CN100569849C - 包含具有高流动性的嵌段共聚物的弹性体双组分纤维 - Google Patents
包含具有高流动性的嵌段共聚物的弹性体双组分纤维 Download PDFInfo
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Abstract
可以在高的生产速率下由熔体连续挤出而制备的具有壳-核形态的双组分纤维,其中壳是热塑性聚合物,核是弹性体型混合料。该弹性体型混合料包含具有高流动性的偶联的、选择性氢化的嵌段共聚物。该嵌段共聚物包含至少一个分子量为5,000-7,000的聚苯乙烯嵌段和至少一个分子量为20,000-70,000的聚二烯烃嵌段,并且具有60mol%或更大的高乙烯基含量。该双组分纤维可用于制备一些制品,例如机织织物、纺粘法无纺织物或过滤器、短纤维、纱线和粘合的梳理纤维网。可以采用包括将热塑性聚合物和弹性体型混合料共挤出的方法在大于800mpm的条件下来制备该双组分纤维,制得具有0.1-50克/9000米旦尼尔的纤维。
Description
相关申请的交叉参考
本申请要求于2004年3月3日提交的题目为“具有高流动性和高弹性的嵌段共聚物”的美国临时专利申请序列号60/549,570的优先权。
发明领域
本发明涉及包含热塑性聚合物壳和弹性体核的双组分纤维。特别地,该弹性体核包含具有高流动性的单链烯基芳烃和共轭二烯烃嵌段的嵌段共聚物。本发明还涉及制备双组分纤维的方法。本发明进一步涉及由双组分纤维制得的制品。
技术背景
我们发现了由弹性材料制得的纤维在从机织织物到纺粘法弹性垫到一次性个人卫生用品中的各种应用。将特别有利的是将苯乙烯类嵌段共聚物用于这些应用。然而,嵌段共聚物典型的相分离性质导致了高的熔体弹性和高的熔体粘度。为了将苯乙烯类嵌段共聚物加工通过例如在纤维喷丝头中发现的小的孔口,将需要昂贵并且特殊的熔体泵设备。另外,高的熔体弹性导致了纤维当其排出模头时断裂,阻止了连续的弹性体纤维的形成。因此,发现在高的加工速率下极其难以将苯乙烯类嵌段共聚物加工成连续的弹性纤维。
伴随着苯乙烯类嵌段共聚物的另一个问题是它们在熔体中固有的粘性。由于该特性,苯乙烯类嵌段共聚物的熔体纺丝纤维在加工期间往往会粘结在一起或者自-粘结。该效果不是所希望的,并且在实际中当单根的连续纤维作为目标时这会成为极大的问题。除了不可接受的纤维产品的结果之外,纤维的自-粘结导致了设备结垢和代价昂贵的停机。迄今为止将苯乙烯类嵌段共聚物用于弹性纤维制备的尝试遭遇了显著的挑战。
Himes在美国专利4,892,903中教导了使用三嵌段/二嵌段共聚物共混物作为制备弹性体纤维的一种方法。已经发现这类组合物具有高的粘度和熔体弹性,这限制了它们形成例如用于熔喷法的无纺应用中的非连续和连续的纤维。
Greak在欧洲专利申请0461726中教导了包含酸官能化的苯乙烯类嵌段共聚物的双组分纤维。酸官能化的常规选择性氢化的苯乙烯类嵌段共聚物被用于与聚酰胺一起形成并列型的双组分纤维。尽管所提供的酸官能化提高了两种组分之间的粘合性,但在本领域中非常公知的是酸官能化导致了与未官能化的嵌段共聚物相比甚至更高的熔体粘度和熔体弹性。另外,Greak教导的并列型形态将不能阻止固有粘结的纤维在加工期间免于自-粘结。
Austin在美国专利6,225,243中教导使用除了其它聚合物之外还包含常规的苯乙烯类嵌段共聚物并且具有各种形态的双组分纤维制备粘合的无纺网。特别地,核由苯乙烯类嵌段共聚物组成的壳-核形态提供了具有适宜低的粘性以形成无纺网的纤维。
然而,常规苯乙烯类嵌段共聚物高的粘度和熔体弹性仍然阻止了连续的弹性体纤维的高速纺丝。本发明通过提供一种能够形成连续的弹性体型双组分纤维的高熔体流动性嵌段共聚物而解决了这些持续已久的需求。
发明概述
在一个方面中,本发明是一种包含热塑性聚合物壳和弹性体核的双组分纤维,其中该弹性体核包含具有S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物:
S-E-S,(S-E1)n,(S-E1)nS,(S-E1)nX
其中:
a.在氢化之前,S嵌段是聚苯乙烯嵌段;
b.在氢化之前,E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段;
c.在氢化之前,E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段;
d.n具有2-6的值,X为偶联剂残基;
e.该嵌段共聚物的苯乙烯含量为13-25wt%;
f.氢化之前聚二烯烃嵌段的乙烯基含量为70-85mol%;
g.该嵌段共聚物包含少于15wt%的具有以下通式的单元:
S-E或S-E1
其中S、E和E1如同已经定义的那样;
h.在氢化之后,约0-10%的苯乙烯双键被氢化,并且至少80%的共轭二烯烃双键被氢化;
i.每一S嵌段的分子量为5,000-7,000;和
j.根据ASTM D1238在230℃和2.16kg重量下,该嵌段共聚物的熔体指数大于或等于12克/10分钟。
在另一个方面中,本发明是一种例如为以下物质的制品:包含有本文中所述的双组分纤维的弹性体单丝、机织织物、纺粘法无纺织物、熔喷法无纺织物或过滤器、短纤维、纱线或者粘合的梳理纤维网。
在另一个方面中,本发明是一种制备双组分纤维的方法,其包括:将热塑性聚合物和包含本文中所述的选择性氢化的嵌段共聚物的弹性体型混合料共挤出,其中在至少500米/分钟的速率下采用单独的熔体泵使热塑性聚合物和弹性体型混合料通过模头以形成一根或多根具有主要由热塑性聚合物组成的壳和主要由弹性体型混合料组成的核的纤维,以使得所得的双组分纤维具有每根长丝为0.1-10克/9000米的旦尼尔。
重要的是,本发明将弹性体型混合料包含在具有高熔体流动性的核中,这使得能够在商业类型的设备上在高速率下制得双组分纤维。该弹性体型混合料核的高熔体流动性可以借助于具有高的乙烯基含量、足够低的分子量的选择性氢化的嵌段共聚物或者通过这些特征的一些组合来实现。
弹性体型混合料核可以进一步包含组成与壳材料相同或不同的热塑性聚合物。将热塑性聚合物掺入弹性体核中可以提高核-壳相容性、提高核-壳粘合性、提高弹性体型混合料的加工性和/或提高材料经济性。
附图简述
图1示出了本发明的双组分纤维束的横截面。热塑性聚合物壳在每一弹性体核的周围表现为环形区域。
优选实施方案的详细描述
本发明的双组分纤维包括热塑性聚合物壳和包含选择性氢化的嵌段共聚物的弹性体型混合料核。该双组分纤维通过其中将热塑性聚合物和弹性体型混合料核分别计量到模头或者喷丝头中的共挤出方法而制备。这类共挤出的双组分纤维可以具有多种形态,这些包括,但不限于壳-核、并列型、天星状、双叶形、三叶形和馅饼截面(pie-section)。
在本发明中,重要的是壳形成了纤维的大部分外表面。特别优选其中壳在核的周围形成覆盖层的壳-核形态。在该优选形态中,核可以处于纤维横截面的中心或者可以偏离中心。壳可以在纤维的周围以完全的方式将核覆盖,或者可以在纤维的周围仅仅部分覆盖。在周围部分覆盖的情况下,该形态与并列型形态的不同在于核占了纤维的大部分体积。在本发明中,壳与核的体积比为5/95-49/51。壳与核体积比的优选范围是10/90-40/60,最优选的范围是20/80-30/70。壳主要由热塑性聚合物组成,核主要由弹性体型混合料组成。本文中使用的“主要由...组成”是指以体积为基准大于80%。
弹性体型混合料核包含具有S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物:
S-E-S,(S-E1)n,(S-E1)nS,(S-E1)nX
其中:(a)在氢化之前,S嵌段是聚苯乙烯嵌段;(b)在氢化之前,E嵌段或E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的聚二烯烃嵌段。该嵌段共聚物可以是线型的或者是具有3-6个臂的星形的。线型构造的通式包括:
S-E-S和/或(S-E1)n和/或(S-E1)nS
其中E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段;E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段;n具有2-6,优选2-4,更优选平均约为3的值。举例来说,具有3和4个臂的星形构造的通式包括:
和
其中E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段;X是偶联剂残基。
本文中使用的术语“分子量”是指以克/摩尔计的聚合物或共聚物的嵌段的真实分子量。在本说明书和权利要求书中引用的分子量可以借助于例如根据ASTM 3536进行的使用聚苯乙烯校正标准的凝胶渗透色谱法(GPC)测量。GPC是一种非常公知的方法,其中根据分子大小(最大的分子首先洗脱)而将聚合物分开。使用可商购获得的聚苯乙烯分子量标准来校正色谱图。采用如此校正的GPC测量的聚合物分子量是苯乙烯当量分子量。当获知了聚合物的苯乙烯含量和二烯烃链段的乙烯基含量时,可以将苯乙烯当量分子量转化成真实分子量。使用的检测器优选是组合的紫外线和折射率检测器。本文中所述的分子量在GPC轨迹的峰处测量、其被转化成真实分子量,并且通常被称作“峰值分子量”。
本发明的嵌段共聚物通过苯乙烯和选自丁二烯、异戊二烯及其混合物的二烯烃的阴离子聚合而制备。通过在约-150℃至约300℃的温度下,优选在约0℃-约100℃的温度下在合适的溶剂中将苯乙烯和二烯烃单体与有机碱金属化合物接触而实现该聚合。特别有效的阴离子聚合引发剂是具有通式RLin的有机锂化合物,其中R是含有1-20个碳原子的脂族烃基、脂环族烃基、芳族或烷基取代的芳族烃基,n具有1-4的值。优选的引发剂包括正丁基锂和仲丁基锂。用于阴离子聚合的方法是非常公知的,并且可以在例如美国专利No.4,039,593和美国重新颁发的专利No.Re27,145的一些参考文献中找到。
本发明的嵌段共聚物可以是线型的、线型偶联的,或者是具有2-6个“臂”的混合物的星形嵌段共聚物。线型嵌段共聚物可以通过将苯乙烯聚合以形成第一S嵌段、加入丁二烯以形成E嵌段,然后加入另外的苯乙烯以形成第二S嵌段而制备。线型偶联的嵌段共聚物通过形成第一S嵌段和E嵌段,然后将该二嵌段与双官能偶联剂接触而制备。星形嵌段共聚物通过使用至少三官能的偶联剂而制备。
可用于制备线型嵌段共聚物的双官能偶联剂包括,例如披露于美国专利No.3,766,301中的苯甲酸甲酯。其它可用于形成星形嵌段共聚物的具有两个、三个或四个官能团的偶联剂包括,例如披露于美国专利Nos.3,244,664、3,692,874、4,076,915、5,075,377、5,272,214和5,681,895中的四氯化硅和烷氧基硅烷;披露于美国专利No.3,281,383中的聚环氧化物、聚异氰酸酯、聚亚胺、聚醛、聚酮、聚酐、聚酯、多卤化物;披露于美国专利No.3,594,452中的二酯;披露于美国专利No.3,880,954中的甲氧基硅烷;披露于美国专利3,985,830中的二乙烯基苯;披露于美国专利No.4,104,332中的1,3,5-苯三羧酸三氯化物;披露于美国专利No.4,185,042中的环氧丙氧基三甲氧基硅烷;和披露于美国专利No.4,379,891中的氧基二丙基双(三甲氧基硅烷)。
在本发明的一个实施方案中,使用的偶联剂是通式为Rx-Si-(OR’)y的烷氧基硅烷,其中x为0或1,x+y=3或4,R和R’相同或不同,R选自芳基、线型烷基和支化的烷基烃基,R’选自线型和支化的烷基烃基。芳基优选含有6-12个碳原子。烷基优选含有1-12个碳原子,更优选1-4个碳原子。在熔融条件下,这些烷氧基硅烷偶联剂可以进一步偶联以产生大于4的官能度。优选的四烷氧基硅烷是四甲氧基硅烷(“TMSi”)、四乙氧基硅烷(“TESi”)、四丁氧基硅烷(“TBSi”)和四(2-乙基己氧基)硅烷(“TEHSi”)。优选的三烷氧基硅烷是甲基三甲氧基硅烷(“MTMS”)、甲基三乙氧基硅烷(“MTES”)、异丁基三甲氧基硅烷(“IBTMO”)和苯基三甲氧基硅烷(“PhTMO”)。在这些当中,更优选的是四乙氧基硅烷和甲基三甲氧基硅烷。
本发明的一个重要方面是聚合物的微观结构。与本发明相关的微观结构是E和/或E1嵌段中高含量的乙烯基。该结构可以通过在二烯烃的聚合期间使用控制剂而获得。典型的试剂是二乙醚。参见美国专利No.Re27,145和美国专利No.5,777,031,其披露内容在此引入作为参考。对于在制备嵌段共聚物领域中的那些普通技术人员而言所公知的可以使用的任何微观结构控制剂可被用于制备本发明的嵌段共聚物。
在本发明的实践中,制备嵌段共聚物以使得它们在氢化之前在E和/或E1嵌段中含有约60-约85mol%的乙烯基。在另一个实施方案中,制备嵌段共聚物以使得它们具有约65-约85mol%的乙烯基含量。在仍然另一个实施方案中,制备嵌段共聚物以使得它们具有约70-约85mol%的乙烯基含量。本发明的另一个实施方案包括以使得它们在E和/或E1嵌段中具有约73-约83mol%的乙烯基含量而制备的嵌段共聚物。
在一个实施方案中,本发明是一种氢化的嵌段共聚物。采用本领域公知的几种氢化方法的任何一种而将本发明的氢化嵌段共聚物选择性氢化。例如,可以采用如在美国专利Nos.3,494,942;3,634,594;3,670,054;3,700,633和Re.27,145中教导的那些方法实现氢化,这些专利的披露内容在此引入作为参考。选择性地用于共轭聚二烯烃嵌段中的双键、而将聚苯乙烯嵌段中的芳族不饱和度保持基本完整的任何氢化方法可用于制备本发明的氢化的嵌段共聚物。
在现有技术中公知的并且可用于制备本发明的氢化的嵌段共聚物的方法涉及到使用合适的催化剂,特别是包含铁族金属原子(特别是镍或钴)和合适的还原剂(例如,烷基铝)的催化剂或催化剂前体。还可以使用的是钛基催化剂体系。一般而言,氢化可以在合适的溶剂中在约20℃-约100℃的温度下和在约100psig(689kPa)-约5,000psig(34,473kPa)的氢气分压下完成。通常采用基于全部溶液以重量计约10ppm-约500ppm的铁族金属的催化剂浓度,并且通常在氢化条件下使接触持续约60-约240分钟的时间。在氢化结束后,将通常使氢化催化剂和催化剂残余物与聚合物分离。
在本发明的实践中,该氢化的嵌段共聚物的氢化度大于80%。这意味着E或E1嵌段中超过80%的共轭二烯烃双键从烯烃被氢化至烷烃。在一个实施方案中,E或E1嵌段的氢化度大于约90%。在另一个实施方案中,E或E1嵌段的氢化度大于约95%。
在本发明的实践中,嵌段共聚物的苯乙烯含量约为13-约25wt%。在一个实施方案中,嵌段共聚物的苯乙烯含量约为15-约24%。处于这些范围内的任何苯乙烯含量可用于本发明。在本发明的实践中,在氢化之后,S嵌段中0-10%的苯乙烯双键被氢化。
在本发明的嵌段共聚物中,每一S嵌段的分子量约为5,000-约7,000。在一个实施方案中,每一S嵌段的分子量约为5,800-约6,600。本发明的嵌段共聚物的S嵌段可以是具有处于这些范围内的任何分子量的聚苯乙烯嵌段。
在本发明的实践中,E嵌段是单个聚二烯烃嵌段。这些聚二烯烃嵌段可以具有约40,000-约70,000的分子量。E1嵌段是分子量约20,000-约35,000的聚二烯烃嵌段。在一个实施方案中,E嵌段的分子量范围约为45,000-约60,000,并且在被偶联之前,偶联的嵌段共聚物的每一E1嵌段的分子量范围约为22,500-约30,000。
本发明优于常规的氢化嵌段共聚物的一个优点在于它们具有高的熔体流动性,这使得它们能够容易地被模塑或者被连续地挤出成成型体或薄膜或者被纺丝成纤维。该性能使得最终使用者避免或者至少限制了使用使性能退化、造成区域污染、发烟并且甚至在模子和模头上形成积聚的添加剂。但是,本发明氢化的嵌段共聚物的会造成这些所不希望的效应的杂质,例如得自于不充分偶联的二嵌段同样非常少。本发明的嵌段共聚物和氢化的嵌段共聚物具有少于15wt%的二嵌段含量,例如具有以下通式的二嵌段:
SE或SE1
其中S、E和E1如前所定义。在一个实施方案中,二嵌段含量少于10%,在另一个实施方案中少于8%。例如,在氢化的嵌段共聚物的结构为(S-E1)2X的情况下,该嵌段共聚物含有少于10%的S-E1类物质。所有百分比以重量计。
本发明氢化的嵌段共聚物的一个特征在于它们具有低的有序-无序温度。本发明氢化的嵌段共聚物的有序-无序温度(ODT)通常小于约250℃。高于250℃,聚合物更难以加工,尽管对于一些应用而言在某些情况下可以采用大于250℃的ODT。一种这样的情形是当将嵌段共聚物与其它组分组合以改进加工性时。这些其它的组分可以是热塑性聚合物、油、树脂、蜡等。在一个实施方案中,ODT小于约240℃。优选地,本发明氢化的嵌段共聚物的ODT约为210℃-约240℃。在某些应用中该性能可能是重要的,因为当ODT低于210℃时,嵌段共聚物可能展现出令人不希望地过多或低强度的蠕变。出于本发明的目的,将有序-无序温度定义为在其上可以通过毛细管流变仪或动态流变仪测量零剪切粘度的温度。
出于本发明的目的,术语“熔体指数”是根据ASTM D1238在230℃和2.16kg重量下聚合物熔体流动性的量度。其以10分钟内通过熔体流变仪孔口的聚合物克数为单位表示。本发明氢化的嵌段共聚物具有所希望的高熔体指数,这使得其与具有较高熔体指数的类似的氢化嵌段共聚物相比更容易加工。在一个实施方案中,本发明氢化的嵌段共聚物的熔体指数大于或等于12。在另一个实施方案中,本发明氢化的嵌段共聚物的熔体指数至少为15。在仍然另一个实施方案中,本发明氢化的嵌段共聚物的熔体指数至少为40。本发明的另一个实施方案包括熔体指数约为20-约100的氢化的嵌段共聚物。本发明的仍然另一个实施方案包括熔体指数约为50-约85的氢化的嵌段共聚物。
在另一个实施方案中,弹性体型混合料核进一步包含热塑性聚合物。在该实施方案中,弹性体核包含至多50wt%的热塑性聚合物,例如聚丙烯、线型低密度聚乙烯、聚酰胺、聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸丁二醇酯)、聚(对苯二甲酸亚丙基酯)和在本文中关于壳组成所描述的其它热塑性物质。
在仍然另一个实施方案中,双组分纤维的弹性体核包含乙烯基含量约20-约60mol%的选择性氢化的嵌段共聚物。在该实施方案中,嵌段共聚物具有总的真实分子量,这使得其具有根据本文中所述的高熔体指数。
本发明包括主要由热塑性聚合物组成的壳。例举的热塑性聚合物包括,例如乙烯均聚物、乙烯/α-烯烃共聚物、丙烯均聚物、丙烯/α-烯烃共聚物、耐冲击聚丙烯共聚物、丁烯均聚物、丁烯/α-烯烃共聚物,和其它的α-烯烃共聚物或互聚物。
代表性的聚乙烯包括例如,但不限于,基本线型的乙烯聚合物、均匀支化的线型乙烯聚合物、非均匀支化的线型乙烯聚合物,包括线型低密度聚乙烯(LLDPE)、超低或甚低密度聚乙烯(ULDPE或VLDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)和高压低密度聚乙烯(LDPE)。
当热塑性聚合物是聚乙烯时,根据ASTM D1238在230℃和2.16kg重量下的熔体流动速率-也被称作熔体流动指数必须至少为25克/10分钟。优选的聚乙烯类型是线型低密度聚乙烯。
代表性的聚丙烯包括例如,但不限于,基本全同立构的丙烯均聚物、其中丙烯以摩尔基准计为主要组分的无规α-烯烃/丙烯共聚物、和其中聚合物基质主要是聚丙烯均聚物或无规共聚物并且橡胶相是α-烯烃/丙烯无规共聚物的聚丙烯耐冲击共聚物。根据ASTM D1238在230℃和2.16kg下,合适的聚丙烯熔体流动速率至少为10克/10分钟。更优选至少为20克/10分钟的熔体流动速率。聚丙烯均聚物是优选类型的聚丙烯。
乙烯/α-烯烃共聚物和丙烯/α-烯烃共聚物的例子包括,但不限于,得自于Dow Chemical的AFFINITY、ENGAGE和VERSIFY聚合物与得自于Exxon Mobil的EXACT和VISTAMAXX聚合物。根据ASTM D1238在230℃和2.16kg重量下,这些共聚物合适的熔体流动速率必须至少为10克/10分钟。
本文中包括的仍然另一些热塑性聚合物是聚氯乙烯(PVC)以及PVC与其它材料的共混物、聚酰胺和聚酯例如聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸丁二醇酯)和聚(对苯二甲酸亚丙基酯)。与特定的类型无关,这些热塑性聚合物必须具有适合于加工成纤维或纤维组分的熔体流动速率。
有时希望将加工助剂和其它添加剂用于弹性体型混合料核中。这些助剂和添加剂的例子是选自以下的物质:其它的嵌段共聚物、烯烃聚合物、苯乙烯聚合物、增粘树脂、聚合物增量油、蜡、填料、增强剂、润滑剂、稳定剂、和其混合物。
在本发明的一些实施方案中,尤其有用的是包括与弹性体型混合料的橡胶E和/或E1嵌段相容的树脂。其起到了促进弹性体型混合料流动的作用。多种树脂是公知的,并且例如在美国专利Nos.4,789,699;4,294,936和3,783,072中论述,这些专利关于树脂的内容在此引入作为参考。可以使用与弹性体型混合料的橡胶E和/或E1嵌段和/或聚烯烃相容并且能够承受高的加工(例如,挤出)温度的任何树脂。一般而言,氢化烃树脂由于它们较好的温度稳定性而因此是优选的树脂。可用树脂的说明性例子是氢化烃树脂,例如低分子量、完全氢化的α-甲基苯乙烯(Eastman Chemical)、P(ArakawaChemical)系列树脂,和萜烯烃例如501Lite(ArizonaChemical)。本发明并不限于使用这里所列出的这些树脂。一般而言,树脂可以选自:C5烃树脂、氢化C5烃树脂、苯乙烯化的C5树脂、C5/C9树脂、苯乙烯化的萜烯树脂、完全氢化或部分氢化的C9烃树脂、松香酯、松香衍生物和其混合物。本领域普通技术人员将理解的是:还可以使用与该组合物的组分相容、能够承受高的加工温度并且能够实现本发明目的的其它树脂。
该双组分纤维还可以包含蜡以提高流动性和/或相容性。合适的蜡是冻凝点为50-70℃的那些。基于弹性体型混合料的重量,蜡的合适含量为0.1-75wt%,优选5-60wt%。可以使用动物蜡、昆虫蜡、植物蜡、合成蜡和矿物蜡,优选的是衍生自矿物油的那些。矿物油蜡的例子包括光亮油含油蜡、中等机油含油蜡、高熔点蜡和微晶蜡。在含油蜡的情况下,可以存在至多25wt%的油。提高蜡的冻凝点的添加剂也可以存在。
该双组分纤维还可以包含油。可以将油掺入以提高纤维的加工性或者增强它的柔软度。尤其优选的是与嵌段共聚物的E和/或E1相容的油类型。尽管较高芳族物质含量的油是令人满意的,但优选的是具有低的挥发性和少于50%芳族物质含量的那些石油基白油。这些油应该进一步具有低的挥发性,优选具有高于约260℃的初始沸点。所使用的油的含量在约0-约300重量份/100重量份橡胶或嵌段共聚物之间变化,优选约为20-约150重量份。
通常通过加入抗氧化剂或者抗氧化剂混合物使弹性体型混合料稳定。通常使用空间位阻酚类稳定剂,或者例如日本专利No.94055772中披露的那样将磷基稳定剂与空间位阻酚类稳定剂组合使用;或者例如日本专利No.94078376中披露的那样使用酚类稳定剂的组合。
其它添加剂例如颜料、染料、荧光增白剂、上蓝剂和阻燃剂可用于本发明的双组分纤维。
本发明的双组分纤维可用于形成多种制品。这些制品包括:弹性单丝、机织织物、纺粘法无纺织物或过滤器、熔喷法织物、短纤维、纱线、粘合的梳理纤维网等。当将它们装备以将两种材料挤出成双组分纤维时,可以采用通常用于制备这些制品的任何方法。
特别地,可以通过本领域公知的任何一种方法来形成无纺织物或纤维网。通常被称作纺粘法一种方法是本领域非常公知的。美国专利4,405,297描述了一种典型的纺粘方法。纺粘方法通常包括:将纤维从熔体中挤出通过喷丝头,采用空气流将纤维骤冷和/或拉伸,并且将无纺纤维网收集和粘合。通常通过可有效地在纤维网的纤维之间产生多处中间粘结的任何热、化学或机械方法,包括水缠结和针穿孔方法来实现无纺纤维网的粘合。还可以采用例如描述于美国专利5,290,626中的熔喷方法来形成本发明的无纺纤维网。可以通过在横穿纵向方向(machine direction)上将无纺纤维网在其自身上折叠和粘合而由无纺纤维网形成梳理的纤维网。
本发明的无纺织物可用于各种弹性织物,例如尿布、腰带、弹力嵌料、一次性衣物、医疗和个人卫生制品、过滤器等。
本发明的弹性单丝是用于各种目的并且可以通过本领域的任何一种公知方法,包括纺丝、拉伸、骤冷和缠绕而成型的连续的、单根双组分纤维。本文中使用的“短纤维”是指连续共挤出的双组分纤维被切割或切断的部分。
可以通过常用方法来形成该双组分纤维的纱线。美国专利6,113,825教导了纱线成型的通用方法。一般而言,该方法包括:将多根纤维从喷丝头中熔融挤出、将长丝拉伸并且缠绕在一起以形成复丝纱线、任选地通过一个或多个热处理区将纱线延伸或拉伸、并且将纱线冷却和缠绕。
可以将本发明的制品单独使用或者与采用双组分纤维或者采用其它类材料制得的其它制品组合使用。作为例子,可以将无纺纤维网与弹性单丝组合以提供弹性的弹力嵌料。作为另一个例子,可以将无纺纤维网粘合在其它非弹性体的无纺纤维网或许多类型的聚合物薄膜上。
在制备本发明的双组分纤维的方法中,使用两个单独的单螺杆挤出机以将壳聚合物和核聚合物挤出到两个单独的熔体泵中。在熔体泵之后,通过一系列的板和隔板在喷丝头中使聚合物处于它们的双组分构造中。在排出喷丝头时,通过冷空气骤冷箱将纤维冷却/骤冷。在骤冷之后,通过吸气器或者一系列冷轧辊将纤维拉伸。在使用冷轧辊的情况下,将纤维卷在络丝机上。在使用吸气器的情况下,将纤维收集在吸气器下面的圆筒中。
本方法的一个重要方面是生产双组分纤维的速率。本发明的纤维所呈现出的高流动特性使得有高的挤出速率。从实际意义出发这是重要的,因为商业上的设备在高的挤出速率下运转。以这种方式可以实现经济的生产量。在本发明中,需要至少800米/分钟(mpm)的挤出速率。更优选约1000mpm或更大的速率,最优选约2000mpm或更大的速率。
对于本文中所披露的应用而言,优选的是细旦尼尔纤维。在非常少量的材料可被用于影响如此组成的制品中的弹性性能的意义上而言,这些细旦尼尔纤维是极其有效的弹性材料。在本发明中,可以制得具有0.1-30旦尼尔(克/9000米纤维)的双组分纤维。更优选的是具有0.5-20克/9000米旦尼尔的纤维,最优选的是具有1-10克/9000米旦尼尔的纤维。
实施例
本文中使用的术语“弹性”是指任何这样的材料:当施加偏压力时其是可拉伸的,即是说可伸长至少约60%(即,拉伸的偏移长度为其松弛的未偏移长度的至少约160%),并且当释放该拉伸、伸长力时其将恢复其至少50%的伸长率。一个假想的例子将是:可伸长至至少1.60英寸(4.06cm)、并且当其伸长至1.60英寸(4.06cm)和释放时其将恢复至不超过1.27英寸(3.23cm)的长度的一(1)英寸的材料样品。许多弹性材料可以伸长大大超过60%(即,大大超过它们的松弛长度的160%),例如伸长100%或更多,并且许多这些材料当释放拉伸力时将基本恢复至它们的初始松弛长度,例如恢复至它们的初始松弛长度的105%之内。
在由双组分纤维形成的纱线上作为100%伸长率下的百分比应变恢复率来测量弹性。纱线由多根的数目为36-144的单根连续纤维组成,该数目取决于喷丝头中孔的号数。手工将纱线拉伸至100%伸长率,然后使其松弛。然后测量纱线的松弛长度并且计算百分比恢复率。以该方法将弹性作为百分比恢复率来确定。
本文中使用的术语“韧度”是指以克/旦尼尔测量的纱线的拉伸强度的测量值。
实施例1-8
根据以下描述制备壳/核比例为30/70和20/80的具有聚丙烯壳和SEBS弹性体核的双组分纤维。该聚丙烯壳是得自于The Dow ChemicalCompany的标称38MFR均聚物(5D49)。该弹性体核(聚合物7)是18%苯乙烯含量、苯乙烯MW为6600并且中间嵌段分子量为60,000的标称50MFR、高乙烯基(乙烯基含量=75mol%)的偶联SEBS共聚物(偶联率=96%)。
采用使用双组分技术和得自于Hills Inc的喷丝头的常规商业类型的高速纺丝方法制备纤维。
表1给出了纤维典型的纺丝性能和机械性能。从表1中我们可以看出能够实现高速纺丝(实施例3、5和8)以及合理的纤维拉伸强度和断裂伸长率(实施例1、2、4、6、7)。另外,可以实现非常高的纺丝速度。壳-核双组分纤维(实施例3和5)在2700mpm下纺丝。
实施例9-13
根据以下描述制备壳/核比例为30/70和20/80的具有聚丙烯壳和SEBS弹性体核的双组分纤维。该聚丙烯壳是得自于The Dow ChemicalCompany的标称38MFR均聚物(5D49)。该弹性体核(聚合物5)是18%苯乙烯含量、苯乙烯MW为6200并且中间嵌段分子量为56,000的31MFR、高乙烯基(乙烯基含量=76%)的偶联SEBS共聚物(偶联率=94%)。
通过使用双组分技术和得自于Hills Inc的喷丝头的常规商业类型的高速纺丝方法制备纤维。
借助于31MFR弹性体(实施例9、11和12)可以实现优良的拉伸性能。可以实现的纺丝速度为1500-1800mpm。
实施例14-25
根据以下描述制备壳/核比例为30/70和20/80的具有聚丙烯壳和SEBS弹性体核的双组分纤维。该聚丙烯壳是得自于The Dow ChemicalCompany的标称38MFR均聚物(5D49)。该弹性体核(聚合物6)是19%苯乙烯含量、苯乙烯MW为6100并且中间嵌段分子量为50,000的标称20MFR、高乙烯基(乙烯基含量=76%)的偶联SEBS共聚物(偶联率=95%)。
通过使用双组分技术和得自于Hills Inc的喷丝头的常规商业类型的高速纺丝方法制备纤维。
表3的结果表明:较低熔体流动性的弹性体对纺丝性能(最大纺丝速度)具有不利的影响,但拉伸性能仍然认为对于弹性纤维而言是合理的。表3还表明:当聚丙烯在纤维横截面中的比例提高时,纺丝性能提高,并且甚至相对低熔体流动性的弹性体可以借助于合适的壳/核比例而提供优良的纺丝性能。另外,聚丙烯当其浓度增加时提高了纤维的拉伸强度,但可能对纤维弹性具有负面影响。
实施例26-36
根据以下描述制备壳/核比例为30/70和20/80的具有聚丙烯壳和SEBS弹性体核的双组分纤维。该聚丙烯壳是得自于The Dow ChemicalCompany的标称38MFR均聚物(5D49)。该弹性体核是聚丙烯(5D49)与弹性体(聚合物7)的共混物。共混物1是10wt%Dow 5D49聚丙烯与90wt%聚合物7的共混物。共混物2是20wt%Dow 5D49聚丙烯与80wt%聚合物7的共混物。
通过使用双组分技术和得自于Hills Inc的喷丝头的常规商业类型的高速纺丝方法制备纤维。表4表明:弹性体与聚丙烯的共混物制得了双组分弹性纤维优良的弹性体核。实现了高的纺丝速度和优良的拉伸性及弹性。
作为比较的单组分纤维(实施例36)也示于表4中。该单组分纤维仅仅由弹性体型混合料(聚合物7)组成,而没有热塑性聚合物壳。需要低的纺丝速度,并且纤维在纺丝过程中展现出不可接受的粘性。所得的单组分纤维自-粘结并且不能被分离。
实施例37-39
还通过单个空气吸气器将双组分纤维纺丝以模拟纺粘方法。吸气器中的空气压力被用于影响最大纺丝速度,即,压力越高,则纺丝速度越高。对于所有实施例而言,每个孔的聚合物产量(0.35克/孔/分钟)是相同的。
实施例37是仅仅包含5D49聚丙烯的作为比较的单组分纤维。在纤维开始断裂之前,最大空气压力达到40psi。该热塑性聚合物的纤维没有弹性。
实施例38使用了比例为20/80的5D49聚丙烯壳和50MFR弹性体核(聚合物7)以制得弹性纺粘法纤维。在长丝开始断裂之前,最大纺丝速度为20psi。实施例39是壳/核比例为40/60的聚丙烯(5D49)和20MFR弹性体(聚合物6)的双组分纤维。在纤维开始断裂之前,最大纺丝速度为25psi。实施例38和39的双组分纤维是弹性的。
实施例40-45
实施例40-44示出了使用Dow ASPUN聚乙烯作为热塑性聚合物壳(6811A)和聚合物7作为弹性体核的壳/核双组分纤维。这些实施例表明:也可以将聚乙烯用作双组分弹性纤维的壳。
通过使用双组分技术和得自于Hills Inc的喷丝头的常规商业类型的高速纺丝方法制备纤维。
实施例46
根据以下描述制备具有相对低的熔体流动速率、低乙烯基含量的弹性体(聚合物8)的双组分弹性纤维。聚合物8是标称9MFR、38%乙烯基的偶联SEBS弹性体。它的苯乙烯嵌段分子量为5000、中间嵌段分子量为47,000,并且偶联率为94%。标称苯乙烯含量为18wt%。该纤维的壳是标称12MFR聚丙烯均聚物。尽管该实施例表明可以使用低乙烯基含量的嵌段共聚物制备双组分纤维,但对于最佳的纺丝性能而言将优选的是较高熔体流动速率的弹性体。
表2.
实施例 | 壳/核比例 | 纺丝速度(mpm) | 韧度(g/dn) | 断裂伸长率(%) | 弹性(%) | 最高纺丝速度 |
9 | 20/80 | 500 | 0.3 | 470 | - | - |
10 | 20/80 | - | - | - | - | 1500 |
11 | 30/70 | 500 | 0.3 | 570 | - | - |
12 | 30/70 | 1400 | 0.7 | 250 | 75 | - |
13 | 30/70 | - | - | - | - | 1800 |
表3
实施例 | 壳/核比例 | 纺丝速度(mpm) | 韧度(g/dn) | 断裂伸长率(%) | 弹性(%) | 最高纺丝速度 | 每根长丝的旦尼尔(dpf) |
14 | 20/80 | 500 | 0.3 | 500 | - | - | 14.5 |
15 | 20/80 | 1000 | 0.5 | 310 | - | - | 7.5 |
16 | 20/80 | - | - | - | - | 1100 | - |
17 | 30/70 | 500 | 0.3 | 490 | - | - | 14.5 |
18 | 30/70 | 1400 | 0.7 | 250 | 80 | - | 5 |
19 | 30/70 | - | - | - | - | 1500 | - |
20 | 40/60 | 500 | 0.5 | 660 | - | - | 14.5 |
21 | 40/60 | 1400 | 0.8 | 320 | - | - | 5 |
22 | 40/60 | - | - | - | - | 1900 | - |
23 | 50/50 | 500 | 0.5 | 660 | - | - | 14.5 |
24 | 50/50 | 1400 | 0.9 | 330 | 50 | - | 5 |
25 | 50/50 | - | - | - | - | 2500 | - |
表5.
实施例 | 壳 | 核 | 壳/核比例 | 最大纺丝速度(psf) | 弹性(%) |
37 | 5D49 | - | 100/0 | 40 | 0 |
38 | 5D49 | 聚合物7 | 20/80 | 20 | - |
39 | 5D49 | 聚合物6 | 40/60 | 25 | 75. |
表6.
实施例 | 壳/核比例 | 纺丝速度(mpm) | 每根长丝的旦尼尔(g/9000m) | 韧度(g/dn) | 断裂伸长率(%) | 弹性(%) | 最高纺丝速度 |
40 | 20/80 | 300 | 17.6 | 0.1 | 660 | - | - |
41 | 20/80 | 500 | 11.6 | 0.1 | 680 | - | - |
42 | 20/80 | - | - | - | - | - | 500 |
43 | 30/70 | 500 | 11.6 | 0.1 | 580 | 60 | - |
44 | 30/70 | 1000 | 5.2 | 0.2 | 360 | 50 | - |
45 | 30/70 | - | - | - | - | - | 1000 |
表7.
实施例 | 壳/核比例 | 纺丝速度(mpm) | 韧度(g/dn) | 断裂伸长率(%) | 弹性(%) |
46 | 20/80 | 500 | 0.02 | 480 | 80 |
Claims (12)
1.一种包含热塑性聚合物壳和弹性体型混合料核的双组分纤维,其中该弹性体型混合料核包含具有S嵌段和E或E1嵌段并且具有以下任一种通式的选择性氢化的嵌段共聚物或其混合物:
S-E-S,(S-E1)n,(S-E1)nS,(S-E1)nX
其中:
a.在氢化之前,S嵌段是聚苯乙烯嵌段;
b.在氢化之前,E嵌段是分子量为40,000-70,000的聚丁二烯、聚异戊二烯和/或其混合物的聚二烯烃嵌段;
c.在氢化之前,E1嵌段是分子量为20,000-35,000的聚丁二烯、聚异戊二烯和/或其混合物的聚二烯烃嵌段;
d.n具有2-6的值,X为偶联剂残基;
e.该嵌段共聚物的苯乙烯含量为13-25wt%;
f.氢化之前聚二烯烃嵌段的乙烯基含量为70-85mol%;
g.该嵌段共聚物包含少于15wt%的具有以下通式的单元:
S-E或S-E1
其中S、E和E1如同已经定义的那样;
h.在氢化之后,0-10%的苯乙烯双键被氢化,并且至少80%的共轭二烯烃双键被氢化;
i.每一S嵌段的分子量为5,000-7,000;和
j.根据ASTM D1238在230℃和2.16kg重量下,该嵌段共聚物的熔体指数大于或等于12克/10分钟。
2.根据权利要求1的双组分纤维,其中该聚苯乙烯嵌段S的分子量为5,800-6,600并且E嵌段是分子量为45,000-60,000的聚丁二烯,或者E1嵌段是两个或更多个偶联的聚丁二烯嵌段,每一聚丁二烯嵌段在偶联之前的分子量为22,500-30,000。
3.根据权利要求1或2的双组分纤维,其中该选择性氢化的嵌段共聚物的结构是(S-E1)nX,并且该嵌段共聚物含有少于10%的未偶联的S-E1类物质。
4.根据权利要求1-2任一项的双组分纤维,其中该弹性体型混合料核进一步包含至多50wt%的热塑性聚合物,该热塑性聚合物是聚丙烯、线型低密度聚乙烯、聚酰胺、聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸丁二醇酯)或聚(对苯二甲酸亚丙基酯)。
5.根据权利要求1-2任一项的双组分纤维,其中该热塑性聚合物壳与该弹性体型混合料核的体积比为5/95-49/51。
6.根据权利要求1-2任一项的双组分纤维,其中根据ASTM D1238在230℃和2.16kg重量下,该嵌段共聚物的熔体流动速率大于15克/10分钟。
7.根据权利要求1-2任一项的双组分纤维,其中根据ASTM D1238在230℃和2.16kg重量下,该嵌段共聚物的熔体流动速率大于40克/10分钟。
8.根据权利要求1-2任一项的双组分纤维,其中该热塑性聚合物是聚丙烯、线型低密度聚乙烯、聚酰胺、聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸丁二醇酯)或聚(对苯二甲酸亚丙基酯)。
9.根据权利要求8的双组分纤维,其中该热塑性聚合物是根据ASTM D1238在230℃和2.16kg下熔体流动速率至少为20克/10分钟的聚丙烯或者熔体流动速率至少为25克/10分钟的线型低密度聚乙烯。
10.根据权利要求1的双组分纤维,其中该弹性体型混合料核包含增粘树脂。
11.一种包含权利要求1-10任一项的双组分纤维的制品,该制品是弹性单丝、机织织物、纺粘法无纺织物、熔喷法无纺织物或过滤器、短纤维、纱线或者粘合的梳理纤维网。
12.一种制备权利要求1-10任一项的双组分纤维的方法,其包括:将热塑性聚合物和弹性体型混合料共挤出,其中在至少500米/分钟的速率下采用单独的熔体泵使热塑性聚合物和弹性体型混合料挤出通过模头以形成一根或多根具有主要由热塑性聚合物组成的壳和主要由弹性体型混合料组成的核的长丝,以使得该双组分纤维具有每根长丝为0.1-30克/9000米的旦尼尔。
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EP0461726A2 (en) * | 1990-06-14 | 1991-12-18 | Shell Internationale Researchmaatschappij B.V. | Bicomponent elastomeric fibres |
US5464695A (en) * | 1991-07-25 | 1995-11-07 | Kuraray Company Limited | Composite fiber containing inorganic fine powder |
WO2000008243A1 (en) * | 1998-08-03 | 2000-02-17 | Bba Nonwoven Simpsonville, Inc. | Elastic nonwoven fabric prepared from bi-component filaments |
US20020147273A1 (en) * | 1999-07-28 | 2002-10-10 | Patel Rajen M. | Hydrogenated block copolymers having elasticity and articles made therefrom |
EP1275891A1 (en) * | 2000-04-21 | 2003-01-15 | Kuraray Co., Ltd. | Multilayered tube and medical supply comprising multilayered tube |
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