CN1756802A - 改进混合物织线强度的玻璃增固尼龙混合物 - Google Patents
改进混合物织线强度的玻璃增固尼龙混合物 Download PDFInfo
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- CN1756802A CN1756802A CN200480005705.7A CN200480005705A CN1756802A CN 1756802 A CN1756802 A CN 1756802A CN 200480005705 A CN200480005705 A CN 200480005705A CN 1756802 A CN1756802 A CN 1756802A
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- polymer alloy
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- polyhexamethylene
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Abstract
本发明提供一种包括以下物质的聚合物合金型:约40wt%-约75wt%的至少一种聚酰胺、约10wt%-约50wt%的聚丙烯、约0.01wt%-约1.0wt%的包括有乙烯基芳族单体和共轭二烯,并且还包括有不饱和的二羧基试剂的至少一种嵌段共聚物、约0.1wt%-约5.0wt%的至少一种嵌段共聚物或三聚物,其中该三聚物可以含有接枝到其上的不饱和二羧基试剂、约0.01%-约7.5%的相容剂和约5wt%-约50wt%的填料。本发明的合金型与现有技术的玻璃纤维增固的尼龙混合物相比展现出改进的织线强度和改进的抗落锤撞击性能。
Description
技术领域
本发明涉及一种聚合物混合物。更特别地,本发明涉及一种包括有聚丙烯的均聚物或共聚物和聚酰胺的纤维加固的聚合物合金型。
背景技术
热塑性聚酰胺例如尼龙6,6已经被广泛地用于形成需要优良的机械性能、高耐热性和良好的耐用性的机械部件和电子部件。尽管热塑性聚酰胺具有良好的耐热性和高的机械强度,但它们也暴露出相对弱的抗冲击性、切口敏感性和耐湿性。
热塑性聚酰胺的抗冲击性有时可以通过将它们与一种或多种其它聚合物混合以形成混合的聚合物组合物或聚合物合金型来提高抗冲击性。就聚合物组合物而言,术语“混合物”和“合金型”在说明书和权利要求书中可互换使用。通常,聚合物的物理性混合不能完全解决聚酰胺的弱的抗冲击性能。一般来说,能提高热塑性聚酰胺抗冲击性的聚合物通常与聚酰胺不混溶,这导致了混合物中聚合物之间弱的粘合力。结果,混合物组分之间的接触面成为模制品中差的区域,导致机械性能失效。
如上所述,热塑性聚酰胺会吸收水分,可导致所需性能的降低。可将聚烯烃与聚酰胺混合作为降低该混合物吸水性的一种方法,因为聚酰胺水分吸收部分会被通常为疏水性的聚烯烃代替。然而,由于聚酰胺与聚烯烃不相容,因此将它们混合的最初的尝试通常是不成功的。
要获得极性聚合物例如热塑性聚酰胺与非极性聚合物例如聚烯烃的组合物的优良分散性是困难的。Lutz等的美国专利4,795,782号描述了一种旨在提高抗冲击性的聚合物混合物,其包括聚酰胺、官能化聚烯烃和官能化弹性体。官能化聚烯烃通过将聚烯烃与不饱和的单一或多羧酸或者其衍生物反应而获得。适合的不饱和单一或多羧酸包括马来酸、马来酸酐、富马酸等。美国专利4,795,782号所描述的官能化弹性体通常为共轭二烯和乙烯基芳族化合物选择性官能化的氢化嵌段共聚物。通过使共聚物接枝上单一或多羧酸化合物例如马来酸、马来酸酐、富马酸等而将该嵌段共聚物官能化。用于引入官能度的其它单体包括乙烯基单体例如丙烯酰胺、丙烯腈、单乙烯基芳族化合物(即苯乙烯)、乙烯基酯、乙烯基醚等。
将相似化学结构的接枝或嵌段共聚物加入混合物组分可以提高分散性能。一般被称为相容剂的这些共聚物添加物通常作为第三组分加入到混合物中。相容剂是这样一种材料,在分子水平上具有可与每一不相容的组成聚合物相容的特定区域。这种相容剂通常包围一个聚合物相,提供了一个到其他聚合物相的化学和/或物理性桥接。由于相容剂可与每一组成聚合物相容,因此通过这种媒介相容相,两个不相容的聚合物相之间的连接有效地加强了。这种通过相容剂相连接的不相容的聚合物系统形成了一种材料,其具有更多所需的组成聚合物的性能。已经提出用马来酸酐接枝的聚丙烯作为聚丙烯/尼龙混合物的相容剂。有关聚乙烯/聚酰胺混合物与马来酸酐接枝的聚丙烯的相容性已经有了报道。
将玻璃纤维添加到合成物以增固和紧固合成物是众所周知的。除了增强潮湿情况下尺寸的稳定性之外,玻璃纤维面料还提供了改进的物理和机械性能。玻璃纤维是最通常地被置于塑料或聚合物基质中的,在基质中高拉伸强度的玻璃纤维使可变形的或者弹性的基质变得更坚硬。为获得玻璃增固的复合材料,要将由短纤维和热塑性树脂粉末或颗粒制成的纤维增固的树脂粒料在挤出机中加工。通过塑料注射成型制得由纤维增固树脂粒料构成的多种合成品。
尽管聚合物合金型技术近来取得了进展,但在合金型领域中还留有实质的改进空间。尽管由这些合金型形成的制品最初展现出优良的增固性能,但这些合金型中的许多在几个月之后就暴露出差的织线强度和弱的抗落锤撞击性能。所以仍然需要一种具有改进的物理和机械性能的玻璃填充聚合物合金型。
发明内容
本发明提供一种由包括以下物质的组合物熔融混合所形成的聚合物合金型组合物:约40wt%-约75wt%的至少一种聚酰胺、约10wt%-约50wt%的聚丙烯、约0.01wt%-约1.0wt%的至少一种包括有乙烯基芳族单体和共轭二烯的嵌段共聚物,并且进一步包括有约0.1wt%-约5.0wt%的至少一种嵌段共聚物或三聚物的不饱和的二羧基试剂的嵌段共聚物,其中该三聚物可以含有接枝到其上的不饱和二羧基试剂、约0.01%-约7.5%的包括有α-烯烃和不饱和的二羧基试剂的相容剂,和约5wt%-约50wt%的填料。
本发明的合金型与现有技术的玻璃纤维增固的尼龙混合物相比展现出改进的织线强度和改进的抗落锤撞击性能。本发明的玻璃纤维增固的尼龙/聚丙烯合金型可将加工玻璃填充的尼龙时由于吸收水分而普遍遇到的负面效果减少到最小。本发明的合金型除了在高湿度情况下尺寸的稳定性之外还具有较低的吸水性,高的耐热性和改进的物理和化学性能,以及一个宽广的适用于各种用途的加工范围。
本发明的前述和其他特征在下文中更完整地描述,特别是在权利要求书、下面详细阐述本发明的某些说明性实施方案的说明书中指出,然而这些只是采用本发明的原则的许多方式中其中的一部分。
优选实施例
除非上下文另作说明,在说明书和权利要求书中,存在的聚合物的量由包含的聚合物组合物中的填料、玻璃或其他非聚合物添加物而确定。因此,每一聚合物的量是通过将聚合物的重量除以存在于组合物中的所有组分的组合重量来确定的。
本发明的玻璃纤维增固的尼龙/聚丙烯合金型与现有技术的玻璃纤维增固的尼龙混合物相比展现出改进的织线强度和改进的抗落锤撞击性能。本发明的玻璃纤维增固的尼龙/聚丙烯合金型可将加工玻璃填充的尼龙时由于吸收水分而普遍遇到的负面效果减少到最小,并且展现出其它的优点,包括在高湿度条件下尺寸的稳定性和高的耐热性。用本发明的聚合物合金型形成的模制品具有改进的物理和化学性能,包括较高的织线拉伸强度、较高的熔体流动速率和较大的拉伸强度。
本发明的聚合物合金型可以由包括以下物质的组合物熔融混合而形成:约40wt%-约75wt%的至少一种聚酰胺(A)、约10wt%-约50wt%的聚丙烯(B)、约0.01wt%-约1.0wt%的包括有乙烯基芳族单体和共轭二烯,并且进一步包括有不饱和的二羧基试剂的至少一种嵌段共聚物(C)、约0.1wt%-约5.0wt%的至少一种嵌段共聚物(D)(i)或三聚物(D)(ii),其中该三聚物(D)(ii)可以含有接枝到其上的不饱和二羧基试剂、约0.01%-约7.5%的包括有α-烯烃和不饱和的二羧基试剂的相容剂(E),和约5wt%-约50wt%的填料(F)。下面将单独讨论这些组分。
聚酰胺(A)
该聚合物合金型组合物包括至少一种聚酰胺树脂(A)。该聚合物混合物通常包括约40wt%-约75wt%,更优选约40wt%-60wt%,最优选约43wt%-约60wt%的至少一种聚酰胺树脂。聚酰胺提供给本发明的聚合物组合物所需的性能例如强度和刚度。
多种聚酰胺树脂适用于本发明的聚合物合金型组合物,这些聚酰胺树脂包括半结晶和无定形或者透明的聚酰胺。这些聚酰胺树脂普遍被称作尼龙。优选极低粘度的聚酰胺树脂。通常,聚酰胺树脂的数均聚合度为至少100或者对于尼龙6而言,数均分子量至少约11,000,对于尼龙6,6而言为22,000。
可以通过等摩尔数量的含有4-12个碳原子的饱和二羧酸与二胺的缩合而制得聚酰胺树脂,其中二胺含有约4-约16个碳原子。在选择方案中,二羧酸可以是芳族二羧酸例如间苯二甲酸或对苯二甲酸。脂族饱和二羧酸的实施例包括癸二酸、十八烷酸、癸二酸、壬二酸、十一烷二酸、戊二酸、庚二酸,尤其是己二酸。
可与二羧酸反应以形成尼龙的二胺的实施例包括这些二胺,例如四亚甲基二胺、五亚甲基二胺、八亚甲基二胺、十亚甲基二胺、十六亚甲基二二胺,特别是六亚甲基二胺。可以使用的芳族胺的实施例包括对-亚苯基二胺和4,4′-二氨基二苯基砜。
也可通过环状内酰胺的开环聚合制得聚酰胺树脂。在聚酰胺中的羧基端基之上过量的二胺可用于提供过量的胺端基。可用于本发明的组合物的特定聚酰胺的实施例包括聚四亚甲基己二酰胺(尼龙4,6)、聚六亚甲基己二酰胺(尼龙6,6)、聚六亚甲基壬二酰胺(尼龙6,9)、聚六亚甲基癸二酰胺(尼龙6,10)、聚六亚甲基十二烷酰胺(尼龙6,12)和通过内酰胺的开环制得的聚酰胺例如聚己内酰胺、聚丁内酰胺、聚新戊内酰胺、聚月桂内酰胺、聚-11-氨基十一烷酸和双(对-氨基环己基)甲烷十二烷酰胺等。
还可以采用通过两种或多种以上聚合物的共聚或者以上聚合物或它们的组分的三聚制得的聚酰胺。例如,合适的聚酰胺是己二酸、间苯二甲酸、六亚甲基二胺共聚物。其它共聚物包括尼龙-6/尼龙-66和尼龙-6/尼龙-12。
通常,聚酰胺将具有至少约200一直到约30,000的数均分子量。在一个实施方案中,优选采用数均分子量至少为5000的聚酰胺。可用的聚酰胺的熔点对于尼龙6而言为约217℃-约223℃,对于尼龙6,6而言为约259℃-约265℃。优选采用作为对于尼龙6而言熔点超过约220℃,对于尼龙6,6而言超过约262℃的线型聚合物的聚酰胺。除了使用共聚物之外,本发明的聚合物组合物还可以含有两种或多种上述聚酰胺的混合物。
聚丙烯(B)
本发明的聚合物组合物包括约10wt%-约50wt%,更优选约10wt%-约40wt%的聚丙烯。该聚丙烯组分优选是聚丙烯的均聚物或共聚物或者均聚物和共聚物的混合物。在本说明书和权利要求书中,术语聚丙烯意在包括聚丙烯和其共聚物。
聚丙烯聚合物的结构可以是半结晶或结晶。聚丙烯聚合物的数均分子量优选超过50,000,更优选超过约225,000。有许多可商购获得、适用于制备本发明聚合物组合物的聚丙烯聚合物。
嵌段聚合物(C)
本发明的聚合物组合物进一步包括至少一种乙烯基芳族单体和共轭二烯的嵌段聚合物,其部分氢化的衍生物或者其选择性氢化的衍生物,该共聚物进一步包括不饱和的二羧基试剂。乙烯基芳族单体和共轭二烯的嵌段聚合物(C)通常以聚合物组合物的约0.01wt%-约1.0wt%的量存在。该嵌段聚合物(C)含有至多约50%的乙烯基芳族单体。
该嵌段聚合物通常是嵌段共聚物,并且可以是二嵌段、三嵌段、多嵌段、星型嵌段、聚嵌段或接枝嵌段聚合物。在本说明书和权利要求书中,关于嵌段聚合物的结构特征的术语二嵌段、三嵌段、多嵌段、聚嵌段和接枝或接枝-嵌段即为文献,例如Encyclopedia of Polymer Science and Engineering,2卷(1985)John Wiley&Sons,Inc.,纽约,325-326页和J.E.McGrath于BlockCopolymers,Science Technology,Dale J.Meier出版,Harwood AcademicPublishers,1979,1-5页中所限定的一般定义。
这些嵌段共聚物可以含有不同比例的共轭二烯与乙烯基芳族单体。因此,多嵌段聚合物可以采用线型或者径向对称或不对称,并且具有由式A-B、A-B-A、A-B-A-B、B-A-B、(AB)0,1,2…BA等表示的结构,其中A是乙烯基芳族单体的聚合物嵌段或者共轭二烯/乙烯基芳族单体锥形聚合物嵌段,B是共轭二烯的聚合物嵌段。
嵌段聚合物可以通过任何公知的嵌段聚合或共聚步骤,包括依次加入单体、增量加入单体或者偶联技术来制备。众所周知,通过利用共聚反应率的不同将共轭二烯和乙烯基芳族单体的混合物共聚而使锥形聚合物嵌段结合到多嵌段共聚物中。
可用于制备嵌段聚合物的共轭二烯含有4-约10个碳原子,更特别地4-6个碳原子。实施例包括1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)、2,3-二甲基-1,3-丁二烯、氯丁二烯、1,3-戊二烯、1,3-己二烯等。也可以使用这些共轭二烯的混合物。优选的共轭二烯是异戊二烯和1,3-丁二烯。
可用于制备嵌段聚合物的乙烯基芳族单体如上所述。优选的乙烯基芳族单体是苯乙烯。许多上述共轭二烯和乙烯基芳族化合物的聚合物可商购获得。氢化之前嵌段聚合物的数均分子量为约20,000-约500,000,优选约40,000-约300,000。
嵌段共聚物中单个嵌段的平均分子量可以在一定界限内改变。在大多数情况下,乙烯基芳族嵌段将具有约2000-约125,000数量级,优选约4000-约60,000的数均分子量。共轭二烯嵌段在氢化之前或在氢化之后将具有约10,000-约450,000数量级,更优选约35,000-150,000的数均分子量。
氢化之前嵌段聚合物的乙烯基含量为约10%-约80%,并且当需要改性的嵌段聚合物表现出橡胶态弹性时,乙烯基含量优选为约25%-约65%,更优选约35%-约55%。可以通过NMR光谱测量嵌段聚合物的乙烯基含量。
二嵌段共聚物的特定实施例包括苯乙烯-丁二烯、苯乙烯-乙烯和其氢化的衍生物。三嵌段聚合物的实施例包括苯乙烯-丁二烯-苯乙烯、苯乙烯-异戊二烯-苯乙烯、α-甲基苯乙烯-丁二烯-α-甲基苯乙烯,和它们部分氢化的衍生物。优选的多嵌段聚合物的实施例包括苯乙烯和异戊二烯或丁二烯的多嵌段聚合物。这些二嵌段、三嵌段、多嵌段和星型嵌段聚合物可在不同的商品名下从各种来源商购获得。
可以通过许多公知的方法来进行嵌段聚合物的选择性氢化,这些方法包括在催化剂例如阮内镍、金属如铂和钯,和可溶性过渡金属催化剂的存在下的氢化。合适的氢化方法是将含有二烯的聚合物或聚合物溶于惰性氢化稀释剂例如环己烷中,并且通过在可溶性氢化催化剂存在下与氢气反应而氢化。这些步骤己被美国专利3,113,986和4,226,952所公开。选择性氢化的聚合物在聚二烯嵌段中的残余不饱和含量为氢化之前它们的原始不饱和含量的约0.5%-约20%。在一个实施方案中,嵌段聚合物的共轭二烯部分至少90%饱和,更通常至少95%饱和,然而乙烯基芳族部分并没有明显氢化。
乙烯基芳族单体和共轭二烯的嵌段聚合物还可以用一种或多种不饱和的单羧基或二羧基试剂接枝。该羧基试剂包括羧酸和它们的官能化衍生物,例如酐、酰亚胺、金属盐、酯等,其能够接枝到嵌段聚合物上。基于嵌段聚合物和接枝羧酸的羧基试剂的总重量,该接枝聚合物将通常占约0.2wt%-约20wt%,优选约0.1wt%-约10wt%。可用的单羧酸和它们的衍生物的特定实施例包括丙烯酸、甲基丙烯酸、氰酰胺酸、巴豆酸、丙烯酸酐、丙烯酸钠、丙烯酸钙、丙烯酸镁等。可用的二羧酸和它们的衍生物的特定实施例包括马来酸、马来酸酐、富马酸、中康酸、衣康酸、柠康酸、衣康酸酐、柠康酸酐、马来酸单甲酯、马来酸单钠等。
为了使羧酸试剂接枝到氢化的嵌段聚合物上,则采用自由基引发剂,并且这些引发剂包括过氧化物和各种有机偶氮化合物。基于组合的聚合物和羧基试剂的组合重量,使用的引发剂的量通常为约0.01wt%-约5wt%。可以通过测定产品总的酸值来测量接枝到嵌段聚合物上的羧酸试剂的量。可以通过在自由基引发剂的存在下将嵌段聚合物和羧酸试剂熔融或者溶液混合来进行接枝反应。
可商购获得的马来酸化选择性氢化的苯乙烯和丁二烯的聚合物的实施例包括可从Kraton Polymers获得的KRATONTM FG1901X,其是基于苯乙烯和乙烯/丁烯的完全线型的三嵌段共聚物,聚苯乙烯含量为30%。
嵌段聚合物或三聚物(D)
本发明的聚合物组合物还包括至少一种嵌段聚合物(D)(i)或三聚物(D)(ii)、其部分氢化的衍生物,或者其选择性氢化的衍生物。嵌段聚合物或三聚物(D)通常以聚合物组合物的约0.1wt%-约5.0wt%的量存在。
嵌段聚合物(D)(i)通常是共聚物,并且可以包括乙烯基芳族单体和共轭二烯,或者是其部分氢化的衍生物或其选择性氢化的衍生物。嵌段共聚物(D)(i)可以含有至多约50%的乙烯基芳族单体。可用的嵌段聚合物的实施例是SEBS嵌段聚合物例如KRATONTMG-1652,其可从Kraton Polymers获得。KRATONTMG-1652是带有聚苯乙烯端嵌段和橡胶态聚(乙烯-丁烯)中间嵌段的三嵌段共聚物。
(D)(ii)的适合的三聚物是EPDM共聚物(或者乙烯-丙烯-二烯,“M”是指饱和的主链结构)。考虑到EPDM共聚物,二烯重复单元的量通常小至至多约10wt%,并且最好为至多约4wt%。因此,共聚物的剩余部分由不同含量的乙烯和丙烯的重复单元所组成。合适的二烯的实施例包括1,4-己二烯、二环戊二烯、亚乙基降冰片烯、甲基降冰片烯等。有许多可商购获得的EPDM三聚物。
任选地,三聚物(D)(ii)可以含有接枝到其上的一种或多种不饱和的单羧基或二羧基试剂。该羧基试剂包括羧酸和它们的官能化衍生物,例如酐、酰亚胺、金属盐、酯等,其能够接枝到嵌段聚合物上。基于三聚物和接枝羧酸的羧基试剂的总重量,该接枝聚合物将通常占约0.2wt%-约20wt%,优选约0.1wt%-约10wt%。可用的单羧酸和它们的衍生物的特定实施例包括丙烯酸、甲基丙烯酸、氰酰胺酸、巴豆酸、丙烯酸酐、丙烯酸钠、丙烯酸钙、丙烯酸镁等。可用的二羧酸和它们的衍生物的特定实施例包括马来酸、马来酸酐、富马酸、中康酸、衣康酸、柠康酸、衣康酸酐、柠康酸酐、马来酸单甲酯、马来酸单钠等。可用的三聚物的实施例是EPDM三聚物,例如可从Uniroyal/Crompton Corporation获得的Royaltuf485,其包括马来酸酐接枝物。
相容剂(E)
本发明的聚合物组合物进一步包括一种或多种相容剂。该相容剂包括至少一种α-烯烃聚合物和不饱和羧酸试剂的反应产物。通常,该聚合物组合物含有约0.01wt%-约7.5wt%的相容剂(E)。
用于相容剂的α-烯烃聚合物是包括均聚物、共聚物、三聚物或其混合物的半结晶或者可结晶的烯烃聚合物,并且含有一个或多个单体单元。优选地,α-烯烃聚合物衍生自α-烯烃例如乙烯、丙烯、1-丁烯等。烯烃聚合物优选是聚乙烯、聚丙烯或其混合物。用于与羧酸试剂反应的聚烯烃的数均分子量通常低于如上作为组分(B)所述的,在本发明的共混聚合物组合物中用作主要组分的聚丙烯的数均分子量。
与聚烯烃反应的羧酸试剂的量可以为基于α-烯烃聚合物重量的约0.2wt%-约20wt%。更通常地,与聚烯烃反应的酸试剂的量将少于10%,最通常为约0.1wt%-约5wt%。不饱和的羧酸试剂可以是α,β-烯属不饱和羧酸试剂。合适的试剂的实施例是如上所述在有关(D)的段落中作为用于接枝到三聚物上的那些合适的试剂。羧基试剂包括羧酸和它们的官能化衍生物,例如酐、酰亚胺、金属盐、酯等。特别优选的α,β-烯属不饱和羧基试剂是马来酸。对应的酐-马来酸酐也是优选的羧基试剂。可商购获得的马来酸酐接枝的聚丙烯的实施例是可从Uniroyal获得的Polybond 3200。Polybond 3200含有1%的马来酸酐。
填料(F)
本发明的聚合物组合物还包括一种或多种填料(F)。该聚合物组合物通常包括约5wt%-约50wt%的一种或多种填料。合适的填料的实施例包括玻璃纤维、碳纤维、云母、合成聚合物纤维、硼纤维、硅灰石、白云石、炭黑、滑石、碳酸钙、颜料例如二氧化钛,和其混合物。优选的填料包括玻璃纤维,其实施例是可从Owens Corning获得的123D-10P Cratec Plus E玻璃短切纤维。玻璃纤维可以用偶联剂处理以提高玻璃纤维与聚合物树脂之间的连结。例如,玻璃纤维可以用材料例如脂肪酸、硅烷、马来酸化的聚丙烯等处理。使用的偶联剂的量是以有效地提高玻璃纤维与聚合物树脂之间的连结为宜。
纤维优选平均直径约5-约25微米,平均长度约0.125″-约0.500″。优选地,纤维的纵横比(即纤维长度与纤维直径的比例)约10-约500。
其他添加剂可以包括在本发明的聚合物组合物中,以改进或者以获得所需的性能。例如,氧化、热和紫外线分解的稳定剂和抑制剂可以包括在聚合物混合物中,以及润滑剂和脱模剂、包括染料和颜料的着色剂、成核剂、增塑剂、阻燃剂等可以包括在聚合物组合物中。
可以在制备聚合物混合物的任意阶段将稳定剂引入该组合物中,并且优选地,稳定剂在开始就加入,以在组合物得到保护之前排除最初的分解。可用于本发明的聚合物混合物的氧化和热稳定剂包括那些通常用于加成聚合物的稳定剂。它们包括,例如基于聚合物混合物的重量至多约1wt%的I族金属卤化物例如钠、钾、锂和亚铜的卤化物(例如氯化物、溴化物和碘化物)、受阻酚、对苯二酚和这些材料的各种取代衍生物及其组合。
基于聚合物混合物的重量,紫外线稳定剂的加入量至多约2wt%。紫外线稳定剂的实施例包括各种取代的间苯二酚、水杨酸酯、苯并三唑、苯甲酮等。
基于聚合物混合物的重量,可加入至多约1wt%的量的适合的润滑剂和脱模剂包括这些材料,例如硬脂酸、硬脂醇、硬脂酸盐、硬脂酰胺、有机染料例如苯胺黑、颜料例如二氧化钛、硫化镉、炭黑等。基于聚合物混合物的重量,可加入至多约20wt%的量的增塑剂包括这些材料,例如二辛基间苯二甲酸盐、联苄基间苯二甲酸盐、丁基苯并间苯二甲酸盐、烃油、磺酰胺例如对-甲苯乙基磺酰胺、正丁基苯磺酰胺等。
本发明的聚合物组合物与现有技术的玻璃纤维增固的尼龙混合物相比展现出提高的织线强度和改进的抗落锤撞击性能。本发明聚合物组合物中的玻璃纤维走向不同于以前的聚合物混合物中的玻璃纤维。虽无特定的理论可以依循,但申请人认为,玻璃纤维不适当的走向会负面影响聚合物混合物的织线强度和耐用性。聚合物合金型中的玻璃纤维的走向在注塑过程中由于过多地偶联到多种官能化聚合物组分上会受到不利的影响。本发明的聚合物合金型的相容剂系统使聚合物相的相容性达到最大,而不促进过多的纤维偶联。过多的纤维偶联被认为尤其在织线时会急剧增加粘度并且不利于合适的纤维走向。本发明的聚合物合金型促进了合适的纤维走向,这对织线强度具有促进作用。
以下实施例仅仅用来解释本发明,并且不应该被认为对权利要求进行了限制。
实施例1
通过Werner-Pfleiderer双螺杆(70mm)挤出机在450rpm下将下面列于表1中的组分组合而制备组合物A和B以及对照样品。然后在540°F下将两种组合物挤出成股线,并在成粒之前使股线通过水浴。在560°F下将粒料注塑成测试样品。对照样品和组合物A的物理性能列于下表2中。
表1
商业说明 | 化学名称 | 对照样品 | 组合物A | 组合物B |
Rhodia 24AE1 | 尼龙6,6树脂,极低粘度(36RV) | 37.1 | 43.0 | 43.0 |
Equistar31S3A | 聚丙烯均聚物,3熔体流动速率 | 18.6 | 11.45 | 11.45 |
KratonFG-1901x | SEBS三聚物,1%马来酸酐接枝 | 3.0 | 0.3 | 0.3 |
Kraton G-1652 | SEBS嵌段共聚物 | ** | 2.0 | ** |
Royaltuf 485 | 马来酸酐接枝的EPDM三聚物 | ** | ** | 2.0 |
OCF 173x 11C | 11微米玻璃纤维,尼龙制备 | 38 | ** | ** |
OCF 123D 10P | 10微米玻璃纤维,尼龙制备 | ** | 40 | 40 |
Irganox B-225 | 苯酚/亚磷酸盐抗氧剂混合物 | 0.4 | 0.25 | 0.25 |
IrganoxB-1171 | 苯酚/亚磷酸盐抗氧剂混合物 | 0.4 | 0.25 | 0.25 |
UniroyalPolybond 3200 | 聚丙烯均聚物,1%马来酸酐接枝 | 1.5 | 2.0 | 2.0 |
PolymerPartners NylonBK | 30%炭黑浓缩物,尼龙6,6载体 | 1.0 | 0.75 | 0.75 |
总重量% | 100 | 100 | 100 |
表2
性能 | 测试方法 | 单位 | 对照样品 | 组合物A |
熔体流动速率@275℃,5 | ASTM D1238 | g/10min | 2.5 | 25.0 |
灰含量 | ASTM D2584 | % | 38 | 38 |
有切口的缺口@23℃ | ASTM D256 | ft-lb/in | 2.9 | 2.9 |
未切口的缺口 | ASTM D4812 | ft-lb/in | 20.5 | 21.6 |
拉伸强度 | ASTM D638 | psi | 20,510 | 22,000 |
断裂伸长率 | ASTM D638 | % | 5.5 | 6.1 |
挠曲强度 | ASTM D790 | psi | 30,120 | 32,930 |
正切模量 | ASTM D790 | psi | 1,223,500 | 1,390,000 |
割线模量,1% | ASTM D790 | psi | 1,188,000 | 1,350,000 |
抗器械撞击强度 | ASTM D3763 | in-lb | 90 | 130 |
比重 | ASTM D792 | -- | 1.34 | 1.35 |
HDT@264psi | ASTM D648 | °F | 472 | 472 |
织线拉伸强度 | ASTM D638 | psi | 6,000 | >13,000 |
将组合物A与对照样品的物理性能作比较,明显的看出组合物A的织线拉伸强度超过对照样品的织线拉伸强度的两倍。除了具有较强的织线强度之外,组合物A与对照样品相比还具有较高的抗器械冲击强度。组合物A还具有较高的熔体流动速率和较高的总拉伸强度。组合物B的物理性能与组合物A的几乎相同。
另外的优点和改进对于本领域那些技术人员而言将是容易想到的。因此,本发明在其较宽的范围内并不限于本文中所示和所述的特定细节和说明性实施例。因此所作的各种改进都不偏离由附属的权利要求书和它们的等价物所定义的总的发明原理的精神或范围。
Claims (18)
1.一种由包括以下物质的组合物熔融混合所形成的聚合物合金型:
(A)约40wt%-约75wt%的至少一种聚酰胺;
(B)约10wt%-约50wt%的聚丙烯;
(C)约0.01wt%-约1.0wt%的包括有乙烯基芳族单体和共轭二烯,并且进一步包括有不饱和的二羧基试剂的至少一种嵌段共聚物;
(D)约0.1wt%-约5.0wt%的(i)嵌段共聚物或(ii)三聚物;
(E)约0.01%-约7.5%的包括有α-烯烃和不饱和的二羧基试剂的相容剂;和
(F)约5wt%-约50wt%的填料。
2.根据权利要求1的聚合物合金型,其中所述组合物包括约43wt%-约60wt%的至少一种聚酰胺(A)。
3.根据权利要求1的聚合物合金型,其中聚酰胺选自:聚六亚甲基己二酰胺、聚六亚甲基癸二酰胺、聚己内酰胺、聚六亚甲基间苯二酰胺、聚六亚甲基对苯二酰胺-共聚-间苯二酰胺、聚四亚甲基己二酰胺和其混合物。
4.根据权利要求1的聚合物合金型,其中(C)的嵌段共聚物是苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
5.根据权利要求1的聚合物合金型,其中D(i)的嵌段共聚物是苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
6.根据权利要求1的聚合物合金型,其中D(ii)的三聚物是乙烯-丙烯-二烯三聚物。
7.根据权利要求1的聚合物合金型,其中(C)的不饱和二羧基试剂包括马来酸酐。
8.根据权利要求1的聚合物合金型,其中D(ii)的三聚物含有接枝到其上的不饱和二羧基试剂。
9.根据权利要求8的聚合物合金型,其中D(ii)的不饱和二羧基试剂包括马来酸酐。
10.根据权利要求1的聚合物合金型,其中(E)的不饱和二羧基试剂包括马来酸酐。
11.根据权利要求1的聚合物合金型,其中(E)的α-烯烃选自丙烯和其共聚物。
12.根据权利要求1的聚合物合金型,其中填料包括玻璃纤维。
13.一种由包括以下物质的组合物熔融混合所形成的聚合物合金型:
(A)约43wt%-约60wt%的至少一种聚酰胺;
(B)约10wt%-约40wt%的聚丙烯;
(C)约0.01wt%-约1.0wt%的包括有乙烯基芳族单体和共轭二烯的嵌段共聚物,并且进一步包括有马来酸酐的至少一种相容剂;
(D)约0.1wt%-约5.0wt%的(i)嵌段共聚物或(ii)三聚物;
(E)约1.5%-约7.5%的包括有聚丙烯和马来酸酐的第三相容剂;和
(F)约5wt%-约50wt%的包括玻璃纤维的填料。
14.根据权利要求13的聚合物合金型,其中聚酰胺选自:聚六亚甲基己二酰胺、聚六亚甲基癸二酰胺、聚己内酰胺、聚六亚甲基间苯二酰胺、聚六亚甲基对苯二酰胺-共聚-间苯二酰胺、聚四亚甲基己二酰胺和其混合物。
15.根据权利要求13的聚合物合金型,其中(C)的嵌段共聚物是苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
16.根据权利要求13的聚合物合金型,其中D(i)的嵌段共聚物是苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
17.根据权利要求13的聚合物合金型,其中D(ii)的三聚物是乙烯-丙烯-二烯三聚物。
18.根据权利要求13的聚合物合金型,其中D(ii)的三聚物含有接枝到其上的马来酸酐。
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CF01 | Termination of patent right due to non-payment of annual fee |