CN104204073B - 由再循环和可再生的成分形成的长纤维热塑性塑料 - Google Patents
由再循环和可再生的成分形成的长纤维热塑性塑料 Download PDFInfo
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Abstract
本发明提供了一种制模组合物配方,包括聚丙烯、玻璃纤维以及一种包括可再生的片状模塑组合物转移膜的聚丙烯替代品。该聚丙烯替代品以1至35总重量百分比存在,也可以包括天然纤维素纤维或粉末。本发明还提供了一种方法,该聚丙烯替代品被混合和均质,然后与聚丙烯和添加剂以及之后的玻璃纤维混合。在纯聚丙烯使用的量的削减方面,相比传统热塑性塑料玻璃纤维填充模具是有减少的。
Description
相关申请
本申请主张提交于2012年1月6日的美国临时申请序列号61/583,808的优先权;据此,其内容通过引用的方式并入。
技术领域
本发明通常涉及到热塑性制模组合物,特别是由再循环和可再生成分形成的压缩可塑的长纤维热塑性塑料。
背景技术
聚丙烯(PP)是一种用于多种应用中的热塑性聚合物,包括:包装业、纺织业、塑料零件以及不同类型的可重复使用容器、实验室设备,以及汽车零部件。热塑性可塑制品包含强化纤维,特别是玻璃纤维以不断增加的频率应用于模具的生产中。在如汽车零部件的应用中,与纤维强化、低密度以及热塑性模具的生产量有关的强度使这些材料成为十分有诱惑力的选择。此类制品的高强度以及韧性提供了许多相对于传统钢冲压件的优点。此类制品是将玻璃纤维绳束与熔化的热塑性薄膜结合,在双带压力机或双螺杆挤压机中生产的。聚丙烯通常的被作为热塑性聚合物用于此类制品模具中。由于表面光洁度要求以及对制品此种汽车部件接收一层均匀的涂料层的通常要求,纯PP常用于此种模具。由于纯PP的实用性以及价格依赖于不稳定的石油价格,这种引进以及这种模具的成本上的不确定因素,以及由于直接依赖于不可再生石油资源的使用,在环境上也是不受欢迎的。作为PP的相对高成本的结果,由于纯PP相对于竞争材料如钢制品以及片状模塑组合物(SMC)的成本,许多会得益于此类模具的应用是不可行的。
虽然已经做出努力使用一部分再循环的PP以减少纤维增强的热塑性模具的成本,由于使用的再循环PP的不均匀性以及与纯的与再循环PP之间的差别熔化特性有关的不均匀性,这些努力获得了有限的成功。由于疏水PP润湿填料,如碳酸钙或碳黑以及事实上许多类型的玻璃纤维很差的困难,从而有损所得制品的强度,添加填料以取代制模组合物中的PP的努力也被证明是不成功的。天然纤维已经被检测用以取代此类模具中的大部分的玻璃,但是这些尝试都是以整体制品的强度为代价的。基质或纤维改性已被认为是必要的,以改善天然纤维和基体之间的相容性。马来酸化的聚烯烃用于改性基质。此类基质改性产生了马来偶联剂的酸酐基团与天然纤维中的羟基基团之间的相互作用。用对不同的耦合剂如硅烷,聚丙烯接枝的(PPgMA)或乙酰化改性的马来酸酐的作用广泛的研究以制造工程零件的目的,已被文献R.Malkapuram et al.,J.强化塑料与复合材料,28卷,No.10/2009,1169页报道。干燥天然纤维以及天然纤维的表面改性的难度增加了相当大的成本以及PP纤维填充模具的可变性,在不有损制品的强度下不能取代PP模具中的玻璃纤维或者碳纤维强化复合材料。
此外,由于熔化的长流向,填充PP的玻璃纤维趋向于适应于内部纤维,制品强度在平行于熔态流动的方向上的减弱通常显著,这一问题被微粒填料或者天然纤维填料中的杂质恶化了。
因此,存在一种对压缩可塑的热塑性塑料的需要,包括:缩小PP的量同时仍旧能够负担与强化玻璃纤维全负载和纯PP相关的强度。还存在一种对一种此类组合物的需要,包括:再循环材料以减少此类模具的环境足迹。
发明内容
本发明提供了一种制模组合物配方,包括:聚丙烯、玻璃纤维以及包括再循环的片状模塑组合物转移膜的聚丙烯替代品。该聚丙烯替代品以1至35总重量百分比存在,也可以包括天然纤维素纤维或粉末。本发明还提供了一种方法,聚丙烯替代品被混合和均质,然后与聚丙烯和添加剂以及之后的玻璃纤维混合。在纯聚丙烯使用的量的削减方面,相比传统热塑性塑料玻璃纤维填充模具是有减少的。
附图说明
通过以下附图进一步详细介绍了本发明。这些附图不应以限制在本发明附图2描述的典型实施例2的范围来解释,而应以其在模具中发明和使用方面来解释。
图1为一种现有技术配方和主要由聚丙烯和玻璃纤维形成压缩可塑长纤维热塑性塑料方法的框图;及
图2为一种创造性的配方和由再循环和可再生成分替代一部分聚丙烯形成的压缩可塑长纤维热塑性塑料方法的框图。
具体实施方式
本发明具有作为一种经济的和环保的替代物用以降低特别包括压缩可塑长纤维热塑性塑料(LFTD)的压缩可塑热塑性塑料中的聚丙烯(PP)成分的作用。引入再循环和可再生的成分替代聚丙烯,降低高成本聚丙烯的使用,帮助降低在聚丙烯生产中可能被释放到环境中的潜在的污染。与常规材料相比,本发明的减少环境足迹是显著的。
能够替代聚丙烯的可再循环材料包括转移膜,其是片状模塑料(SMC)生产过程中的副产品,在此被称为“再循环SMC薄膜”。该再循环SMC薄膜其自身由聚丙烯形成,因此增加了压缩可塑热塑材料的聚丙烯的另外来源,同时省去了生产额外聚丙烯的需要以及丢弃再循环SMC薄膜。较佳地,该再循环材料具有至少35%重量百分比的聚丙烯成分。
在本发明的一些实施例中,纤维素粉末填料作为基础配方中的聚丙烯成分替代品被引入压缩可塑热塑性塑料。此类有效的纤维素天然填料此处说明性的包括椰子壳粉末、树坚果壳粉末、花生壳、谷物外壳或外皮如稻谷、小麦以及椰子皮纤维。
在本发明的一些实施例中,纤维素纤维可以作为基础配方中的聚丙烯成分替代品被引入压缩可塑热塑性塑料。此类有效的纤维素天然纤维此处说明性的包括椰子纤维、竹纤维、甘蔗纤维、香蕉皮纤维、大麻、甘蔗、黄麻、蚕丝以及椰子壳。
现在请参照附图1,反映了一种主要由聚丙烯10和玻璃纤维14形成的压缩可塑长纤维热塑性塑料的典型的现有技术配方以及现有技术方法的框图。在图1的标准配方中,聚丙烯10以及添加剂12在双螺杆挤出机16中被混合和复合,然后在挤出机18中与玻璃纤维14结合。图1中的压缩可塑长纤维热塑性塑料的现有技术常规配方为大部分聚丙烯10,其给定载荷量在45至80重量份,示范的如图1中所示的全部热塑性组合物的63重量份。玻璃纤维14在一个10至40重量份的典型载荷量下被提供以赋予所得制品的强度。如图1所示,玻璃纤维14以35重量份存在。小批量的添加剂12可选择的被提供用以控制聚丙烯的材料性能。添加剂12典型地以0至10重量份的载荷量被提供。未改性PP的典型添加剂包括抗酸剂如硬脂酸钙、壬酸钙、氧化锌或二水方解石。这些化合物用来中和那些可以另外形成会侵蚀加工设备的酸的催化剂残留物。抗氧化剂也通常存在PP中用以保护聚合物以避免加工或老化中的断链。有代表性的抗氧化剂为受阻酚。还有其他添加剂,包括澄清剂、阻燃剂、紫外线稳定剂、抗静电剂、炭黑、光滑剂以及增塑剂。除了炭黑超过2%的水平,大多数常规添加剂都在低于1%的水平下使用,在许多情况下低于0.01%。如图1所示,添加剂12以2重量份存在。典型与较优现有技术配方如表1所示:
表1.常规聚丙烯压缩模塑组合物
材料 | 典型量以重量份计 | 图1中的示范量以重量份计 |
聚丙烯 | 45-80 | 63 |
添加剂 | 0-10 | 2 |
玻璃纤维 | 10-40 | 35 |
应当理解的是,在有关于本发明的范围值被提供的情况下,该范围旨在不仅包含范围的末端值,而且范围的中间值也明确的被包含在该范围之内并且被该范围的有效数字改变。举例来说,例举范围1至4旨在包含1-2、1-3、3-4以及1-4。
图2为一种再循环和可再生成分替代一部分聚丙烯10形成的压缩可塑性长纤维热塑性塑料的创造性配方和方法的框图。图2中,再循环和可再生成分包括典型载荷量在1到25之间重量份的再循环片状模塑组合物(SMC)PP转移膜20。该膜20具有0.5至1.5密耳间的厚度,是SMC生产中的副产品,通过加工作为载体和SMC树脂膏的苯乙烯屏障使用,然后通常会被丢弃。该膜20被切成各种形状,包括长宽比为2-1000:1的条,或多边形,如直线型或六边形、圆圈形、三角型,或它们的组合,其最长线性尺寸和最短线性尺寸之间纵横比在1-2:1之间。为了促进混合,该薄膜20的尺寸典型的设置在聚丙烯原料颗粒一个数量级(10%到1000%)内。如图2所示,该薄膜20被说明性地以15重量份作为示范性载荷量存在。
纤维素粉末22以0至15重量份的典型载荷量被提供。如图2所示,纤维素粉末22说明性地以6重量份作为示例性载荷量存在。粉末22说明性地为椰子壳粉;稻谷壳;小麦壳;扁桃、榛子、胡桃、阿月浑子、松子、山核桃的坚果壳粉;棉籽壳;洋麻粉;橄榄核或者它们的组合。典型的粉末尺寸在2至1000微米之间。粉末22是干燥的,不经表面改性起效以使得粉末表面具有疏水性。在其他具有创造性的实施例中,PP被马来酸化以加强PP和粉末22之间的共价键,或者粉末22通过形成氨基甲酸乙酯键或为粉末22提供一个疏水面的键被改性。
纤维素纤维24也以典型载荷量为0至15之间的重量份被提供,如图2所示,纤维素纤维24被解释为以6重量份作为示范性载荷量。纤维24说明性地为纤维素纤维、木纤维、亚麻、大麻、剑麻、椰子纤维、洋麻、竹纤维、枣椰纤维、甘蔗纤维、香蕉皮纤维、或它们的组合,在某些创造性实施例中,纤维素纤维24为椰子和/或竹纤维。典型的天然纤维的直径在10至500微米之间。有些实施例中纤维24的长度被选择具有的平均长度为玻璃原丝的长度的一个数量级(10%到1000%),存在于制品中。至少一种纤维素粉末22和该纤维素纤维24存在于一种创造性配方中。较佳地,该纤维素粉末22以及该纤维素纤维24均在一种创造性配方中存在。更佳地,该纤维素粉末22以及该纤维素纤维24分别独立的以3至10重量份存在。
纤维24在挤出机18A中被混合和复合形成替代组合物26。该挤出机18A被描述为双螺杆挤出。可以理解的是另外的常规挤出机如单螺杆或双螺杆挤出机提供了一个通过操纵挤出机的控制参数控制的均匀度。旨在不被特定的理论所束缚,薄膜20被认为可封装填料粉末22和填料纤维24,作为目前解决亲水填料与PP基质的界面互相作用弱的现有技术问题。剩余的SMC膏状材料与薄膜20结合提高封装性。所得的替代组合物26随后与聚丙烯10和PP加工添加剂12借助于挤出机16结合形成一种均匀的组合物。挤出机18结合玻璃纤维14与其他成分形成创造性的用于模具和进一步加工的LFTD。进一步加工较佳地包括压缩成型以在模子中形成制品。不同成分的示范性载荷量描述于图2。可以理解的是该玻璃纤维14可以有多种形式,说明性地包括短纤维、粗纱以及草席。
采用再循环和可再生成分形成的替代组合物26使得创造性的LFTD中纯聚丙烯10在量上相对于图1的传统的LFTD减少。通过对替代组合物26特性的控制,形成了一种LFTD制品,其具有物理特性与传统LFTD的物理特性相似,而且纯PP的使用量减少了20至65%之间。类似的添加剂的量也减少了。可详细在图1和2间的示例性量上注意到,PP使用量的减少了57%。在一种全配制的组合物中,配方中30-40%是常规PP,聚丙烯替代品呈现多达配方的25、甚至多达30总重量百分比,剩余物为PP加工添加剂和玻璃纤维。
此创造性组分相对于表1所示的常规组份如表2所示。
表2.创造性组合物典型值.
材料 | 重量百分比的量 | 重量份的典型量 | 图2中的示例量的重量份 |
聚丙烯 | 表1量的35-80% | 25-70 | 36 |
添加剂 | 表1量的0%至100% | 0-2 | 2 |
玻璃纤维 | 表1量的15%至50% | 5-50 | 35 |
再循环SMC转移膜 | 1%至35% | 1-25 | 15 |
纤维素粉末 | 0%至25% | 0-15 | 6 |
纤维素纤维 | 0%至25% | 0-15 | 6 |
值得注意的是,该创造性LFTD的配方独立组分的百分比可以在不同的实施例参照LFTD预期应用改变。
在说明书中提到的专利文献和出版物提示了本领域技术人员的本发明的从属的认知水平。这些文件和出版物在此引入作为参考,其程度如同每一个单独的文件或出版物被具体地和单独地通过引用方式并入本文。
前面的描述是用于说明本发明的具体实施例,但并不意味着是在实践中的限制。以下的权利要求,包括所有的相同物旨在确定本发明的范围。
Claims (10)
1.一种制模组合物,包括:
聚丙烯,所述的聚丙烯占制模组合物的质量比为25%~70%;
玻璃纤维,所述的玻璃纤维占制模组合物的质量比为5%~50%;
一种包括再循环片状模塑组合物转移膜的聚丙烯替代品,所述的再循环片状模塑组合物转移膜的载荷量在1至35的总重量百分比且膜厚度在0.5至1.5密耳之间,所述的再循环片状模塑组合物转移膜为SMC树脂膏的苯乙烯屏障使用的转移膜,所述的再循环片状模塑组合物转移膜被切成长宽比为2-1000:1的条,或多边形,且最长线性尺寸和最短线性尺寸之间纵横比在1-2:1之间,所述的聚丙烯替代品还包括一种由至少一种天然纤维素纤维结合所述的再循环片状模塑组合物转移膜而成的纤维素天然填料,
所述的聚丙烯替代品占制模组合物的质量比为1%~25%。
2.根据权利要求1所述的制模组合物,其特征在于,所述的天然纤维素纤维为椰子壳粉、胡桃壳粉或稻谷壳中的至少一种。
3.根据权利要求1所述的制模组合物,其特征在于,所述的天然纤维素纤维进一步的为椰子纤维、竹纤维、甘蔗纤维或香蕉皮纤维中的至少一种。
4.根据权利要求1至3中任一项所述的制模组合物,其特征在于,所述的组合物是一种压缩可塑的长纤维热塑性塑料(LFTD)。
5.根据权利要求1所述的制模组合物,其特征在于,所述的聚丙烯的质量比例为所述的组合物的30%至40%。
6.一种生产权利要求1所述的制模组合物的方法,包括:
混合再循环片状模塑组合物转移膜用以形成一种聚丙烯替代组合物,所述的聚丙烯替代组合物还包括一种由至少一种天然纤维素纤维结合所述的再循环片状模塑组合物转移膜而成的纤维素天然填料;
将所述的聚丙烯替代组合物与聚丙烯、一种或多种添加剂以及玻璃纤维结合以形成一纤维组合物;并且
所述的纤维组合物为长纤维热塑性塑料(LFTD)压缩模塑的。
7.根据权利要求6所述的方法,其特征在于,所述的混合是由双螺杆挤出机来完成的。
8.根据权利要求6所述的方法,其特征在于,所述的天然纤维素纤维为椰子壳粉末、胡桃壳粉末或稻谷壳中的至少一种。
9.根据权利要求6所述的方法,其特征在于,所述的天然纤维素纤维为椰子纤维、竹纤维、甘蔗纤维或香蕉皮纤维中的至少一种。
10.根据权利要求6所述的方法,其特征在于,所述的聚丙烯的质量比例为所述的组合物中的30%至40%。
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