CN1140571C - 挤出贴面结构 - Google Patents

挤出贴面结构 Download PDF

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CN1140571C
CN1140571C CNB988032112A CN98803211A CN1140571C CN 1140571 C CN1140571 C CN 1140571C CN B988032112 A CNB988032112 A CN B988032112A CN 98803211 A CN98803211 A CN 98803211A CN 1140571 C CN1140571 C CN 1140571C
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extrusion coating
coating structure
ethylene
multimodal
polymer
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CN1250458A (zh
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M·塞尼奥
E·莱霍
M·韦海莱
H·萨尔米南
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Borealis Technology Oy
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Abstract

一种挤出贴面结构，其特征在于至少一层是由一种包含多峰线性乙烯聚合物的聚合物组合物制得，该多峰线性乙烯聚合物含有80～100wt%的乙烯重复单元和0～20wt%的C3-C10α-烯烃重复单元，其密度为0.920～0.960g/cm3，并且是至少两种不同乙烯聚合物的共混物，该乙烯聚合物共混物的熔体流动速率MFR2是1～30g/10min。

Description

挤出贴面结构
本发明涉及多峰乙烯聚合物基挤出贴面组合物和其用于贴合纸张或纸板基材的用途。
本发明的目的是提供一种聚乙烯组合物，用于具有良好加工性能和良好机械性能的挤出贴面体。
目前市场上通用的聚乙烯挤出贴面等级聚合物是由高压法得到的低密度聚乙烯。一般，此类低密度聚乙烯具有良好的加工性能，但与线性聚乙烯相比，却具有较差的耐环境致裂(ESCR)和密封强度以及差的热粘着性。
一些线性聚乙烯、高密度、中密度和线性低密度聚乙烯也被用于挤出贴面应用中。然而，挤出贴面组合物通常通过将线性材料与高压低密度聚乙烯共混而制得以获得足够的加工性能。线性材料的问题是它们的差的加工性能。通过将线性材料与高压低密度聚乙烯共混在一定程度上克服了这一问题。线性聚乙烯的优点是它们可允许较薄贴面的较好强度。
将高压低密度聚乙烯(PE-LD)加入到线性高密度或低密度聚乙烯(PE-HD或PE-LLD)中通常会导致机械性能和防护性能方面的损失。共混物的另一缺点是由于附加的混合步骤而引起的过高费用，其中该步骤制成了PE-HD或PE-LLD和高压PE-LD的共混物。
本发明的目的是在挤出贴面中使用一种双峰或多峰线性聚乙烯材料，而不需要加入任何高压PE-LD。本发明乙烯聚合物的双峰性或多峰性确保了足够的产量，同时保持了线性聚乙烯的优良机械性能。该材料特别适合于共挤塑。
本发明的目的已通过包含多峰线性乙烯聚合物的聚合物组合物而实现，其中该多峰线性乙烯聚合物含有80～100wt％的乙烯重复单元和0～20wt％的C3-C10α-烯烃重复单元，其密度为0.920～0.960g/cm3，并且是至少两种不同乙烯聚合物的共混物。
与本发明有关的多峰乙烯聚合物指的是具有宽分子量分布的乙烯聚合物，其通过将具有不同分子量的两种或多种乙烯聚合物组分共混或通过以具有两个或多个串联反应器的工艺将乙烯聚合成不同分子量而制得。相反地，如挤出贴面中惯常所用的那些的单峰聚乙烯，是由仅一步法制得的唯一的乙烯聚合物组分得到的。
本发明的挤出贴面组合物是多峰乙烯聚合物。按照定义多峰乙烯聚合物是至少两种具有不同分子量的乙烯聚合物的共混物。按照本发明的一个重要实施方案，该共混物是包含至少两步的聚合方法的产物。在该方法中，第一乙烯聚合物是在第一步中在催化剂体系存在下通过聚合乙烯而制得，第二聚合物是在第二步中在催化剂体系存在下通过(共)聚合乙烯和任选的一种较高级α-烯烃而制得。所述步骤能够按照任何次序完成。
本发明的目的能够通过使用各种乙烯聚合反应催化剂例如铬催化剂、Ziegler-Natta催化剂或金属茂催化剂而实现。一般的催化剂体系例如按照引入本文供参考的WO91/12182和WO95/35323制备。优选的单一位聚合反应催化剂体系是基于第4族金属的金属茂和铝氧烷(alumoxane)。
当进行包含至少两步骤的所述聚合方法时，能够使用可以相同或不同的一种或多种催化剂体系。优选的是，如果乙烯聚合物的共混物是所述聚合方法的产物，那么在随后的步骤中使用相同的催化剂体系。
在多步聚合反应过程中控制分子量的最便利方法是使用氢，其通过介入到聚合反应机理的插入步骤中而用作链转移剂。氢可以以合适的量加入到多步聚合反应的任何步骤中。
已知的是在两个或多个串联聚合反应器中制备多峰、特别是双峰烯烃聚合物。这样的方法被引入本文供参考的EP040992、EP041796、EP022376和WO92/12182所例举，这些都是关于用于所要求的挤出贴面材料的多峰乙烯聚合物的制备方法。按照这些资料，所述聚合步骤中的每一步都能够在液相、淤浆或气相中进行。
按照本发明，优选以淤浆聚合和气相聚合的结合来进行所述聚合步骤。优选第一步是淤浆聚合且第二步是气相聚合。
淤浆聚合优选在所谓的环流反应器中进行。气相聚合在气相反应器中进行。聚合步骤之前可任选地先进行预聚合反应，于是形成至多20wt％并优选1-10wt％的总的乙烯聚合物量。
按照本发明的另一重要实施方案，多峰乙烯聚合物能够通过混合至少两种具有不同平均分子量的乙烯聚合物而制得。
乙烯聚合物共混物的适合熔体流动速率MFR2是1～30g/10min。
多峰乙烯聚合物的分子量分布曲线显示出或是几个峰或是一个宽峰，缺少少部分的非常低和非常高分子量的部分。
当然，完成的聚合反应或混合产物可被进一步处理，以便根据所用材料的用途改进其平均分子量和分子量分布。
本发明的聚合物组合物适合于纤维基材料如纸张和纸板的挤出贴面。纸张或纸板基材的每平方米克重一般是20g/m2～400g/m2。
挤出贴面中所用的基材也可以是由聚酯、聚酰胺、赛璐玢、聚丙烯和定向聚丙烯制得的塑料薄膜。当使用塑料薄膜基材时，其厚度一般是10μm～80μm。
另外，也可以使用铝基材，且基材的厚度是6μm～300μm。
本发明的聚合物组合物可被用作基材上唯一的挤出贴面层，或可被用于多层产品中的一层或几层。
取决于最终产品，当然有可能使用其中多峰乙烯聚合物共混物与某一其它聚乙烯一起使用的挤出贴面结构。所述其它乙烯聚合物可以是高压低密度乙烯聚合物或共聚物或单峰线性乙烯聚合物。多峰聚合物和其它聚合物在挤出贴面之前被混合。
按照下面的实施例更详细地描述本发明。
实施例中所用材料：LE7518＝PE-LD贴面等级，MFR2＝7.5g/10min，密度为0.918g/cm3LE4524＝PE-LD贴面等级，MFR2＝4.5g/10min，密度为0.923g/cm3Dowlex3010＝PE-LLD，生产者是Dow聚合物A＝中等密度多峰乙烯聚合物聚合物B＝线性低密度多峰乙烯聚合物聚合物C＝线性低密度多峰乙烯聚合物
表1中给出了聚合物A、B和C的性能。
除Dowles3010之外的所有聚合物都由Borealis Polymers Oy.生产。
                      表1
  聚合物  A   B   C
  环管内MFR，g/10min  130   100   100
  环管内密度，kg/m3  960   941   941
  最终MFR，g/10min  10   13   9
  最终密度，kg/m3  942   930   931
多峰聚合物的制备：
实施例1(聚合物A)：
在环流反应器中制备MFR2为130g/10min、密度为960kg/m3的聚乙烯。然后将含有活性催化剂的聚合物转移到气相反应器中，其中进行聚合反应的条件应使得最终聚合物A的MFR2为10g/10min、密度为942kg/m3。
实施例2(聚合物B)：
在环流反应器中制备MFR2为100g/10min、密度为941kg/m3的聚乙烯。然后将含有活性催化剂的聚合物转移到气相反应器中，其中进行聚合反应的条件应使得最终聚合物B的MFR2为13g/10min、密度为930kg/m3。
实施例3(聚合物C)：
在环流反应器中制备MFR2为100g/10min、密度为941kg/m3的聚乙烯。然后将含有活性催化剂的聚合物转移到气相反应器中，其中进行聚合反应的条件应使得最终聚合物C的MFR2为9g/10min、密度为931kg/m3。贴合试验：
实施例4：
使用Beloit-pilot挤出贴合操作线进行贴合试验。在试验中，使用每个具有L/D 24D/114 mm螺杆、最大产量450kg/h的两个挤出机。
将所有试样首先加工成单层贴面，这意味着在两个挤出机中使用相同材料。使用相同方法进行较高密度多峰聚合物(＝聚合物A)和基本PE-LD贴面等级聚合物的干燥共混物的试验。干燥共混物中PE-LD的比例是15wt％。
在多峰MD产物(聚合物A)的贴合方法中，可以看出与本申请中的贴面PE-LLD等级(Dowlex3010)的处理相比，其挤出机的电动机负载较低。聚合物A的最大螺杆速度是100rpm，而常规PE-LLD等级聚合物仅达到90rpm的水平。当为多峰中密度乙烯聚合物(A)设定的熔体温度(300℃)比为常规PE-LLD(315℃)设定的熔体温度低时，优点变得更突出。
除了也作为共挤出材料的单层试验之外，试验较低密度含量的多峰产物(＝聚合物B和C)。在共挤出试验中，挤出机I被用于PE-LD，挤出机II被用于多峰材料。在该方法中，多峰材料变成所述结构的外层。用聚合物B和C进行所有试验。
考虑每一试样的MFR2来设定最佳的熔体温度。测试带有各种贴合重量和线速度的材料。所有试验中所用基材都是棕色70g/m3UG-纸。
贴面聚合物的贴合重量、边缘迂回和缩幅数值都在非常适当的水平，并具有LE7518+多峰LLD(B和C)共挤出结构。在试验中可以看出带有多峰LLD(聚合物B和C)层的2g/m2LE7518支承层是8g/m2是适当的。
与高压PE-LD挤出贴面聚合物相比，当检测多峰材料的最终产品性能时，是有许多优点的。特别地，其热粘着强度明显较高；当PE-LD LE4524具有数值2.5N/15mm时，共挤出LE7518+多峰LLD(B和C)、15+15g/m2结构的数值是3.5N/15mm。共挤出多峰LLD的击穿强度指数是4.9，而LE4524的指数为3.1。与LE4524的仅为2.1％相比，共挤出的多峰LLD的轴向伸长是6.3％。横向伸长也明显更好，数值是9.2％，而LE4524的极限值为4.7％。甚至当贴合重量低至10g/m2(2g/m2LE7518+8g/m2聚合物C)时，在共挤出多峰LLD贴面中也没有针孔。

Claims (14)

1、一种挤出贴面结构，其特征在于至少一层是由一种包含多峰线性乙烯聚合物的聚合物组合物制得，该多峰线性乙烯聚合物含有80～100wt％的乙烯重复单元和0～20wt％的C3-C10α-烯烃重复单元，其密度为0.920～0.960g/cm3，并且是至少两种不同乙烯聚合物的共混物，该乙烯聚合物共混物的熔体流动速率MFR2是1～30g/10min。
2、权利要求1的挤出贴面结构，其特征在于乙烯聚合物共混物是下面方法的产物：第一乙烯聚合物是在第一步中在催化剂体系存在下通过聚合乙烯而制得，第二聚合物是在第二步中在催化剂体系存在下通过聚合乙烯而制得。
3、权利要求1的挤出贴面结构，其特征在于乙烯聚合物共混物通过混合至少两种具有不同平均分子量的乙烯聚合物而制得。
4、权利要求1-3的挤出贴面结构，其特征在于贴面结构的基材是纤维基状纸张或纸板。
5、权利要求4的挤出贴面结构，其特征在于纸张或纸板基材的每平方米克重是20g/m2～400g/m2。
6、权利要求1-3的挤出贴面结构，其特征在于贴面的基材是由聚酯、聚酰胺、聚丙烯或赛璐玢制得的塑料薄膜。
7、权利要求6的挤出贴面结构，其特征在于塑料薄膜基材的厚度是10μm～80μm。
8、权利要求1-3的挤出贴面结构，其特征在于贴面的基材由铝制得。
9、权利要求8的挤出贴面结构，其特征在于铝基材的厚度是6μm～300μm。
10、上述权利要求中任一的挤出贴面结构，其特征在于乙烯聚合物共混物被用作挤出贴面结构中唯一的贴面层。
11、上述权利要求中任的挤出贴面结构，其特征在于乙烯聚合物共混物被用作共挤出贴面结构中的层。
12、上述权利要求中任一的挤出贴面结构，其特征在于乙烯聚合物共混物被用于与某一其它聚乙烯混合。
13、权利要求12的挤出贴面结构，其特征在于其它乙烯聚合物是高压低密度乙烯聚合物或共聚物。
14、权利要求12的挤出贴面结构，其特征在于其它乙烯聚合物是单峰线性乙烯聚合物。
CNB988032112A 1997-01-10 1998-01-07 挤出贴面结构 Expired - Fee Related CN1140571C (zh)

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CN1250458A (zh) 2000-04-12
WO1998030628A1 (en) 1998-07-16
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NO993400L (no) 1999-07-09
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CA2277145A1 (en) 1998-07-16
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FI970121A0 (fi) 1997-01-10
ZA9833B (en) 1998-07-07
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