CN102471941B - 聚烯烃构件及其制备方法 - Google Patents
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Abstract
本发明涉及一种用于制备高性能聚烯烃构件的改进方法。该方法包括下列步骤:制备包含聚烯烃和溶剂的溶液;使该溶液挤出或纺丝进入空气隙从而形成流体构件;冷却所述流体构件以形成含溶剂的凝胶构件;并且在拉伸所述构件之前、期间和/或之后,从所述凝胶构件中除去至少部分溶剂从而形成固体构件。此外,所述方法包括含有芳基磺酸或烷基萘磺酸的消泡剂的存在。本发明还涉及包含芳基磺酸或烷基萘磺酸的凝胶挤出的聚烯烃构件。
Description
技术领域
本发明涉及聚烯烃构件,例如包含聚烯烃材料的纤维、带或片材构件,的制备。更具体地,本发明涉及所述构件的凝胶挤出。此外,本发明还涉及一种用于制备所述构件的方法。
背景技术
聚烯烃构件可以通过如下方法制备:挤出聚烯烃在溶剂中的溶液,随后拉伸。这种方法被称为凝胶挤出法(geltrusion process),将产生高强度的纤维材料,例如纤维、带和片材构件。凝胶挤出从根本上不同于制备高性能聚烯烃纤维用的其他主要方法,例如熔融纺丝和固态成形。用于制备纤维的凝胶挤出法在例如EP 1699954中公开了,而用于制备片材构件的凝胶挤出法在例如EP 0500173和EP 0504954中公开了。
发明目的
本发明的目标是提供一种改善的聚烯烃构件。
本发明的另一个目标是提供一种用于制备聚烯烃构件的改进方法。
所述改进可以例如为增大构件或制备方法的再现性并且/或者改善构件或制备方法的质量。
发明内容
本发明上述和/或其他目标中的一个或更多个通过一种用于制备聚烯烃构件的方法实现,所述方法包括:制备包含聚烯烃和溶剂的溶液,使该溶液挤出或纺丝进入空气隙从而形成流体构件。流体构件随后被冷却形成含溶剂的凝胶构件,继而形成固体构件。从构件中至少部分除去溶剂之前、期间和/或之后,进一步拉伸构件。所述冷却包括将流体构件转移到冷却浴中。在本发明的第一实施方式中,冷却浴包含有机相和水基相以及含芳基磺酸的消泡剂。优选地,所述消泡剂包含烷基苯磺酸或烷基萘磺酸,例如二壬基萘磺酸或十二烷基苯磺酸。
已令人惊讶地发现:这种消泡剂的加入改善了所制构件的质量。例如,芳基磺酸的加入降低了聚合物片材构件的表面缺陷的数量。已发现使用包含烷基苯磺酸和/或芳基萘磺酸的消泡剂很有效,并且可以推测,较少的芳族部分与烷基部分的组合为高亲水的磺基提供适当的平衡,但并不限于此。该组中特别优选的实例为包含二壬基萘磺酸和/或十二烷基苯磺酸的消泡剂,如那些以下列商品名可商购的Innospec Inc的产品:例如Stadis(诸如Stadis450)、Statsafe(诸如Statsafe6000)。在这些之中,商品名为Statsafe6000的十二烷基苯磺酸是优选的,这是因为由于制备稳定的工业用溶液使用最多的溶剂是庚烷并且不需要大量苯或甲苯因而从环境的观点来说它更可接受。
消泡剂可以包含一种或更多种其他组分。例如,消泡剂可以包含其他活性组分,例如消泡试剂(如十二烷基苯磺酸与另一种烷基苯磺酸或另一种消泡剂的组合)、表面活性剂、溶剂、悬浮助剂、防污剂等。
优选地,冷却浴为两相冷却浴,具有主要的水基相和有机相。消泡剂应以活性量(active amount)添加。通常,活性量大于约3ppm。换句话说,每kg冷却液(水基相和有机相之和)中包含多于约3mg的含至少一种上述化合物的消泡剂。在一个优选的实施方式中,加入消泡剂使其在冷却浴中的浓度介于4ppm和20ppm(基于质量)之间。该浓度适合大部分聚烯烃。为了制备高性能聚乙烯和聚丙烯纤维基构件,优选使用在冷却浴中为5ppm-15ppm的消泡剂浓度,因为这样能实现所需的消泡效果同时使所制构件和回收利用的有机材料(溶剂和/或冷却液)的污染限制在可接受的水平。
冷却浴也可以是单相冷却浴,其中水相是优选的,因为水的高热容和热传导。在这种情况下也可以加入消泡剂以防止溶剂液滴或泡沫在冷却浴的表面上形成。
加入之后,消泡剂的浓度可能难以测定,特别是当所述方法在过程环境下回收利用该过程的一个或更多组分(例如聚烯烃或溶剂和/或冷却浴中的有机相)进行时。因此要认识到本发明人还规定了活性量为冷却浴中有机相的电导率。已发现:活性量导致至少为800pS/m[皮西门子/米]的电导率。按实验部分描述的方法测量电导率。在一个优选的实施方式中,有机相的电导率为1000pS/m-3000pS/m。该电导率适合大部分聚烯烃。为了制备高性能的聚乙烯和聚丙烯纤维基构件,优选地将冷却浴中有机相的电导率调至1500pS/m-2500pS/m,最优选地,有机相的电导率为2000pS/m-2300pS/m,因为这样能实现所需的消泡效果同时使所制构件和回收利用的有机材料(溶剂和/或冷却液)的污染限制在可接受的水平。
挤出之后,从聚烯烃构件中至少部分除去溶剂。这可以在拉伸聚烯烃构件之前、期间和/或之后进行。溶剂可以例如通过蒸发或挤出而被至少部分除去。
沿着聚烯烃的原纤拉伸构件,从而如强度和杨氏模量的性能得到改善。拉伸可以在一个或更多个阶段中以连续方式或间歇方式进行。优选地以连续方式使用多个拉伸阶段,因为这是更有成本效益的方法。
拉伸比取决于聚烯烃构件的形状和期望的应用。通常,以至少2的因子在纵向(machine direction)上拉伸聚烯烃构件。为了进一步增强原纤在纵向的排列,优选地,以至少10的因子在纵向上拉伸聚烯烃构件。特别是对薄的带状构件和纤维来说,优选地以至少100的因子在纵向上拉伸聚烯烃构件;而对于纤维聚烯烃构件来说,发现高拉伸比(例如1000-5000的因子)对于产生非常高的纤维比强度来说非常有利。在另一个实施方式中,聚烯烃构件是片状构件,并且通过至少8的面积因子双轴拉伸聚烯烃构件。例如如果需要非常高的强度,已发现通过至少25的面积因子(例如纵向上6.25的因子与横向上4的因子相结合)双轴拉伸聚烯烃构件很有利。原则上片材也可以在其他方向上(例如与纵向成45°角)被拉伸,但这不是优选的实施方式。高拉伸比(例如15-50的面积因子)有利于产生高比强度和高开孔率(例如70-95%)。
在一个特别优选的实施方式中,由聚烯烃和溶剂制成的溶液还包含选自由芳基磺酸组成的组中的消泡剂。这使得本发明第二方面的优势包含在本发明的第一方面中。在一个非常优选的实施方式中,溶液中所含的消泡剂与冷却浴中所含的消泡剂相同(组合)。通过这种方式,至少部分消泡剂可以通过凝胶挤出的构件提供给冷却浴。例如当溶液中使用的溶剂被回收利用时这样可能很有利,因为降低了废物的产生量并且减少了回收利用之前溶剂的清洁要求。
在本发明的另一个实施方式中,本发明的一个或更多个上述目标和/或其他目标通过一种用于制备聚烯烃构件的方法而实现,其中所述溶液还包含含有芳基磺酸的消泡剂,所述消泡剂包含烷基苯磺酸和烷基萘磺酸,例如二壬基萘磺酸或十二烷基苯磺酸。一种或更多种上述消泡剂的加入防止或减少了在溶液制备期间泡沫的形成,并且增强了稳定溶液的形成。由于降低了(表面)缺陷(例如由未溶聚烯烃颗粒的存在导致的)的浓度,这样便导致了改善的可加工性以及在某些情况下改进的产品。
优选地,加入一定量的消泡剂将溶液的电导率调节至至少800pS/m。更优选地,加入一定量的消泡剂将溶液的电导率调节至1000pS/m-3000pS/m。该电导率适合大部分聚烯烃。为了制备高性能的聚乙烯纤维基构件,优选地加入消泡剂将溶液的电导率调至1500pS/m-2500pS/m,最优选地,加入消泡剂将溶液的电导率调至2000pS/m-2300pS/m。
非常优选地,所述冷却浴是如本发明的第一方面所述的具有两相的类型,并且优选地包含如本发明第一方面所述的消泡剂。根据本发明第二方面制备的构件还应该被拉伸,并且相同优选的实施方式如本发明的第一方面一样施加到本发明的第二方面。
本发明另一方面涉及消泡剂在聚烯烃构件的制备中的用途,其中所述消泡剂包含芳基磺酸,优选地,消泡剂包含烷基苯磺酸或烷基萘磺酸,例如二壬基萘磺酸或十二烷基苯磺酸。用途可以如本发明的第一方面和第二方面所述。本发明人发现这种类型的消泡剂在基于聚乙烯(特别是UHMwPE)的聚乙烯构件的制备中特别有利,因为UHMwPE易于形成高粘度的溶液所以特别难以加工。
本发明还涉及包含0.01ppm-100ppm芳基磺酸的凝胶挤出的聚烯烃构件。优选地,所述构件包含烷基苯磺酸或烷基萘磺酸,例如二壬基萘磺酸或十二烷基苯磺酸。
在一个优选的实施方式中,凝胶挤出的聚烯烃构件包含IV大于5dl/g经拉伸的UHMwPE纤维,因为这提供机械性能非常好(例如高拉伸强度、模量和断裂能量吸收)的构件。更优选地,选择IV大于10dl/g的聚乙烯。这是因为通过凝胶纺丝所述UHMwPE而制成的纱线提供了下列性能的组合:高强度、低相对密度、良好的耐水解性以及优异的耐磨性。适合的UHMwPE的特性粘度通常为至少5dl/g,优选介于8和40dl/g之间,更优选介于10和30、或12和28、或15和25dl/g之间。
UHMwPE的凝胶纺丝在如下各种出版物中均有描述,包括EP0205960A、EP 0213208A1、US 4413110、WO 01/73173A1和AdvancedFibre Spinning Technology,Ed.T.Nakajima,Woodhead Publ.Ltd(1994),ISBN 1-855-73182-7以及其中所引用的参考文献。这些出版物通过引用结合于此。因此,根据本发明的一个方面,流体组合物是UHMwPE在溶剂中的溶液,并且本发明方法包括至少部分除去溶剂的步骤。
在本方法中,可以使用用于UHMwPE凝胶纺丝的任何已知溶剂。纺丝溶剂的适当实例包括脂族烃和脂环族烃,例如辛烷、壬烷、癸烷和石蜡,包括其异构体;石油馏分;矿物油;煤油;芳族烃,例如甲苯、二甲苯和萘,包括其氢化衍生物,例如十氢化萘和四氢化萘;卤化烃,例如一氯代苯;和环烷烃或环烯烃,例如蒈烯(careen)、芴、莰烯、孟烷、二戊烯、萘、苊烯(acenaphtalene)、甲基环戊二烯、三环癸烷、1,2,4,5-四甲基-1,4-环己二烯、芴酮、联萘胺(naphtindane)、四甲基-对-苯并二醌、乙基芴(ethylfuorene)、荧蒽和萘酮。还可以使用上面所列举的纺丝溶剂的组合用于UHMWPE的凝胶纺丝,其中为了简化,溶剂的组合也被称为纺丝溶剂。在一个实施方式中,所选择的纺丝溶剂在室温下具有低蒸汽压,例如石蜡油。还发现,本发明的方法对于在室温下相对挥发性的纺丝溶剂例如十氢化萘、四氢化萘和煤油而言尤其有利。最优选,纺丝溶剂为十氢化萘。
纵向拉伸的凝胶纺丝UHMwPE带具有非常高的韧性(tenacity)。优选地,UHMwPE带的韧性为至少20cN/dtex,优选为至少25cN/dtex,甚至更优选为至少30cN/dtex,最优选为至少35cN/dtex。因为带是经拉伸的UHMwPE带,所以可得到如此高的韧性。
此外,纵向拉伸的凝胶纺丝UHMwPE带具有非常高的模量。优选地,带的模量为至少600cN/dtex,更优选为至少900cN/dtex,甚至更优选为至少1300cN/dtex。
聚烯烃可以为聚乙烯、聚丙烯或可以根据本发明的方法凝胶挤出的任何其他合适的聚合物。在一个优选的实施方式中,聚烯烃为高分子量聚乙烯(HMwPE)或超高分子量聚乙烯(UHMwPE)。HMwPE或UHMwPE带表示包含占最终干燥构件总重量75wt%的HMwPE或UHMwPE的带。该比例优选地为至少90wt%,最优选为100wt%。当构件由HMwPE和UHMwPE的组合制成时,所产生的构件可以是HMwPE带或UHMwPE带,这取决于HMwPE和UHMwPE的比例。
本文中“高分子量聚乙烯(HMwPE)”指的是分子量为50000-400000的聚乙烯。本文中“超高分子量聚乙烯(UHMwPE)”定义为分子量为至少400000的聚乙烯。UHMwPE可以具有多达几百万的分子量。除非另外指出,本文中“分子量”指的是重均分子量(Mw)。
特性粘度可用于确定分子量。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。根据方法PTC-179(Hercules Inc.Rev.Apr.29,1982)来测定IV,测试条件为:在135℃下,十氢化萘中,溶解时间为16小时,采用用量为2g/l溶液的DBPC作为抗氧化剂,并且将在不同浓度下测量的粘度外推得到零浓度下的粘度。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EP 0504954A1),4.5dl/g的IV相当于约4.2×105g/mol的Mw。
因为它们的长分子链,IV大于5dl/g、经拉伸的UHMwPE纤维具有非常好的机械性能,例如高拉伸强度、模量和断裂能量吸收。更优选地,选择IV大于10dl/g的聚乙烯。这是因为通过凝胶纺丝所述UHMwPE而制成的纱线提供了下列性能的组合:高强度、低相对密度、良好的耐水解性以及优异的耐磨性。合适的UHMwPE的特性粘度通常为至少5dl/g,优选介于8和40dl/g之间,更优选介于10和30、或12和28、或15和25dl/g之间。
优选地,本发明中的HMwPE和UHMwPE是线性聚乙烯,即每100个碳原子具有小于1个侧链或支链、优选每300个碳原子具有小于1个侧链的聚乙烯,其中侧链通常包含至少10个碳原子。优选地,只存在聚乙烯,但可供选择地聚乙烯可以还包含至多5mol%的可与其共聚或不能与其共聚的烯烃,例如丙烯、丁烯、戊烯、4-甲基戊烯或辛烯。聚乙烯可以还包含至多15重量%、优选1-10重量%的对于所述纤维来说常用的添加剂,例如抗氧化剂、热稳定剂、着色剂等等。
实施例
●电导率:冷却浴中有机相的电导率是通过EMCEE Electronic Model1152 Digital Conductivity Meter在20℃下测量的。
●IV:根据方法PTC-179(Hercules Inc.Rev.Apr.29,1982)来测定特性粘度,测试条件为:在135℃下,十氢化萘中,溶解时间为16小时,采用用量为2g/l溶液的DBPC作为抗氧剂,其中将在不同浓度下测量的粘度外推得到零浓度下的粘度。
●侧链:UHMwPE样品中侧链的数量通过FTIR在2mm厚的压塑膜上测定,通过使用基于NMR测量(在例如EP 0269151中)的校准曲线来量化在1375cm-1处的吸收。
实施例1:UHMwPE纤维材料的制备
UHMwPE粉末和消泡剂在溶剂(十氢化萘)中混合产生约为10%UHMwPE的最终浓度,从而形成所述溶液。随后使用双叶片挤出机将溶液挤出以产生流体构件,该流体构件被冷却并拉伸以形成固体构件。该方法在WO2005/066401中进一步描述了。
观测冷却浴中溶液性能和起泡行为。
*Stadis 450包含10-30%二壬基萘磺酸
**Statsafe 6000包含5-10%十二烷基苯磺酸
本文所述的本发明一个实施方式中的单个特征或特征的组合及其明显的变体可以与本文所述的其他实施方式的特征组合或互换,除非本领域普通技术人员立即认识到所得实施方式实际上不可行。
Claims (16)
1.消泡剂在聚烯烃构件的制备中的用途,所述制备通过如下步骤:
-制备包含聚烯烃和溶剂的溶液;
-使所述溶液挤出或纺丝进入空气隙从而形成流体构件;
-冷却所述流体构件形成含溶剂的凝胶构件;
-在拉伸所述构件之前、期间和/或之后,从所述凝胶构件中至少部分除去溶剂,从而形成固体构件,
其中所述消泡剂包含芳基磺酸。
2.根据权利要求1所述的消泡剂在聚烯烃构件的制备中的用途,其中所述消泡剂包含烷基苯磺酸或烷基萘磺酸。
3.一种用于制备聚烯烃构件的方法,其包括下列步骤:
-制备包含聚烯烃和溶剂的溶液;
-使所述溶液挤出或纺丝进入空气隙从而形成流体构件;
-冷却所述流体构件形成含溶剂的凝胶构件;
-在拉伸所述构件之前、期间和/或之后,从所述凝胶构件中至少部分除去溶剂,从而形成固体构件
其中
-所述溶液还包含含有芳基磺酸的消泡剂。
4.如权利要求3所述的方法,其进一步包括下列步骤:加入所述消泡剂将所述溶液的电导率调至1000pS/m-3000pS/m。
5.如权利要求3所述的方法,其中以至少3的因子在纵向上拉伸所述聚烯烃构件。
6.如权利要求3所述的方法,其中所述聚烯烃构件是片材构件,并且以至少10的面积因子双轴拉伸所述聚烯烃构件。
7.如权利要求3至6中任意一项所述的方法,其中所述聚烯烃是特性粘度为至少5dl/g的超高分子量聚乙烯。
8.一种用于制备聚烯烃构件的方法,其包括下列步骤:
-制备包含聚烯烃和溶剂的溶液;
-使所述溶液挤出或纺丝进入空气隙从而形成流体构件;
-冷却所述流体构件形成含溶剂的凝胶构件;
-在拉伸所述构件之前、期间和/或之后,从所述凝胶构件中至少部分除去溶剂,从而形成固体构件,
其中
-所述冷却包括将所述流体构件转移到包含有机相和水基相的冷却浴中;并且
-所述冷却浴包含含有芳基磺酸的消泡剂。
9.如权利要求8所述的方法,其中所述冷却浴中消泡剂的浓度介于4ppm和20ppm之间。
10.如权利要求8所述的方法,其中以至少2的因子在纵向上拉伸所述聚烯烃构件。
11.如权利要求8所述的方法,其中所述聚烯烃构件是片材构件,并且以至少8的面积因子双轴拉伸所述聚烯烃构件。
12.如权利要求8所述的方法,其中所述溶液还包含含有芳基磺酸的消泡剂。
13.如权利要求8至12中任意一项所述的方法,其中所述聚烯烃是特性粘度为至少5dl/g的超高分子量聚乙烯。
14.一种包含0.01ppm-100ppm芳基磺酸的凝胶挤出的聚烯烃构件。
15.如权利要求14所述的聚烯烃构件,其中所述构件是凝胶纺丝的聚烯烃纤维、聚烯烃带或凝胶挤出的片材构件。
16.如权利要求14或15所述的聚烯烃构件,其中所述聚烯烃是特性粘度为至少5dl/g的超高分子量聚乙烯。
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NL8006994A (nl) * | 1980-12-23 | 1982-07-16 | Stamicarbon | Filamenten met grote treksterkte en modulus en werkwijze ter vervaardiging daarvan. |
US4413110A (en) | 1981-04-30 | 1983-11-01 | Allied Corporation | High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore |
JPS6045607A (ja) * | 1983-08-19 | 1985-03-12 | Toyobo Co Ltd | 高強力,高モジユラス繊維又はフイルムの製造方法 |
JPS60106846A (ja) * | 1983-11-14 | 1985-06-12 | Mitsui Petrochem Ind Ltd | ポリエチレン組成物 |
WO1986004936A1 (en) | 1985-02-15 | 1986-08-28 | Toray Industries, Inc. | Polyethylene multifilament yarn |
EP0205960B1 (en) | 1985-06-17 | 1990-10-24 | AlliedSignal Inc. | Very low creep, ultra high moduls, low shrink, high tenacity polyolefin fiber having good strength retention at high temperatures and method to produce such fiber |
IN170335B (zh) | 1986-10-31 | 1992-03-14 | Dyneema Vof | |
AU642154B2 (en) * | 1989-09-22 | 1993-10-14 | Mitsui Chemicals, Inc. | Molecular orientation articles molded from high-molecular weight polyethylene and processes for preparing same |
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US20100249831A1 (en) * | 2007-10-05 | 2010-09-30 | Martin Pieter Vlasblom | Low creep, high strength uhmwpe fibres and process for producing thereof |
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