的测量负载(例如,力)将介于测力传感器能力的10%和90%之间(通常为25N或50N的测力传感器)。
将1×1英寸(2.5×2.5cm)的样本从基底上冲切下,使用砧液压式冲压模来用冲模将薄膜切割成单个样本。生成基本上不含明显缺陷(如气泡、洞、内含物和切口)的最少三个样本。每个样本必须具有光滑且基本无缺陷的边缘。测试在具有23℃(±1℃)的温度和50%(±2%)的相对湿度的空调房间内进行至少2小时。测试之前使样本在空调房间内平衡至少2小时。
设置装有2.54cm方形胶面平钳的张力检验器的气动式夹具以给出2.54cm的标距。给样本施加足以消除可观察到的松驰但小于0.05N的张力。以25.4cm/分钟的恒定夹头速度拉伸样本,直至样本完全断裂。如果检测到样本在钳的界面处断裂或者在钳内滑动,则舍弃数据并用一个新样本重复测试,且钳压要适当调整。样本运行至少三次以抵消薄膜可变性。
将所得张力-位移数据转化成应力-应变曲线。将峰值载荷定义为样本断裂时的最大应力并记录下来,单位为牛顿每厘米宽度的样本(当平行于夹具测量时)。给定基底的峰值载荷为来自基底的每个样本的各自值的平均值。
湿气透过率(MVTR)测试
湿气透过率测试方法测量在具体温度和湿度下透过薄膜的水汽量。透过的蒸汽被CaCl2干燥剂吸收并用重量法测定。样本与已确定渗透性的参照薄膜样本(Exxon Exxaire microporous material #XBF-110W)一起重复评价三次,参照薄膜样本用作阳性对照物。
该测试利用法兰杯(制造于Delrin(McMaster-Carr Catalog #8572K34))和无水CaCl2(Wako Pure Chemical Industries,Richmond,Va.;Catalog030-00525)。
杯子的高度为55mm,具有30mm的内径和45mm的外径。杯子装有硅树脂垫圈和包含3个用于大头螺丝的孔的封盖以完全密封杯子。
该杯状物填充有CaCl2至顶部1cm内。在台面上敲击杯子10次,使CaCl2表面水平。调整CaCl2的量直至薄膜表面与CaCl2上部之间的顶部空间为1.0cm。将薄膜越过开口(30mm)放置在杯子顶部,并利用硅树脂垫圈、挡圈和大头螺丝固定。适当安装后,样本应不起皱或拉伸。
薄膜必须完全覆盖杯口A,其为0.0007065m2。
样本组合件用分析天平称重并记录至±0.001g。将样本设置在恒定温度(40±3℃)和湿度(75±3%RH)的室中5.0小时±5分钟。将样本组合件取出,覆盖Saran 并用橡皮筋固定。将样本平衡至室温30分钟,移除塑料包裹物,并对组合件重新称重,记录重量至±0.001g。所吸收的水分Ma为初始组合件重量与最终组合件重量之间的差值。湿气透过率,单位为g/m2/24小时(g/m2/24小时),计算为:
对重复结果平均化并圆整至100g/m2/24小时,例如本文中将2865g/m2/24小时圆整为2900g/m2/24小时,将275g/m2/24小时圆整为300g/m2/24小时。
水头
水头测试方法测量基底(例如,尤其是非织造材料)的耐水渗透性。利用题目为“Standard Test Method for Evaluation of Water Resistance(HydrostaticPressure)Test”的World Strategic Partners(WSP)测试方法80.6(05)。WSP方法为EDANA与Association of the Nonwoven Fabrics Industry(INDA)制定的折衷测试方法。测试在自来水流速为10±0.5cm水/分钟下进行。
X.实施例
实施例1-聚烯烃
一种适当的聚烯烃可依据以下方法生产。一种示例性可再生资源为玉米。清洗玉米并且可去胚芽。研磨玉米以生产适用于酶处理的细粉(如玉米粗粉)。将玉米给料水解(例如,液化和糖化)以得到发酵糖为农业和生物发酵领域所熟知。适当的制备路线公开于美国专利4,407,955中。通过将水添加到研磨玉米和硫酸水溶液(按重量计98%的酸)中制备干燥研磨玉米的浆液。应添加足够的硫酸以提供约1.0至约2.5pH的浆液。将浆液加热至约140℃至约220℃并加压至至少约50磅/平方英寸;然而,约100磅/平方英寸至约1,000磅/平方英寸的压力会导致淀粉更多地转换成发酵糖。浆液在上述温度和压力下保持几秒钟,最多约10分钟。浆液可流过一个或多个减压容器,以降低水解浆液的压力和温度。使浆液经过标准分离技术,例如通过离心机,以得到发酵糖浆。该糖浆通常具有至少75的右旋糖当量。所得糖浆依据技术人员熟知的方法利用适当的酵母菌株(例如,酵母属)进行发酵。所得乙醇可通过诸如蒸发或蒸馏的标准分离技术从水溶液分离出。
通过用过量浓硫酸加热乙醇至约170℃的温度而使乙醇脱水形成乙烯。也可通过使乙醇蒸汽在加热的氧化铝粉末之上通过形成乙烯。
利用任何熟知的聚合技术对所得乙烯进行聚合,例如自由基聚合、齐格勒-纳塔聚合、或茂金属催化剂聚合。支链型低密度聚乙烯(LDPE)经常通过自由基乙烯聚合来制备。线性低密度聚乙烯(LLDPE)通过称作齐格勒-纳塔聚合的更复杂步骤来制备。可对所得聚乙烯或其共混物进行加工以得到期望的最终产品如薄膜、纤维或长丝。
例如,线性低密度聚乙烯通过用其它较长链的烯烃共聚合乙烯来制备,以得到具有约0.915g/cm3至约0.925g/cm3密度的聚合物。制备49g/m2(gsm)的浇铸挤出薄膜,其包含线性低密度聚乙烯与按重量计约35%至按重量计约45%的碳酸钙(以命名SupercoatTM得自English China Clay,America,Inc.)。可通过几种路线将薄膜制成多孔的。可利用熟知的伸长方法和机械使薄膜变温并伸长至薄膜初始长度的500%。所得微孔薄膜能够表现出至少2000g/m2/24小时的湿气透过率。作为另外一种选择,可根据美国专利6,605,172中公开的方法将薄膜逐渐拉伸。所得微孔薄膜应表现出至少2000g/m2/24小时的湿气透过率。
可依据本领域熟知的方法(例如由美国专利4,405,297和4,340,563所证实)形成非织造纺粘纤维网。形成的纤维网具有约5gsm至约35gsm的基重。单根长丝可具有约5或更小的平均旦尼尔。单根长丝可具有多种横截面形状。适当的横截面形状为美国专利4,753,834中公开的银杏形状。可通过在非织造材料中掺入表面活性剂而使得所得非织造材料更具亲水性,如美国依法注册的发明H1670中所述。处理得更具亲水性的非织造材料适于用作吸收制品中的顶片。所述非织造材料应表现出小于约4秒的液体透湿时间。可通过利用表面涂层使得所得非织造材料更具疏水性,如美国公布2005/0177123A1中所述。处理得更具疏水性的非织造材料适于用作吸收制品中的箍基底。处理过的非织造材料应表现出至少约5mbar的水头。
实施例2-超吸收聚合物
甘油的制备
低芥酸菜子油通过压榨低芥酸菜子的种子获得。将大约27.5kg的低芥酸菜子油、5.3kg的甲醇和400g的甲醇钠填充到50L的圆底烧瓶中,其装备有加热套、温度计、氮入口、机械搅拌器、以及回流冷凝器。安放玻璃导出管(浸料管),以便可借助蠕动泵将液体由烧瓶底部移除。用氮气吹扫烧瓶并边搅拌边将烧瓶中的混合物加热至65℃。使混合物回流2.5小时,随后关闭加热,停止搅拌并使混合物静置20分钟。用泵将底层从烧瓶抽出并保存用于进一步使用(镏分1)。将大约1.4kg的甲醇和230g的甲醇钠添加到烧瓶中,重新开始搅拌,将所述混合物在65℃下回流另外2个小时。停止加热,将大约2.8L的水添加到烧瓶中并搅拌混合物1分钟。关闭搅拌器并将所述混合物静置20分钟。随后用泵将底层从烧瓶抽出并保存用于进一步使用(镏分2)。将大约1.6L的水添加到烧瓶中,并搅拌混合物1分钟。关闭搅拌器并将所述混合物静置20分钟。随后用泵将底层从烧瓶抽出并保存用于进一步使用(镏分3)。将镏分1、2和3组合在装备有磁力搅拌器的适当的烧瓶中。搅拌组合镏分以形成均匀混合物并加热至82℃。缓慢添加氢氧化钠溶液(50%)直至混合物的pH为11至13,温度在82℃下进一步维持10分钟。检查pH,如果小于11则添加更多的NaOH溶液。将溶液在115℃时于大约40mm Hg的真空下浓缩,直至泡沫消失(水含量小于5%)。将溶液转移到圆底烧瓶中,并利用旋转蒸发器对甘油进行真空蒸馏,其中油浴温度为170℃,冷凝器温度为130℃至140℃。控制真空度以实现适中的蒸馏速度。收集蒸馏甘油的中间镏分。
丙烯醛的制备
将大约200g的熔融氧化铝(6至12US标准筛,主要为α-相)与50g 20%的磷酸溶液混合一个小时。借助油浴温度为80℃的旋转蒸发器将混合物真空干燥。用干燥颗粒填充具有大约15mm内径和大约60cm伸直长度的不锈钢管(色谱柱)。将柱子装到气相色谱仪中,其中入口连接至注射口,出口连接至冷凝器和收集容器。将柱子和注射口加热至300℃,并以40mL/h的速度注入衍生自低芥酸菜子油的20%的甘油水溶液。任选地利用诸如氦的惰性载气以有助于传送蒸汽通过柱子。冷凝并收集来自柱子出口的蒸汽。通过分馏或本领域的技术人员已知的其它适当的方法将丙烯醛从冷凝物中分离出。
丙烯酸的制备
大约12cm×2.5cm OD的Pyrex玻璃反应器(装备有热电偶套管)装有31g(30mL总体积)催化剂,所述催化剂包含支撑在矾土上的2%重量的钯和0.5%重量的铜。反应器在152℃下的油浴中加热。使由按体积计3.4%的丙烯醛、14.8%的氧、22.9%的水汽以及58.5%的氮组成的气流以使得表面接触时间为约5秒钟的速度通过加热的催化剂。反应混合物随后通过保持在0℃下的两个串联连接的水洗器。组合收集的水溶液,并通过分馏将丙烯酸由混合物分离出。
超吸收聚合物的制备
将L-抗坏血酸(0.2081g,1.18mmol)添加到100mL的容量瓶中并溶解于蒸馏水(大约50mL)中。大约十分钟后用蒸馏水稀释溶液至容量瓶的100mL标记处,倒转量瓶并搅动以确保溶液均匀。
向3L的夹套树脂锅内加入TMPTA(0.261g,0.881mmol)、丙烯酸(296.40g,4.11mol)和蒸馏水(250g)。水借助保持在25℃下的循环水浴通过树脂锅的夹套循环。向该单体溶液中加入标准的5当量浓度的氢氧化钠溶液(576mL,2.88mol)。用含有几个端口的封盖盖住树脂锅。利用中心端口内的气密性轴衬架起悬臂式机械搅拌器。将温度计插穿另一个端口内的密封件,使得温度计的感温球在整个反应过程中均浸没于混合物内。利用悬臂式机械搅拌器搅拌溶液,并利用烧结的气体分散管用氮气吹扫大约15分钟。利用插穿封盖隔膜的18号注射器针头将氮气由树脂锅放出。
大约15分钟之后升高烧结的气体分散管在单体溶液表面之上,并使氮气流过树脂锅的顶部空间。用注射器加入蒸馏水(5mL)配制的过硫酸钠(0.4906g,2.06mmol)溶液,随后加入少量的L-抗坏血酸溶液(1mL,1.18mmol)。当聚合物溶液中的涡旋由于溶液粘度的增加而消失时(加入L-抗坏血酸溶液后几秒钟)停止机械搅拌器。利用25℃下的循环浴使聚合反应进行30分钟。30分钟后水浴的温度增加至40℃,再另外持续30分钟。水浴的温度随后增加至50℃,再另外持续一小时。静态聚合的峰值温度为大约70℃。
50℃下一小时过后关闭循环水浴。打开树脂锅;取出聚丙烯酸酯凝胶并破碎成直径约2cm的小块。利用厨房用搅拌器(Proline型号KSM5)上的具有4.6mm孔的食物研磨器附件将这些破碎成较小颗粒。蒸馏水由喷射瓶定时添加到研磨器的横切部分,以有利于整体凝胶通过研磨器。大约200g蒸馏水用于此目的。将破碎的凝胶在两个单独的聚酯目筛网(每个尺寸为大约56cm×48cm)上铺展成薄层,并在通风烘箱内以使得空气通过网孔的形式于150℃下干燥90分钟。
然后通过实验室用Wiley研磨机利用20目筛网将干燥凝胶研磨。注意确保研磨过程中筛网不被堵塞。对研磨的干燥凝胶筛分以获得其中颗粒通过20号美国标准测试筛且保留在270号美国标准测试筛上的部分。丢弃“留在20号上”和“通过270号”的部分。
在室温下真空干燥所得“通过20号”且“留在270号上”的自由流动的粉末部分直至进一步使用。
通过将10.0克的碳酸乙二酯(1,3-二氧杂环戊烷-2-酮)溶解于10.0克蒸馏水中制备50%的碳酸乙二酯溶液。
将100.00克上述干燥的“通过20号”且“留在270号上”的粉末添加到厨房用搅拌器(Proline型号KSM5)的不锈钢搅拌钵(大约4L)(其装备有不锈钢搅打器)中。调整搅拌钵的高度直至搅打器恰好接触钵。启动搅打器并调整到“6”的速度设置以搅动颗粒。之后立即用带有四英寸22号针头的10mL塑料注射器将15克上述50%重量的碳酸乙二酯溶液添加到搅拌的AGM中。几秒钟过后将溶液直接添加到搅拌的颗粒上。在添加溶液之前和之后称量注射器以确定添加到颗粒上的量。添加溶液之后,搅动混合物大约三十秒以确保均匀涂敷。所得混合物相当均匀,没有明显的大块物质或残余的干燥粉末。随后将混合物立即转移到特氟隆内衬的20cm×35cm金属盘中,铺展成薄层并置于185℃下的通风烘箱中一个小时。
一个小时后,将混合物从烘箱中取出并使其冷却大约一分钟。冷却后,将粉末置于12cm直径的研钵中,用研杵将任何附聚片轻轻破碎。将所得粉末筛分以获得通过20号美国标准筛但保留在270号美国标准筛上的部分。
在室温下真空存储所得“通过20号”且“留在270号上”的超吸收聚合物颗粒直至进一步使用。该材料的耐压吸收值依据EDANA测试方法442.2-02进行测量,而盐水流动传导率值依据上述盐水流动传导率测试方法进行测量。耐压吸收值据发现为约21g/g,而盐水流动传导率值据发现为约50×10-7cm3·秒/g。
在发明详述中引用的所有文件都在相关部分中以引用方式并入本文中。对于任何文件的引用不应当解释为承认其是有关本发明的现有技术。当本发明中术语的任何含义或定义与以引用方式并入的文件中术语的任何含义或定义矛盾时,应当服从在本发明中赋予该术语的含义或定义。
虽然已经举例说明和描述了本发明的特定实施方案,但是对于本领域技术人员来说显而易见的是,在不背离本发明实质和范围的情况下可以做出多个其他改变和变型。应当清楚的是,所述实施方案和特征的组合是可能的,并且可在本发明的范围内进行实施。因此,权利要求书意欲包括在本发明范围内的所有这样的改变和变型。
Claims (13)
1.一种具有相对的纵向边缘的吸收制品,所述吸收制品包括:
a)顶片,
b)与所述顶片接合的底片,
c)设置在所述顶片与所述底片之间的吸收芯,和
d)通过至少一种第一中间化合物衍生自第一可再生资源的第一聚合物,其中所述第一聚合物为合成的,并且其中所述第一中间化合物为单体,并且其中所述第一聚合物设置在或结合到所述吸收制品的一个或多个元件中,所述元件选自所述吸收芯、所述顶片、所述底片和阻挡腿箍。
2.如权利要求1所述的吸收制品,其中所述第一聚合物为超吸收体并设置在所述吸收芯中,所述第一聚合物表现出:
i)至少约30×10-7cm3·秒/g的盐水流动传导率值;和
ii)至少约15g/g的耐压吸收值。
3.如前述任一项权利要求所述的吸收制品,其中所述第一聚合物包含约50mol%至约100mol%被中和的轻度交联的聚丙烯酸。
4.如前述任一项权利要求所述的吸收制品,其中所述第一聚合物表现出约1.0×10-14或更大的14C/C比。
5.如前述任一项权利要求所述的吸收制品,其中所述第一中间化合物选自:有机酸、糖、单官能醇、多官能醇、有机醛和有机酯。
6.如前述任一项权利要求所述的吸收制品,其中所述第一聚合物通过第一中间化合物、第二中间化合物和第三中间化合物衍生自第一可再生资源,其中所述第一中间化合物为甘油,所述第二中间化合物为丙烯醛,并且所述第三中间化合物为丙烯酸。
7.如前述任一项权利要求所述的吸收制品,所述吸收制品还包括通过至少一种第二中间化合物衍生自第二可再生资源的第二聚合物,其中所述第二聚合物设置在或结合到所述吸收制品的一个或多个元件中,所述元件选自所述吸收芯、所述顶片、所述底片和所述阻挡腿箍。
8.如权利要求1所述的吸收制品,其中所述第一聚合物为聚烯烃,并且其中所述顶片包括所述聚烯烃,其中所述顶片表现出小于约4秒的液体透湿时间。
9.如权利要求1所述的吸收制品,其中所述第一聚合物为聚烯烃,并且其中所述底片包括所述聚烯烃,所述聚烯烃为薄膜形式,其中所述薄膜表现出至少约0.5N/cm的纵向拉伸强度。
10.如权利要求1所述的吸收制品,其中所述第一聚合物为聚烯烃,并且其中所述底片包括所述聚烯烃,所述聚烯烃为可透气薄膜形式,其中所述可透气薄膜表现出至少约2000g/m2/24小时的湿气透过率。
11.如权利要求1所述的吸收制品,其中所述第一聚合物为聚烯烃,并且其中所述阻挡腿箍包括箍基底,并且其中所述箍基底包括所述聚烯烃,并且其中所述箍基底表现出至少约5mbar的水头。
12.如前述任一项权利要求所述的吸收制品,其中所述第一聚合物表现出约1.0×10-13或更大的14C/C比。
13.如前述任一项权利要求所述的吸收制品,其中所述第一聚合物表现出约1.0×10-12或更大的14C/C比。
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US8705450B2 (en) * | 2008-07-30 | 2014-04-22 | Koninklijke Philips N.V. | Method for discovering paths with sufficient medium time in wireless mesh networks |
US20100311179A1 (en) | 2009-06-03 | 2010-12-09 | Sarah Coulter | Method of Using 14C Measurements to Determine the Percent Natural of Cleaning Compositions |
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2007
- 2007-03-15 US US11/724,341 patent/US20070219521A1/en not_active Abandoned
- 2007-03-16 CA CA002647293A patent/CA2647293A1/en not_active Abandoned
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- 2007-03-16 CN CN2007800177141A patent/CN101442965B/zh not_active Expired - Fee Related
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2010
- 2010-12-22 US US12/975,973 patent/US20110152812A1/en not_active Abandoned
- 2010-12-22 US US12/976,101 patent/US20110139659A1/en not_active Abandoned
- 2010-12-22 US US12/976,043 patent/US20110139662A1/en not_active Abandoned
- 2010-12-22 US US12/975,914 patent/US20110139658A1/en not_active Abandoned
- 2010-12-22 US US12/975,838 patent/US20110139657A1/en not_active Abandoned
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2013
- 2013-08-06 US US13/959,841 patent/US20130313149A1/en not_active Abandoned
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2016
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2018
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2019
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2021
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- 2022-02-24 US US17/679,408 patent/US20220178124A1/en active Pending
Cited By (7)
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CN102482187A (zh) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | 从丙三醇制备生物来源化的丙烯酸的方法 |
CN102482187B (zh) * | 2009-07-22 | 2015-05-20 | 阿肯马法国公司 | 从丙三醇制备生物来源化的丙烯酸的方法 |
CN103328334A (zh) * | 2011-01-25 | 2013-09-25 | 宝洁公司 | 用于消费品的可持续的包装 |
CN103328334B (zh) * | 2011-01-25 | 2015-06-17 | 宝洁公司 | 用于消费品的可持续的包装 |
CN107261194A (zh) * | 2016-03-30 | 2017-10-20 | 巴斯夫欧洲公司 | 流体吸收制品 |
CN107261194B (zh) * | 2016-03-30 | 2021-11-30 | 巴斯夫欧洲公司 | 流体吸收制品 |
CN110035723A (zh) * | 2016-12-06 | 2019-07-19 | 诺沃梅尔公司 | 具有较高生物基含量的可生物降解卫生用品 |
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US20110152812A1 (en) | 2011-06-23 |
US10920407B2 (en) | 2021-02-16 |
US20110139659A1 (en) | 2011-06-16 |
US10166312B2 (en) | 2019-01-01 |
WO2007109128A2 (en) | 2007-09-27 |
US20110139662A1 (en) | 2011-06-16 |
US20210198881A1 (en) | 2021-07-01 |
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US10815653B2 (en) | 2020-10-27 |
US20190085543A1 (en) | 2019-03-21 |
WO2007109128A3 (en) | 2007-11-22 |
US20200063415A1 (en) | 2020-02-27 |
US20110139658A1 (en) | 2011-06-16 |
US20070219521A1 (en) | 2007-09-20 |
US20200063417A1 (en) | 2020-02-27 |
US20160206774A1 (en) | 2016-07-21 |
CA2647293A1 (en) | 2007-09-27 |
CN101442965B (zh) | 2013-06-19 |
US20210131086A1 (en) | 2021-05-06 |
US10501920B2 (en) | 2019-12-10 |
US10822783B2 (en) | 2020-11-03 |
US20110139657A1 (en) | 2011-06-16 |
US20200063416A1 (en) | 2020-02-27 |
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