CN107057388A - 聚合物复合材料 - Google Patents
聚合物复合材料 Download PDFInfo
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Abstract
本发明涉及一种聚合物复合材料。具体地,本发明涉及一种包含65至90重量%的硫酸盐化学木浆纤维和热塑性聚合物的组合物,以及所述组合物的制造方法。在一种实施方式中,将量为约5‑10%以及在另一种实施方式中将量为约0.2‑5%的偶联剂掺入到复合材料配方和可熔融加工的组合物中。可以向纤维/聚合物掺混物添加填充剂和化学木浆纤维之外的纤维,以赋予所需物理特征或降低用于给定应用所需的聚合物的量。
Description
本申请是国际申请日2012年2月10日、国际申请号PCT/US2012/024705于2013年8月14日进入中国国家阶段、申请号201280008898.6、发明名称“聚合物复合材料”的申请的分案申请。
与相关申请的交叉引用
依据35U.S.C.§119,本申请有权享有并且要求2011年2月14日提交的题为“聚合物复合材料(Polymeric Composites)”的美国临时专利申请系列号61/442,716的优先权,所述临时专利申请的内容在此引为参考。
发明领域
本发明涉及源自于聚合物基质与化学木浆纤维的熔融加工的聚合物复合材料。
发明背景
在复合聚合物材料的模制中存在三个步骤。第一步骤是形成母料材料。第二步骤是将母料材料调合成调合材料。第三步骤是将调合材料模制成最终模制产品。在某些情况下,步骤1和2可以合并。
附图简述
图1–5是用于制造聚合物复合材料的球粒的示意图。
图6是混合器的示意图。
图7和8是造粒机的示意图。
图9是可用于制造本发明球粒的单螺杆挤出机的示意图。
详细描述
本发明涉及一种解决方案,其为从化学木浆板生产包含65至90重量%化学木浆纤维的复合聚合物材料提供经济的手段。本发明的复合材料具有均匀地分散在聚合物基质中的化学木浆纤维。
在一种实施方式中,化学木浆纤维是漂白的化学木浆纤维。使用漂白的化学木浆纤维而不是未漂白的木浆纤维有几个原因。
一个原因是颜色。漂白的化学木浆纤维基本上完全是纤维素和半纤维素。纤维素和半纤维素本身没有颜色,因此它们为复合材料赋予很少颜色或不赋予颜色。另一方面,未漂白的纤维例如天然纤维如洋麻纤维或全木纤维具有高达50%的木质素和在其天然状态下可以着色或在加热至热塑性处理温度时变得有色的其他化合物。具有未漂白的天然或全木纤维的复合材料将变得有色,可能为暗棕色。
另一个原因是气味。纤维素没有气味,因此具有漂白的木浆纤维的复合材料具有非常低的由纤维素造成的气味。未漂白纤维中的木质素和其他组分在熔融加工时具有强的特征性气味,赋予得到的复合材料以强烈气味,限制了它在封闭区域例如汽车内部中的使用。
存在着与化学木浆纤维在整个聚合物基质中均匀分散相关的问题。纤维最初是在干燥过的木浆板中。干燥使木浆纤维塌陷。干燥也引起木浆纤维通过氢键键合在一起。为了获得基本上单个的纤维,必须将氢键打断。一些纤维将保持键合。这些根据大小被称为结节(knot)或编结(knit)。在打断纤维之间的氢键后,通常存在少量残留的结节和编结。
还存在着与提供水平为纤维/聚合物混合物的总重量的65重量%以上的化学木浆纤维相关的问题。更少量的聚合物意味着更难将纤维分散在聚合物基质中。更少量的聚合物意味着更难将纤维均匀地分散在整个聚合物基质中。随着纤维量的增加,纤维/聚合物混合物变得更加粘稠,因此更难将纤维在基质内移动以提供分散。目的是具有非常少的纤维团块。
待解决的问题是在聚合物基质中提供基本上单个形式的纤维,并将纤维以基本上均匀的量计量加入到聚合物中,以便木浆纤维/复合材料具有基本上均匀分散在整个复合材料中的木浆纤维。本发明携带从木浆板获得的化学木浆的切碎粒子,将它们计量加入到聚合物中,并在将木浆与聚合物混合时将木浆纤维基本上单个地分割开(singulate)。
聚合物基质起到主体聚合物的作用,并且是包含化学木浆原料的可熔融加工的组合物的组分。使用熔融加工将聚合物与化学木浆纤维合并。在熔融加工中,将聚合物加热并熔化,并将化学木浆纤维与聚合物合并。
聚合物是热塑性的。
在本技术领域中常规认识到的适用于熔融加工的广泛类型的聚合物,可用作聚合物基质。聚合物基质基本上包括有时被称为难以熔融加工的聚合物,特别是当与干扰要素或另一种不混溶聚合物合并时。它们包括烃类和非烃类聚合物两者。有用的聚合物基质的实例包括但不限于高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、聚丙烯(PP)、聚烯烃共聚物(例如乙烯-丁烯、乙烯-辛烯、乙烯-乙烯醇)、聚苯乙烯、聚苯乙烯共聚物(例如高抗冲聚苯乙烯、丙烯腈丁二烯苯乙烯共聚物)、聚丙烯酸酯、聚甲基丙烯酸酯、聚酯、聚氯乙烯(PVC)、含氟聚合物、液晶聚合物、聚酰胺、聚醚酰亚胺、聚苯硫醚、聚砜、聚缩醛、聚碳酸酯、聚苯醚、聚氨酯、热塑性弹性体、环氧树脂、醇酸树脂、三聚氰胺类、酚醛树脂、脲、乙烯基酯或其组合。在某些实施方式中,最适合的聚合物基质是聚烯烃。
源自于再生塑料的聚合物基质也是适用的,因为它们通常成本较低。然而,由于这样的材料通常源自于来自多种废物流的材料,因此它们可能具有非常不同的熔体流变性质。这可能使材料的加工非常困难。向再生聚合物基质添加纤维素质原料将提高熔体粘度并降低总体变化性,因此改善了加工。
可以利用纤维素木浆纤维的塑料或聚合物材料的部分名单,可以包括聚烯烃、聚乙烯、聚丙烯、聚氯乙烯、ABS、聚酰胺、它们的混合物、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚对苯二甲酸丙二酯、乙烯-一氧化碳和苯乙烯共聚物掺混物例如苯乙烯/丙烯腈和苯乙烯/马来酸酐热塑性聚合物、聚缩醛、纤维素丁酸酯、丙烯腈-丁二烯-苯乙烯、某些甲基丙烯酸甲酯和聚三氟氯乙烯聚合物。可以利用纤维素木浆纤维的热固性或热塑性材料的完整名单,对于本领域技术人员来说是已知的。
在一种实施方式中,将化学木浆原料与不相容的聚合物基质(例如聚烯烃)进行熔融加工。在另一种实施方式中,将化学木浆原料与相容的聚合物基质(例如改性的纤维素质聚合物)进行熔融加工。例如,已发现当将本发明的化学木浆原料与纤维素丙酸酯(TeniteTM350E)进行熔融加工时,得到的复合材料具有出色的纤维分散性和机械性质。
本发明还设想了在复合材料配方中使用偶联剂。偶联剂通常用于提高填充剂与聚合物基质的界面润湿。添加偶联剂或增容剂通常改进得到的复合材料的机械性质。正如常规已知的,本发明利用偶联剂提高本发明的化学木浆纤维与聚合物基质之间的润湿。然而,我们还发现,偶联剂的添加改善了本发明的化学木浆原料与某些聚合物的熔融加工和分散性。
与聚烯烃一起使用的优选偶联剂是聚烯烃接枝马来酸酐共聚物。在一种实施方式中,将聚合物基质和纤维素质原料与聚烯烃接枝马来酸酐共聚物一起进行熔融加工。本发明的可商购的偶联剂包括在商品名PolybondTM(Chemtura)、ExxelorTM(Exxon Mobil)、FusabondTM(DuPont)、LotaderTM(Arkema)、BondyramTM(Maroon)、Integrate(Equistar)下销售的产品。除了化学木浆原料之外,聚合物基质可以含有一种或多种填充剂。接枝共聚物中的聚烯烃与在聚合物基质中用作聚合物的聚烯烃相同。例如,聚乙烯接枝马来酸酐与聚乙烯一起使用,聚丙烯接枝马来酸酐与聚丙烯一起使用。
在一种实施方式中,将量为约5-10%以及在另一种实施方式中将量为约0.2-5%的偶联剂掺入到复合材料配方和可熔融加工的组合物中。
可以向纤维/聚合物掺混物添加填充剂和化学木浆纤维之外的纤维,以赋予所需物理特征或降低用于给定应用所需的聚合物的量。填充剂通常含有水分,因此降低了聚合物基质中存在的增容剂的功效。填充剂和纤维的非限制性实例包括木粉、化学木浆纤维之外的天然纤维、玻璃纤维、碳酸钙、滑石粉、二氧化硅、粘土、氢氧化镁和氢氧化铝。
在本发明的另一方面,可熔融加工的组合物可能含有其他添加剂。常规添加剂的非限制性实例包括抗氧化剂、光稳定剂、纤维、起泡剂、发泡添加剂、防结块剂、热稳定剂、抗冲改性剂、杀生物剂、阻燃剂、增塑剂、增粘剂、着色剂、加工助剂、润滑剂、增容剂和颜料。添加剂可以以粉末、球粒、颗粒形式或任何其他可挤出或可调合的形式掺入到可熔融加工的组合物中。可熔融加工的组合物中常规添加剂的量和类型可能随着聚合物基质和最终组合物的所需物理性质而变。熔融加工领域的技术人员能够选择与特定聚合物基质匹配的添加剂的适合的量和类型,以便获得最终材料的所需物理性质。
在一种实施方式中,通过将化学木浆板材机械性切成方块来生产本发明的化学木浆原料。在一种实施方式中,将化学木浆原料切成六边形形状,其便于与常规的进料设备一起使用。在其他实施方式中,形状可以是三角形、矩形或五边形形状的粒子。本发明的复合材料通过对聚合物基质和化学木浆原料进行熔融加工来生产。在一种实施方式中,在熔融加工后将化学木浆原料均匀分散在聚合物基质中。
本发明涉及一种解决方案,其为生产含有良好分散的化学木浆纤维的复合材料提供经济的手段。这通过利用具有增加的堆积密度并能够使用常规进料技术进料到熔融加工设备中的化学木浆原料来实现。本发明的复合材料具有良好分散在聚合物基质内的化学木浆纤维。
本发明可以利用大量树种作为木浆、纸板和纸纤维的来源。可以使用针叶和阔叶树种及其混合物。它们也被称为软木和硬木。典型的软木树种是各种云杉(例如美国西加云杉)、冷杉(道格拉斯冷杉)、各种铁杉(西部铁杉)、美洲落叶松、落叶松、各种松树(南方松、白松和加勒比松)、柏树和红杉或其混合物。典型的硬木树种是白蜡树、山杨、三叶杨、椴树、桦树、山毛榉、栗树、胶树、榆树、桉树、枫树、橡树、白杨树和悬铃木或其混合物。
软木或硬木树种的使用可以部分取决于所需的纤维长度。硬木或阔叶树种具有1-2mm的纤维长度。软木或针叶树种具有3.5至7mm的纤维长度。道格拉斯冷杉、大冷杉、西部铁杉、西部落叶松和南方松具有4至6mm范围内的纤维长度。由于纤维断裂,制浆、漂白和切块可能略微降低平均长度。
在浆粕制造中,将木质材料在化学制浆过程中分解成纤维。然后可以任选地将纤维漂白。然后将纤维与水在贮浆池中合并以形成浆液。然后将浆液通过压头箱,然后置于金属丝网上,脱水并干燥,以形成浆板。可以将添加剂在贮浆池、压头箱或两者中与纤维合并。也可以在脱水和干燥之前、期间或之后将材料喷洒在浆板上。在木浆制造中通常使用硫酸盐制浆方法。
纤维素质木浆纤维可以采取商品化纤维素质木浆的形式。材料通常以卷或捆的形式投送。浆板的厚度是能够决定粒子厚度的一种因素。浆板具有两个相对的基本上平行的面,这些面之间的距离将是粒子的厚度。典型的浆板厚度可以为0.1mm至4mm。在某些实施方式中,厚度可以是0.5mm至4mm。影响粒子厚度的其他因素之一是对纤维板的任何预处理的存在。因此,粒子可以比纤维板更厚或更薄。
纤维板和粒子可以具有12g/m2(gsm)至2000g/m2的基重。在一种实施方式中,粒子可以具有600g/m2至1900g/m2的基重。在另一种实施方式中,粒子可以具有500g/m2至900g/m2的基重。对于纸板来说,一种实施方式可以具有70gsm至120gsm的基重。在另一种实施方式中,纸板可以具有100gsm至350gsm的基重。在另一种实施方式中,用于特殊用途的纤维板可以具有350gsm至500gsm的基重。
浆粕添加剂或预处理也可能改变粒子的特点。用剥离剂处理的浆粕与不具有剥离剂的浆粕相比将提供更松散的粒子。更松散的粒子在将与其合并的材料中可能更容易分散。
粒子具有六边形形状,其一种实施方式示出在图1中。所述六边形可以是任何类型,从全等边至全不对称。如果它不是等边的,长轴可以为4至8毫米(mm),短轴可以为2至5mm。所述六边形的一些边可以具有相同长度,并且一些或所有边可以具有不同长度。所述六边形的外周或周长可以为12mm至30mm,粒子的上表面或下表面24或26的面积可以为12至32mm2。在一种实施方式中,粒子可以具有0.1至1.5mm的厚度、4.5至6.5mm的长度、3至4mm的宽度和一个面上15至20mm2的面积。在另一种实施方式中,粒子可以具有1至4mm的厚度、5至8mm的长度、2.5至5mm的宽度和一个面上12至20mm2的面积。
示出了六边形粒子的两个实例。
在图1-3中,粒子10是六边形的,并且具有两条相对的边12和18,其长度相等并且长于其他四条边14、16、20和22。其他四条边14、16、20和22可以如所示具有相同长度,或者所述四条边可以具有不同长度。所述边中的两条,每端各一条,例如14和20或14和22可以具有相同长度,每端的另外两条边16和22或16和20,可以具有相同长度或具有不同长度。在这些变化形式的每种中,边10和18可以具有相同长度或不同长度。粒子的边缘可以是尖锐或圆滑的。
粒子10的顶面24与底面26之间的距离可以为0.1mm至4mm。
图4和5示出了六边形的六条边的每一条具有不同长度的实施方式。示出的实施方式是示例性的,边的长度顺序和边的长度尺寸可以改变。
上述形状、尺寸和基重的粒子可以在本领域公知的重量损失和体积进料***中计量。
纤维在粒子中的排列可以平行于六边形的长轴或垂直于六边形的长轴,或者采取其间的任何取向。
所述六边形粒子可以在Henion切块机上形成,但是可以使用其他手段来生产六边形粒子。
然后将氢键键合的纤维素木浆纤维分散在聚合物中。一种方法是制造富含纤维的母料,其具有65至85重量%的纤维素木浆纤维和15至35重量%的聚合物。如果需要的话,部分的聚合物可以是增容剂。然后将这种材料在相同位置或不同位置处调合,以减少纤维素木浆纤维的量并增加聚合物的量。可以在调合操作中向所述材料添加其他添加剂和填充剂。然后对调合后的材料进行模制。
纤维素木浆纤维向聚合物的最初添加是两步操作。
在第一步中,将六边形球粒与聚合物在混合操作中合并和混合。混合可以在热动力混合器或Gelimat混合器中进行。材料中化学纤维素木浆纤维的量为65至85重量%,聚合物的量为15至35重量%。如果使用增容剂,那么从聚合物的量中减去增容剂的量。如果使用5重量%的增容剂,那么聚合物的量将减少5重量%。非极性聚合物例如烯烃,将使用增容剂。典型的增容剂是接枝共聚物例如马来酸酐聚丙烯或马来酸酐聚乙烯。如果聚合物是聚丙烯,那么也使用最高0.5重量%的抗氧化剂。纤维和聚合物作为松软的材料离开热动力混合器。
图6中示出了混合器30。混合器30具有进料斗32,通过其将材料进料。材料由螺旋进料器34带入混合仓36中,在其中叶片38被马达40快速旋转。叶片38旋转通过混合物,由叶片38产生的离心力将材料朝着混合仓壁42向外移动。摩擦热使得聚合物材料、聚合物和增容剂熔化,并将纤维与聚合物混合。在混合后,将聚合物通过门44从混合仓36中放出.
可以在第一步中使用的另一种方法是具有开口载模板的双螺杆挤出机。双螺杆挤出机在出口端上具有开口载模板(open die plate),使得材料从挤出机的流动不受阻碍。纤维、聚合物和增容剂的量与对热动力混合器所描述的相同。材料作为团块材料离开双螺杆挤出机。
然后将这种材料在造粒机例如California造粒机或单螺杆挤出机例如Bonnot单螺杆挤出机中进一步处理。
图7和8中示出了实验室用造粒机。造粒机50具有进料斗52,来自于热动力混合器或双螺杆挤出机的纤维/聚合物复合材料54被转移到其中。复合材料54落于穿孔板56上。穿孔板56上的孔隙58的尺寸是挤出的球粒60的直径。一对转轮62迫使复合材料通过孔隙58以形成球粒60。转轮62固定在轴64上。轴64固定在转子66上。转子66由马达(未示出)转动,以使转轮62绕着穿孔板56转动。将球粒60从装置中排出并收集。
需要数次实验来确定如何使用单螺杆挤出机来提供纤维素木浆纤维分散在整个聚合物中的材料。在高纤维水平下纤维倾向于团集在一起。已发现,为了获得纤维的分散,必需将通过挤出机的材料流分开。这通过放置从挤出机的外壁延伸到挤出机腔内的钉来进行。迫使材料从装置通过模具孔,以形成挤出的球粒。材料可能倾向于阻塞在载模板后方而不以高效方式通过模具。在模具面背侧添加擦具(wiper),以更高效的方式使材料通过模具孔移动。
图9中示出了单螺杆挤出机。挤出机80具有进料斗82,来自于混合器的纤维复合材料置于其中。进料斗82与桶84相连,螺杆86延伸通过桶84。螺杆86由马达(未示出)转动,并朝向载模板88驱动桶中的材料。螺杆的设计能够在其通过桶移动时在复合材料上施加或多或少的压力。沿着桶放置钉90。钉90可能向内或向外移动以分开通过桶的材料流并协助纤维在聚合物内的分散。载模板86具有许多孔隙92,材料通过所述孔隙形成球粒。
在一种实施方式中,第一双螺杆混合器可以直接连接到第二单螺杆挤出机,并且材料直接从第一混合器通往第二挤出机。可用同一马达来运行两者。
母料球粒含有65至90重量%的化学木浆纤维和15至35重量%的聚合物。
Claims (13)
1.一种组合物,其包含75至90重量%的硫酸盐化学木浆纤维和热塑性聚合物,其中所述纤维以基本上单个形式分散在所述热塑性聚合物内,其中不包括端点75重量%。
2.权利要求1的组合物,其中所述化学木浆纤维具有剥离剂。
3.权利要求1的组合物,其中所述化学木浆纤维不含剥离剂。
4.权利要求1的组合物,其中所述化学木浆纤维是漂白的化学木浆纤维。
5.权利要求1的组合物,其还包含增容剂。
6.权利要求1的组合物,其还包含抗氧化剂。
7.权利要求1的组合物,其中所述化学木浆纤维的量为所述组合物的70重量%至85重量%。
8.权利要求1的组合物,其中所述组合物是球粒。
9.权利要求1的组合物,其中所述聚合物不是聚氯乙烯。
10.一种制造组合物的方法,所述方法包括:
向热动力混合器提供粒子形式的化学木浆纤维,
向所述热动力混合器提供热塑性聚合物,
其中对于提供到所述混合器的每100重量%的材料来说,所述木浆纤维为所述材料的65重量%至90重量%,
将纤维粒子与所述聚合物在所述混合器中混合,以形成纤维以基本上单个形式分散在聚合物内的纤维/聚合物掺混物,
然后将所述纤维/聚合物掺混物成型成球粒。
11.权利要求10的方法,其中
将掺混物成型成球粒的步骤包括:
将所述纤维/聚合物掺混物在第二混合装置中进一步混合,
其中所述第二混合装置利用分导流将所述纤维分散在所述掺混物中,并且
随后将所述掺混物成型成球粒。
12.一种制造组合物的方法,所述方法包括:
向具有至少两个相互啮合的转子的第一混合装置提供粒子形式的硫酸盐化学木浆纤维,
向所述第一混合装置提供热塑性聚合物,
其中对于提供到所述混合器的每100重量%的材料来说,所述木浆纤维为所述材料的65重量%至90重量%,
将所述纤维与所述聚合物在所述第一混合装置中混合,以形成纤维以基本上单个形式分散在聚合物内的纤维/聚合物掺混物,
然后将所述纤维/聚合物掺混物成型成球粒。
13.权利要求12的方法,其中
将掺混物成型成球粒的步骤包括:
将所述纤维/聚合物掺混物在第二混合装置中进一步混合,
其中所述第二混合装置利用分导流将所述纤维分散在所述掺混物中,并且
随后将所述掺混物成型成球粒。
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KR20180116478A (ko) | 2018-10-24 |
KR20170007550A (ko) | 2017-01-18 |
BR112013018613B1 (pt) | 2021-05-25 |
US20120208933A1 (en) | 2012-08-16 |
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US8722773B2 (en) | 2014-05-13 |
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CA2824137A1 (en) | 2012-08-23 |
MX2013009371A (es) | 2013-09-26 |
KR20130124358A (ko) | 2013-11-13 |
EP2675952B1 (en) | 2020-06-24 |
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CA2824137C (en) | 2021-09-21 |
KR20170137228A (ko) | 2017-12-12 |
EP2675952A1 (en) | 2013-12-25 |
KR101808014B1 (ko) | 2017-12-12 |
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WO2012112398A1 (en) | 2012-08-23 |
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