CN100473516C - 聚烯烃系列树脂膜、其制备用的组合物、其制备用的组合物的制备方法以及其制备用的设备 - Google Patents
聚烯烃系列树脂膜、其制备用的组合物、其制备用的组合物的制备方法以及其制备用的设备 Download PDFInfo
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Abstract
聚烯烃[A]的重均分子链长为2850nm或更长,其密度为ρ1(g/cm3),聚烯烃蜡[B]的重均分子量为700~6000,其密度为ρ2(g/cm3),聚烯烃和聚烯烃蜡以[A]/[B]=90/10~50/50(重量比)混合,且ρ1和ρ2满足下述条件:0.92≤ρ1≤0.94,0.91≤ρ2≤0.93,-0.01≤(ρ1-ρ2)≤0.03。
Description
技术领域
本发明涉及聚烯系列树脂的技术,更具体地涉及聚烯烃系列树脂膜、其制备用的组合物、其制备用的组合物的制备方法以及其制备用的设备。
相关背景技术描述
作为一种高强度和高弹性膜的材料,超高分子量聚烯烃是公知的。由于其高分子量,这种超高分子量聚烯烃的熔体粘度高,且膜的形成例如变薄和拉伸(牵引)很困难。由于该原因,通常是通过对类似于块状的树脂进行切片的方法制备商品可得的超高分子量聚烯烃膜。
然而,尽管可以通过对超高分子量聚烯烃进行切片获得膜,但损害了其厚度精确性,局部地形成低强度和低弹性的部分,因此很难制备高强度和高弹性膜。
发明概述
本发明的一个目的是提供一种高强度和高弹性的聚烯烃系列树脂膜,以及制备高强度和高弹性的聚烯烃系列树脂膜用的组合物。
本发明的另一目的是提供一种制备高弹性的树脂组合物用的螺杆捏合设备,当模塑成膜并拉伸时,该设备几乎不产生例如孔洞和破裂的缺陷,并提供用该设备制备树脂用的组合物的制备方法。
为开发高弹性的聚烯烃系列树脂膜,本发明人进行了深入的研究,结果发现,通过使用以特定比例混合具有特定分子链长的聚烯烃和聚烯烃蜡得到的组合物,可以解决上述问题,由此完成了本发明。
即,本发明的聚烯烃系列树脂膜的特征在于:
重均分子链长为2850nm或更长,其密度为ρ1(g/cm3)的聚烯烃[A],重均分子量为700~6000,其密度为ρ2(g/cm3)的聚烯烃蜡[B],二者以[A]/[B]=90/10~50/50(重量比)混合,且ρ1和ρ2满足下述条件:
0.92≤ρ1≤0.94,
0.91≤ρ2≤0.93,
-0.01≤(ρ1—ρ2)≤0.03。
当[A]/[B]超过90/10以提高聚烯烃[A]的比例时,可加工性受到损害且聚烯烃蜡[B]的比例增加。当[A]/[B]小于50/50时,所得膜的物理性能降低。
此外,制备聚本发明的烯烃系列树脂膜用的组合物的特征在于:
重均分子链长为2850nm或更长,其密度为ρ1(g/cm3)的聚烯烃[A],重均分子量为700~6000,其密度为ρ2(g/cm3)的聚烯烃蜡[B],二者以[A]/[B]=90/10~50/50(重量比)混合,且ρ1和ρ2满足下述条件:
0.92≤ρ1≤0.94,
0.91≤ρ2≤0.93,
-0.01≤(ρ1—ρ2)≤0.03。
再者,本发明的螺杆捏合设备包括:
机筒,
螺杆,该螺杆在机筒内且其具有至少一个全螺线螺杆和一个捏合段,其L/D为30或更大,
其中捏合段的Ln/D为5或更大,全螺线螺杆的Lf/D为3或更大,且满足下述等式:
35≤α≤60,
0.15≤(M/D)≤0.25,
其中α为全螺线螺杆的螺纹角(°),M为全螺线螺杆的螺杆沟槽深度(mm),L为螺杆的全长(mm),Ln为捏合段的总长(mm),Lf为全螺线螺杆的总长(mm),D为机筒的直径(mm)。
为开发制备具有高弹性的树脂组合物的工艺,其中当模塑成膜并拉伸时,该工艺几乎不产生例如孔洞和破裂的缺陷,本发明人进行的深入的研究,结果发现,通过使用具有上述特定螺杆设计的螺杆捏合设备可以实现上述目的。
本发明树脂组合物的制备方法包括,用具有上述实质特征的螺杆捏合设备,将100份重量满足下述条件的混合树脂与10~300重量份无机填料进行捏合。
即,重均分子链长为2850nm或更大的聚烯烃[A]与重均分子量为700~6000的聚烯烃蜡[B]的重量比[A]/[B]为50/50~90/10。
在用于捏合热塑性树脂的通用捏合设备中,很难以上述比例均匀地捏合聚烯烃[A]和聚烯烃蜡[B]。然而,通过使用本发明的螺杆捏合设备,可以均匀地捏合通过以上述比例混合得到的混合树脂。
通过在这种条件下进行捏合,可以得到具有高弹性的树脂组合物,该树脂组合物可以被转变成膜并可进一步拉伸得到所需的多孔膜。
作为本发明适宜的实施方案,其中存在一个实施方案,在满足下述等式的条件下使用本发明上述的捏合设备,将上述混合树脂与上述无机填料进行捏合:
5×104≤[E/(D/1000)3]≤3×105,
其中E为从捏合设备中排出的树脂的量(kg/hr),D为捏合设备的机筒的直径(mm)。
通过在该条件下进行捏合,可以得到具有高弹性的树脂组合物。按照下述测定排出量:
(1)取得经36秒钟从模头排出的树脂。
(2)用电子称测定其重量。
(3)将其转变成每1小时的排出量(kg/hr)。
附图的简要说明
图1显示了制备聚烯烃系列树脂的方法实例的示意图。
图2显示了螺杆捏合设备的螺杆的细节的视图。
图3显示了螺杆捏合设备的全螺线盘的构造的视图。
图4显示了螺杆捏合设备的捏合盘的构造的视图。
优选实施方案的详细描述
本发明中的聚烯烃[A]的特征在于其重均分子链长为2850nm(28500埃)或更大。当其重均分子链长小于2850nm时,聚烯烃中分子链的缠结不够,当由本发明的组合物制备膜时,很难得到高强度和高弹性的膜。
本发明中聚烯烃蜡[B]的特征在于其重均分子量为700~6000。当使用重均分子量小于700的聚烯烃蜡时,在由聚烯烃[A]和聚烯烃蜡[B]组成的组合物中,二者均容易分离,聚烯烃蜡容易从组合物中渗出。
当使用重均分子量大于6000的聚烯烃蜡时,混合聚烯烃[A]和聚烯烃蜡[B]时的熔体粘度变大,难以得到均匀的组合物。并且当由所得的组合物制备膜时,局部形成低强度或低弹性的部分,由此很难得到高强度和高弹性的膜。
本发明中聚烯烃[A]的密度ρ1(g/cm3)和聚烯烃蜡[B]的密度ρ2(g/cm3)满足下述条件:
0.92≤ρ1≤0.94,
0.91≤ρ2≤0.93,
-0.01≤(ρ1—ρ2)≤0.03。
当密度ρ1和ρ2不满足上述条件时,聚烯烃[A]和聚烯烃蜡[B]是不相容的,当由本发明的组合物制备膜时,局部地生成低强度或低弹性的部分,由此难以获得高强度和高弹性的膜,因此是不优选的。
构成用于本发明中的聚烯烃[A]的烯烃的实例包括乙烯、丙烯、丁烯和己烯。特别优选使用超高分子量聚乙烯或超高分子量聚丙烯。
聚烯烃蜡[B]的实例包括聚乙烯系列树脂如低密度聚乙烯、线性聚乙烯(乙烯-α-烯烃共聚物)、高密度聚乙烯等的蜡,聚丙烯系列树脂如聚丙烯、乙烯-丙烯共聚物等的蜡,以及聚(4-甲基戊烯-1)、聚(丁烯-1)和乙烯-醋酸乙烯酯共聚物的蜡。
由GPC(凝胶渗透色谱法)测定聚烯烃的分子链长、重均分子链长、分子量和重均分子量,可以通过对GPC测试得到的分子量分布曲线进行积分,得到在特定分子链长范围内或特定分子量范围内的聚烯烃的混合比例(%重量)。
按照需要,制备本发明的聚烯烃系列树脂膜用的组合物可含有各种添加剂或填料。例如,可含有作为添加剂的抗氧剂、紫外线吸收剂、颜料、染料、无机填料和有机填料如树脂精细粉末。
优选本发明的聚烯烃系列树脂膜和聚烯烃系列树脂膜用的组合物含有10%重量或更多的分子链长为2850nm或更长的聚烯烃系列树脂。由于分子链长为2850nm或更长的聚烯烃系列树脂特别是在强度上极佳,因此当该树脂的含量为10%重量或更多,更优选20%重量或更多时,可以得到强度极佳的聚烯烃系列树脂膜。
可以用具有高剪切的捏合设备,通过捏合作为原料的聚烯烃[A]和聚烯烃蜡[B],得到制备本发明的聚烯烃系列树脂用的组合物。更具体地,可列举的有班伯里混合机、捏合机、捏合辊、以及捏合热塑性树脂用的螺杆捏合设备。
当使用螺杆捏合设备时,优选使用具有至少一个全螺线螺杆和一个捏合段的、螺杆的L/D为30或更大的设备,其中捏合段的Ln/D为5或更大,全螺线螺杆的Lf/D为3或更大,并满足下述条件的方程式:
(条件方程)
35≤α≤60,
0.15≤(M/D)≤0.25,
其中α为全螺线螺杆的螺纹角(°),M为全螺线螺杆的螺杆沟槽深度(mm),L为螺杆的全长(mm),D为机筒的直径(mm),Ln为捏合段的单元长度(mm)(条件是,当一个螺杆中含有2个或多个捏合段时,是指其总的单元长度),Lf为全螺线螺杆的单元长度(mm)(条件是,当一个螺杆中含有2个或多个全螺线螺杆时,是指其总的单元长度)。
不同于使用班伯里混合机或捏合机的情形,当使用螺杆捏合设备时,可以连续地设定制备膜所必需的加工步骤,例如在捏合之后的压延加工步骤和拉伸步骤。
按照以前的加工方法,当向100份重量混合树脂中加入10~300份重量无机填料时,会产生例如熔体破裂和形成类似于藤条遮蔽状孔洞(rattan blind-likehole)的问题,由此不能得到具有更好的膜厚度精确性的膜。然而按照本发明的方法,可以得到不仅具有更好的膜厚度精确性,而且刚性极佳的膜。当加入的无机填料小于10份重量时,该量不足以改进刚性。甚至当填料的加入量大于300份重量时,对于加入的量来说,改进刚性的效果较低。
作为无机填料,可使用碳酸钙、滑石、粘土、高岭土、二氧化硅、水滑石、硅藻土、碳酸镁、碳酸钡、硫酸钙、硫酸镁、硫酸钡、氢氧化铝、氢氧化镁、氧化钙、氧化镁、氧化钛、氧化铝、云母、沸石、玻璃粉和氧化锌。
接下来,通过使用作为捏合设备的螺杆捏合设备的实例,来解释本发明的实施方案。
制备膜的方法
图1显示了制备聚烯烃系列树脂膜的制备路线的示意图。该制备路线由按照加工顺序的捏合步骤1、辊压步骤2、第一纵切步骤3、拉伸步骤4和第二纵切步骤5组成。
在捏合步骤1中,使用螺杆捏合设备10,该捏合设备提供有加入重均分子链长为2850nm或更大的聚烯烃PE1和聚烯烃蜡PE2的第一料斗11。该捏合设备可提供有加入添加剂如无机填料的第二料斗12。螺杆捏合设备10配有双轴螺杆13,该螺杆将从料斗11加入的混合树脂向前挤出,同时强力捏合树脂。将通过捏合制备聚烯烃系列树脂膜用的组合物进行造粒。
在辊压步骤2中,使用螺杆挤出设备20。该设备20提供有放置由捏合步骤1得到的树脂组合物粒料的料斗21以及螺杆22。该设备20将树脂组合物向前挤出,经模头23排出棒状或片状的熔融树脂,并用辊压机24对树脂进行辊压,得到膜。
在第一纵切步骤3中,在宽度方向上将辊压步骤2得到的膜切割成2片。例如,由宽度为600mm的膜得到2个宽度为300mm的膜。
在拉伸步骤4中,在预先确定的温度条件下,将上述宽度为300mm的膜在宽度方向上拉伸4~5倍。由此可以得到在宽度方向上拉伸的聚烯烃系列树脂膜。
在第二纵切步骤5中,将在拉伸步骤4中得到的聚烯烃系列树脂膜切割成所需的宽度大小。
螺杆捏合设备的螺杆的构造
接下来将说明捏合设备10的螺杆13的详细构造,捏合设备10适合于制备本发明聚烯烃系列树脂膜制备用的组合物。图2显示了螺杆13的详细内容。
通过在称作螺杆轴的轴上安装称作单元的部件来构造螺杆13。
在图2中,表征为P的单元为一全螺线螺杆。全螺线螺杆是在其全长上螺旋地形成沟槽的螺杆片段。表征为DP的单元显示了全螺线螺杆,其中形成了较表征为P的全螺线螺杆更深的沟槽。通过使用这种更深沟槽的全螺线螺杆,可以延长树脂的停留时间。全螺线螺杆具有图3所示的形状,并且通常其作用是使加入的捏合物料向前,也就是捏合设备的下游方向。图3中,D为机筒的直径(内径)(mm),Ds为螺杆的直径(mm),M为沟槽的深度(mm),α为螺杆的螺纹角(°),H为机筒内表面与螺杆沟槽底之间的间距(mm),σf为螺杆螺线与机筒内表面之间的间距(mm)。
在上述参数中,α与树脂供应的速度有关。随着α的减小,树脂供应的速度降低。结果树脂的停留时间变长,由此树脂的捏合程度被改进,其条件是当α太小时,生产效率受到损害。M的大小是涉及树脂供应速度和捏合强度的参数。
表征为ND的单元为捏合段。如图4所示,捏合段通常有这样多个捏合盘的形状几何中心,具有相同截面形状的捏合盘放置在同一直线上,这些盘围绕着直线以指定的方向并以指定的角度偏斜堆积。各捏合盘的厚度可相同或不同。
在螺杆被安放在机筒内的状态下,构成捏合段的捏合盘与机筒之间的间距有一分布,捏合材料在该间距最小的地方被施加以最强的剪切应力。
表征为LND的单元为具有这样一种形状的捏合段,即捏合盘的堆积使得扭曲与表征为ND的捏合段中捏合盘堆积的扭曲方向相反。与一种捏合段的情形相比,通过结合使用两种捏合段ND和LND,可以使捏合材料的停留时间更长,由此可赋予更强的剪切应力。
符号SND表征的单元也是捏合段。其特征在于捏合设备的捏合盘的下游比捏合盘的上游薄,当比较邻接的捏合盘时。通过使用这种捏合段SND,可调整捏合材料向下游流动的速率,并对捏合材料赋予更强力的压缩和伸长作用。
图4(a)和(b)显示了在双轴挤出机(省略了螺杆轴)所提供的状态下的捏合段的视图。图4(b)显示了树脂J的运动以及伴随的机筒14和15中捏合盘16和17的移动。
在适合于制备本发明的聚烯烃系列树脂膜制备用的组合物的螺杆捏合设备中,整个螺杆的L/D设定为30或更大,捏合段的Ln/D设定为5或更大,全螺线螺杆的Lf/D设定为3或更大。而且,在全螺线螺杆中,参数的设定还应当使得35≤α≤60,以及0.15≤(M/D)≤0.25。随着L/D的增大,停留时间变长。这里,Ln为捏合段的单元长度(mm)(条件是,当一个螺杆中含有2个或多个捏合段时,是指其总的单元长度),Lf为全螺线螺杆的单元长度(mm)(条件是,当一个螺杆中含有2个或多个全螺线螺杆时,是指其总的单元长度)。
通过如上所述选择参数,可以得到聚烯烃系列树脂组合物,通过模塑成膜,该组合物可以形成高弹性的膜。
当使用具有上述构造的螺杆捏合设备对混合树脂和上述无机填料进行捏合时,优选在满足下述方程式的条件下进行捏合:
5×104≤[E/(D/1000)3]≤3×105,
其中E为从捏合设备中排出的树脂组合物的量(kg/hr),D为捏合设备的机筒的直径(mm)。由此可以得到具有高弹性的树脂组合物。参数排出量E显示的是有多少量的树脂在捏合设备中的机筒内被向前挤出。
尽管最优选本发明的捏合设备为含两个由完全相同的螺杆单元组成的螺杆的双轴螺杆,但可以使用不负担过重(untaxed)的螺杆或者3个或多个螺杆,只要能满足本发明的要求即可。
在由2个或多个螺杆组成的捏合设备中,最优选的是所谓的配合型,其中螺杆的转动方向是相同的,轴中心之间的间距小于螺杆单元的最大直径的总和,每一螺杆单元的凸凹部分如图4所示安装。然而,也可以使用所谓的非配合型螺杆形式,其中转动方向相同且轴中心之间的间距大于螺杆单元的最大直径的总和。或者可以使用2个或多个螺杆的转动方向不同的非配合型螺杆形式。
Claims (5)
1.一种螺杆捏合设备,该设备包括:
机筒,和
螺杆(13),
该螺杆在机筒内且其具有至少一个全螺线螺杆(P)和一个捏合段,其L/D为30或更大,
其中捏合段的Ln/D为5或更大,其特征在于:
全螺线螺杆(P)的Lf/D为3或更大,且满足下述等式:
35≤α≤60,
15≤(M/D)≤0.25,
其中α为全螺线螺杆的螺纹角,其单位为°;M为全螺线螺杆的螺杆沟槽深度,其单位为mm;L为螺杆的全长,其单位为mm;Ln为捏合段的总长,其单位为mm;Lf为全螺线螺杆的总长,其单位为mm;D为机筒的直径,其单位为mm。
2.权利要求1所述的螺杆捏合设备,其特征在于:
捏合段包括多个段的组合。
3.权利要求1或2所述的螺杆捏合设备,其特征在于:
构成捏合段的捏合盘的构造是,上游侧较下游侧薄。
4.权利要求1或2所述的螺杆捏合设备,其特征在于:
螺杆(13)由2个或多个螺杆组成。
5.权利要求3所述的螺杆捏合设备,其特征在于:
螺杆(13)由2个或多个螺杆组成。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102373648A (zh) * | 2010-08-23 | 2012-03-14 | 佛山市正大天地环保材料有限公司 | 用于生产石头纸的压延机 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5318307B2 (ja) * | 2001-03-30 | 2013-10-16 | 住友化学株式会社 | ポリオレフィン系樹脂フィルム及びポリオレフィン系樹脂フィルム用組成物 |
US20070190198A1 (en) * | 2006-02-16 | 2007-08-16 | Hyundai Mobis Co., Ltd. | Apparatus for processing polypropylene compound containing glass bubble |
DE202006004690U1 (de) * | 2006-03-24 | 2007-04-12 | Murtfeldt Kunststoffe Gmbh & C | Polyethylenbasiertes Kunststoffmaterial |
DE102006014692B3 (de) * | 2006-03-28 | 2007-08-02 | Berstorff Gmbh | Schneckenelement |
JP2013244668A (ja) * | 2012-05-25 | 2013-12-09 | Daikyo Seiko Ltd | ゴム成形品 |
FR3101568B1 (fr) * | 2019-10-03 | 2022-08-05 | Aleph Sas | Procede de fabrication d’un film comportant des cavites avec determination de profils d’etirage, de masse volumique, d’epaisseur et/ou de porosite du film |
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CN1043144A (zh) * | 1988-11-21 | 1990-06-20 | 三井石油化学工业株式会社 | 改性聚烯烃颗粒及其制备方法 |
CN1046116A (zh) * | 1989-04-14 | 1990-10-17 | 汎塑料株式会社 | 制备热塑性树脂组合物的方法 |
US5728337A (en) * | 1995-07-19 | 1998-03-17 | Toshiba Machine Co., Ltd. | Twin screw extruder and an extruding method using the same |
US5851065A (en) * | 1993-10-29 | 1998-12-22 | Toyota Jidosha Kabushiki Kaisha | Apparatus for recycling resin scrap |
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JP5318307B2 (ja) * | 2001-03-30 | 2013-10-16 | 住友化学株式会社 | ポリオレフィン系樹脂フィルム及びポリオレフィン系樹脂フィルム用組成物 |
-
2002
- 2002-03-11 US US10/093,534 patent/US7049361B2/en not_active Expired - Lifetime
- 2002-03-13 TW TW091104737A patent/TWI228071B/zh not_active IP Right Cessation
- 2002-03-13 KR KR1020020013588A patent/KR100846648B1/ko active IP Right Grant
- 2002-03-14 EP EP08100008A patent/EP1905798A3/en not_active Withdrawn
- 2002-03-14 EP EP02005363A patent/EP1241220A3/en not_active Withdrawn
- 2002-03-14 CN CNB021056587A patent/CN100473516C/zh not_active Expired - Lifetime
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US3382536A (en) * | 1965-02-13 | 1968-05-14 | Werner & Pfleiderer | Screw extruder |
CN1043144A (zh) * | 1988-11-21 | 1990-06-20 | 三井石油化学工业株式会社 | 改性聚烯烃颗粒及其制备方法 |
CN1046116A (zh) * | 1989-04-14 | 1990-10-17 | 汎塑料株式会社 | 制备热塑性树脂组合物的方法 |
US5851065A (en) * | 1993-10-29 | 1998-12-22 | Toyota Jidosha Kabushiki Kaisha | Apparatus for recycling resin scrap |
US5728337A (en) * | 1995-07-19 | 1998-03-17 | Toshiba Machine Co., Ltd. | Twin screw extruder and an extruding method using the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102373648A (zh) * | 2010-08-23 | 2012-03-14 | 佛山市正大天地环保材料有限公司 | 用于生产石头纸的压延机 |
CN102373648B (zh) * | 2010-08-23 | 2015-10-21 | 佛山市正大天地环保材料有限公司 | 用于生产石头纸的压延机 |
Also Published As
Publication number | Publication date |
---|---|
EP1905798A3 (en) | 2008-08-27 |
CN1377907A (zh) | 2002-11-06 |
EP1905798A2 (en) | 2008-04-02 |
EP1241220A3 (en) | 2003-01-02 |
TWI228071B (en) | 2005-02-21 |
US20020149132A1 (en) | 2002-10-17 |
KR100846648B1 (ko) | 2008-07-16 |
US7049361B2 (en) | 2006-05-23 |
KR20020073303A (ko) | 2002-09-23 |
EP1241220A2 (en) | 2002-09-18 |
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