CN1585693A - 注坯吹塑的单层金属茂聚乙烯容器 - Google Patents

注坯吹塑的单层金属茂聚乙烯容器 Download PDF

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CN1585693A
CN1585693A CNA028206320A CN02820632A CN1585693A CN 1585693 A CN1585693 A CN 1585693A CN A028206320 A CNA028206320 A CN A028206320A CN 02820632 A CN02820632 A CN 02820632A CN 1585693 A CN1585693 A CN 1585693A
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埃里克·梅齐尔斯
瓦莱丽·斯米茨
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Abstract

一种单层中空包装物，主要含有用金属茂生产的聚乙烯，并用注坯吹塑法生产，其特征在于该中空包装物的外光泽度和内光泽度至少为30，该金属茂生产的聚乙烯的密度为0.910至0.966g/cm3或高至均聚物的密度，熔体指数MI2为0.5至2.5g/10分钟。

Description

注坯吹塑的单层金属茂聚乙烯容器
本发明涉及具有改进光学性能的中空包装物，特别涉及将聚乙烯进行注坯吹塑而形成高光泽度瓶子、罐子等等的生产方法。
已经寻求过若干方法来生产具有良好加工性和良好机械性能的高光泽度瓶子，但迄今全部的融合和所采用的技术均具有各种缺点。
已经使用了高光泽度、高密度聚乙烯(HDPE)：它可以用非常窄的分子量分布来表征，其值典型地低于8，可以用由凝胶渗透色谱法获得的曲线来完整地定义分子量分布。通常，分子量分布(MWD)可更简单地以称作分散指数D的参数来定义，分散指数D是重均分子量(Mw)与数均分子量(Mn)之间的比值。分散指数构成分子量分布宽度的一个尺度。人们知道，分子量分布窄的树脂将生产非常高光泽度的塑料容器，但同时这种树脂很难加工，而且这种树脂的特点是机械性能非常差。已经观察到这种树脂具有很差的机械性能，特别是非常低的环境应力开裂耐受性(Modern Plastic International，August1993，p.45)。
高密度聚乙烯(HDPE)与薄的聚酰胺外层的共挤塑法已被用于生产非常高光泽度的瓶子，但这方法的主要缺点是在HDPE与聚酰胺层之间需要一层粘合剂。
高密度聚乙烯与低密度聚乙烯外层的共挤塑导致瓶子的光泽还算好。但是这些瓶子具有令人不舒适的触感，而且抗刮性很差。
待审的欧洲专利申请00201155.9号所公开的另一方法中，制造了高光泽度的塑料容器，它具有含有聚烯烃的内层和含有苯乙烯组分的外层，此苯乙烯组分的含量以外层重量计为40～85重量％。
因此，需要有这样一种方法：它能用注塑法有效生产具有非常高光泽度及良好加工性能和机械性能的中空包装物。
本发明的目的是生产中空包装物，其同时具有所期望的光泽外观和良好的抗刮性。
本发明的又一目的是获得具有良好加工性和良好机械性能的带光泽的中空包装物。
本发明提供单层中空包装物，它们主要用金属茂生产的聚乙烯组成，此聚乙烯的密度由0.915g/cm3，优选由0.925g/cm3高至0.966g/cm3，或高达均聚物的密度，其熔体指数MI2为0.2～5g/10分钟，优选为0.5～2.5g/10分钟，最优选为0.5～2g/10分钟，其特征在于该中空包装物用注坯吹塑法生产，其外层和内层光泽度至少为30。
在本说明书中，聚乙烯的密度用ASTM D1505的方法在23℃下测定。
熔体指数MI2采用ASTM D1238的方法在190℃下用2.16kg负荷测定。高负荷熔体指数HLMI采用ASTM D1238方法在190℃下用21.6kg负荷测定。
已公开了用于制备聚乙烯特别是适于注坯吹塑的中密度聚乙烯(MDPE)和高密度聚乙烯(HDPE)的众多不同金属茂催化剂。在现有技术中已经知道，聚乙烯产品的物理性能特别是机械性能取决于用于制造聚乙烯的是什么催化体系。
HDPE可以用能够生产单-或双-或多-模式分布的金属茂催化剂体系进行聚合而得到，或例如用EP-A-0881237中所述的以两步法进行，或者例如用EP-A-0619325中所述的以双-或多-部位催化剂在单一反应器中进行。现有技术中公知的任何金属茂催化剂均可用于本发明中。此催化剂可以用下列通式表示：
I.(Cp)mMRnXq
式中Cp是环戊二烯环，M是4b，5b或6b族过渡金属，R是含有1至20个碳原子的烃基或烃氧基，X是卤素，而m＝1-3，n＝0-3，q＝0-3，且m+n+q的总值等于此金属的氧化态。
II.(C5R′k)gR″s(C5R′k)MQ3-g
III.R″s(C5R′k)2MQ′
式中(C5R′k)是环戊二烯基或取代的环戊二烯基，每个R′彼此相同或不同，是氢或烃基，例如含有1至20个碳原子的烷基、链烯基、芳基、或芳烷基，或者两个碳原子连接在一起形成一个C4-C6环，R″是C1-C4亚烷基、二烷基锗或二烷基硅或二烷基硅氧烷、或烷基膦或胺基桥接的两个(C5R′k)环，Q是烃基例如含1至20个碳原子的芳基、烷基、链烯基、烷芳基、或芳烷基，含有1至20个碳原子的烃氧基，或卤素，而且彼此可以相同或不同，Q′是含有1至20个碳原子的亚烷基，s是0或1，g是0、1或2，当g是0时s是0，当s是1时k是4，而当s是0时k是5，以及M如上面所定义。
在用于本发明的优选金属茂中，人们可以从例如EP-A-870048所公开的单-、双-、或三-取代的亚乙基双-(四氢茚基)二氯化锆、亚乙基双-(茚基)二氯化锆或双-(正丁基环戊二烯基)二氯化锆中引用。
此金属茂可以按照现有技术中公知的任何方法进行荷载。在进行荷载的情况下，在本发明中所用的载体可以是任何有机固体或无机固体，特别是多孔载体，如滑石、无机氧化物及树脂载体材料如聚烯烃。优选的是此载体材料是微细形状的无机氧化物。
必须通过加入具有离子化作用的活化剂去形成活性部位。
优选的是，在聚合过程中使用铝氧烷作为活化剂，任何在现有技术中公知的铝氧烷均是适用的。
优选的铝氧烷包括下列通式所表示的低聚直链和/或环状烷基铝氧烷：
Figure A0282063200051
低聚直链铝氧烷，而 低聚环状铝氧烷，
式中n是1-40，优选为10-20，m是3-40，优选为3-20，而R是C1-C8烷基，优选为甲基。
优选使用甲基铝氧烷。
当不使用铝氧烷作为助催化剂时，使用通式AlRX代表的烷基铝，式中每个R可以相同或不同，选自卤化物或含有1至12个碳原子的烷氧基或烷基，而X是1至3。特别适用的烷基铝是三烷基铝，最优选的是三异丁基铝(TIBAL)。
当需要制备本发明的高光泽度中空包装物时，用于生产聚乙烯的金属茂催化剂可以用于气相、溶液或淤浆聚合中。优选的是，在淤浆相聚合反应条件下进行聚合过程。聚合温度范围为20至125℃，优选为60至95℃，压力范围为0.1至5.6MPa，优选为2至4Mpa，而聚合时间为10分钟至4小时，优选为1至2.5小时。
聚合反应在该聚合物于稀释剂中仍维持悬浮固态的温度下，在稀释剂中进行是优选的。
优选使用连续回路反应器进行此聚合反应，也能使用多回路反应器。
通过在聚合过程中加入氢气而控制平均分子量。加到聚合反应器中的氢气和烯烃的相对数量，以氢气和烯烃的总存在量计，为0.001～15摩尔％的氢气，和99.999至85摩尔％的烯烃，优选为0.2至3摩尔％的氢气，和99.8至97摩尔％的烯烃。
以加进反应器中的共聚单体的数量来调整聚乙烯的密度。可以使用的共聚单体的例子包括1-烯烃如丁烯、己烯、辛烯、4-甲基戊烯，等等，最优选的是己烯。
制备本发明的中空包装物所需的聚乙烯的密度范围为由0.915g/cm3，优选由0.925g/cm3，至0.966g/cm3，高或至均聚物密度。
通过加至反应器中的氢气数量来调整聚乙烯的熔体指数。适用于本发明的熔体指数范围为0.2至5g/10分钟，优选为0.5g/10分钟至2.5g/10分钟。
用于本发明的聚乙烯树脂可以用单部位金属茂催化剂生产，也可用多部位金属茂催化剂生产，因此它或者具有单模式或者双模式分子量分布。分子量分布为2至20，优选为2至7，最优选为2至5。
根据上述方法生产的聚乙烯树脂具有使它们特别适于用作注坯吹塑级聚乙烯的物理性质。此外，人们已惊异地发现，甚至当它们的分子量分布窄时，它们也具有优异的加工性能。
本发明的聚乙烯树脂优选用于生产容量为0.0005至2升范围的容器。它们更优选用于生产食品包装物，例如奶瓶或果汁瓶、化妆品或药品包装物，以及家用包装物。
注塑机可以是任何通常用作注坯吹塑的机器，例如JOMAR机和UNILOY机。它们是连续注坯吹塑顶出机，带有多达16个注坯吹塑模头，这些模头能用于生产容量高达0.8升的聚乙烯容器。
本发明的中空包装物的特征在于其内表面和外表面均具有很高的光泽度(用ASTM D2457-90检验法所测定的)，低的光雾度(用ASTM D1003-92所测定的)，以及显著的耐坠落性。此外，因为具有非常光滑的内表面，它可以提高倒出速度，降低留在包装物中的残留量。
按照标准检验法ISO 8256于-30℃下在模板上测定冲击强度。
此外也很令人惊异的是，甚至在熔体指数低时生产率也是很高的。本方法是很稳定的，而且以优异的成功率生产包装物。
                           实施例
制备了若干聚乙烯树脂并检验了光泽度、光雾度、冲击强度及坠落性。
                           树脂R1
在回路淤浆反应器中用连续聚合反应制得了聚乙烯R1，使用了载在载体上的已离子化的金属茂催化剂，此催化剂用两步法制得：首先将MAO与SiO2反应生产SiO2·MAO，然后将94重量％的第一步生产的SiO2·MAO与6重量％的亚乙基双-(四氢茚基)二氯化锆反应。把干催化剂在异丁烷淤浆化，并在加入到反应器中之前与三异丁基铝(TIBAL，在己烷中，10重量％)预接触。反应在淤浆回路反应器中进行，聚合反应温度维持在90℃。操作条件如下：
TIBAL浓度(ppm)：100-200
iC4进料(kg/h)：1940
C2进料(kg/h)：3900
C6进料(g/kgc2)：22
H2进料(g/t)：42
其中，C2是乙烯，C6是1-己烯，iC4是异丁烷，而TIBAL是三异丁基铝。
                         树脂R2
按照与聚合树脂R1所用的相同方法，制得聚乙烯树脂R2，不同的是金属茂催化剂是双-(丁基环戊二烯基)二氯化锆。助催化剂也是TIBAL(在己烷中，10重量％)，聚合反应的温度为90℃。操作条件如下：
IC4进料(kg/h)：24
C2进料(cc/h)：9
C6进料(cc/h)：27
H2进料(NI/h)：1.9
TIBAL浓度(ppm)：292
                        树脂R3
树脂R3是使用铬催化剂生产的单模式聚乙烯，以名称Finathene 5502市场供应：它是用载体上的铬催化剂制得的。
                        树脂R4
树脂R4是低密度聚乙烯树脂，Dupont以名称Dupont 20-6064生产，用于注坯吹塑。
树脂R1至R3用己烯作为共聚单体而制备。
这些树脂的性能总结于表1中。
按照标准检验法ISO 8256，在-30℃的温度下在模板上测定冲击强度。
                                                    表I
 树脂   密度g/cm3  HLMI g/10′   MI2 g/10′      Mn     Mw     Mz   冲击强度kj/m2     MWD
  R1     0.934     25.1     0.96     34083    88134   167888       170     2.6
  R2     0.950     27     1.6     34624    92729   201616       130     2.7
  R3     0.953     17.65     0.19     19620    153558   1333100       80     7.8
  R4     0.92     n.a.     1.9     n.a.    n.a.   n.a.       n.a.     n.a.
n.a.：未得到
用UNILOY注坯吹塑机，在表II概述的操作条件下，将树脂R1和R3进行注坯吹塑。
用得自Jomar的15型注坯吹塑机(IBM)加工树脂R2和R4。注塑模塑过程分为三个工序：
1.注塑工序，其中将熔融聚合物通过喷嘴注入到热的预成形模具中，形成外部形状，该模具绕着芯棒被压紧，形成内部形状。
2.吹塑工序，其中让芯棒压空气进入预成形物中，使吹胀至冷却后的吹塑模形状；及
3.顶出工序：其中在冷却之后将生产的物品从芯棒取出。
所用机器及模具的特点总结在表III之中。通用混合螺杆的直径为25.4mm，长度与直径的比值L/D为30∶1。
挤出物均具有很高的光泽度和优异的冲击强度。
                              表II
   树脂     物质温度   循环时间  内光泽度60°  外光泽度60°
       ℃       S       ％       ％
    R1     200-210     16.49       72       38
    R2     210-220     15.07       n.a.       62
    R3     230-240     19.30       20       22
    R4     180-200     15.13       n.a.       n.a.
n.a.：未得到
操作过程中，树脂R1和R2具有很高的加工稳定性，良好成形瓶子的百分比很高，重量恒定性良好。所得瓶子与用树脂R3和R4所制得的瓶子相比具有很高的光泽度。这可以从图1清楚地看出看出，图1表示分别用以金属茂催化剂亚乙基双-(四氢茚基)二氯化锆制得的低密度聚乙烯和用Dupont生产的低密度聚乙烯经注坯吹塑制造的瓶子；这也可以从图2看出，图2表示分别用金属茂催化剂亚乙基双(四氢茚基)二氯化锆制得的中密度聚乙烯和用锆催化剂制得的中密度聚乙烯经注坯吹塑制造的瓶子。
               表III
预成形合模，141kg/cm2(吨)     11.4
铸塑区，246kg/cm2(cm2)，387kg/cm2(cm2)     4629
吹塑合模，141kg/cm2(吨)     2.9
闭模高度(mm)     203.2
压机行程(mm)     101.6
最大模座尺寸(mm)     254×286
Tigger棒长度(mm)     166
最大回转长度(mm)     356
注射量(g)a     50
马达大小(kw)     15
用美国的Jomar设备检验了另外的5种金属茂生产的聚乙烯树脂R5至R9。树脂R5和R6用双(丁基环戊二烯基)二氯化锆制得，树脂R7至R9用亚乙基双(四氢茚基)二氯化锆制得。
为了比较用铬基催化剂体系生产的聚乙烯树脂R10和用齐格勒-纳塔催化剂体系制的聚乙烯树脂R11，也将它们在相似条件下进行检验。
这些树脂的性能总结在表IV中。
                                  表IV
 树脂 MI2g/10′   密度g/cm3     Mn    Mw     Mz     MWD
  R5     2.36     0.954   31628   80859   155635     2.6
  R6     11     0.958   20417   51223   94478     2.5
  R7     2.04     0.949   25937   68841   138233     2.7
  R8     0.85     0.934     23882     80224     201417     3.4
  R9     0.65     0.947     32034     87444     182364     2.7
  R10     0.3     0.955
  R11     1.2     0.962
为检验这些树脂的注坯吹塑性能，使用了两种不同模具：
-一种装有四个空腔的1盎司(28.35g)香波瓶模具体系，及
-一种装有10个空腔的3盎司(85.05g)圆罐模具体系。
所得结果证实了用树脂R1至R4已观察到的倾向：
-金属茂生产的树脂R5至R9的光学性能明显好于分别用铬基催化剂和齐格勒-纳塔催化剂制得的树脂R10和R11；
-金属茂生产的树脂R5至R9的循环时间明显短于树脂R10和R11的循环时间；
-树脂熔体指数MI2的增大缩短了循环时间，但是使加工范围变窄，基于金属茂的树脂R5至R9加工范围变窄，比基于铬和基于齐格勒-纳塔的树脂R10和R11，不那么严重。
-用亚乙基双(四氢茚基)二氯化锆制得的树脂R7至R9，比起用双(丁基环戊二烯基)二氯化锆制得的树脂R5和R6，具有更短的循环时间和更低的剪切粘度(在1000秒-1的剪切速率范围内)，因此具有更好的加工性。
-树脂R7至R9比树脂R11具有更好的模塑复制性。
此外，对每个1盎司(28.35g)瓶子评估了它们的下列特性：
-重量
-壁厚分布
-光泽度
-高度
-瓶子直径
-颈直径
变动熔化温度、熔体指数MI2及模具而测定光泽度：用了抛光的模具和喷砂处理过的模具。
光泽度测量结果示于表V中，而其他测量结果总结在表VI。
                                 表V
   树脂    MI2 g/10′   熔体温度℃  喷砂处理过的模具   抛光模具
    R5      2.36      185       33.6     62.9
    R5      2.36      215       28.8     63.4
    R7      2.04      185       33.5     67.2
    R8      0.85      185       25.4     71.6
    R8      0.85      215       21.3     81.7
    R10      0.3      215       32.1     47.9
    R11      1.2      215       24.8     73
从表V能得出结论：对抛光模具来说，在相似熔体指数下，随着提高熔体温度，其光学性能改善了。当树脂R8在高温下就抛光模具和喷砂处理过的模具得到的光泽度进行比较时，正如能够推断到的，上面的事实是由于模塑重复性更好的缘故。提高熔体温度会降低光学性能，当比较树脂R7和R8使用抛光模具场合所测得光泽度结果时，人们能明白这一点。
                                    表VI
 树脂  熔体温度℃     重量g     高度mm   瓶子直径mm  颈部直径mm
  R5     185     6.19     80.41     25.74     15.29
  R5     215     6.06     80.39     25.78     15.18
  R7     185     6.19     80.44     25.77     15.29
  R8     185     6.1     80.27     25.76     15.27
  R8     215     6.04     80.23     25.73     15.19
  R10     195     -     80.43     25.83     15.36
  R10     215     6.06     80.36     25.03     15.27
  R11     215     6.08     80.36     25.76     15.33
从表VI可以得出结论：用金属茂制得的聚乙烯树脂R5、R7和R8比树脂R10和R11，能生产瓶颈直径较小的瓶子。人们也观察到：降低熔体温度导致瓶子重量稍稍增加。
也研究了1盎司(28.35g)瓶子的厚度分布。为此目的，已将瓶高度分为四个相等部分，对这四个高度中的每一个，在瓶子圆周的四个距离相同的点上，测定其厚度，瓶壁的厚度约为1mm。业已观察到，树脂R5至R9受熔体温度影响很小，具有优异的厚度分布，这比用树脂R10和R11生产的瓶子所得的结果更好。也已观察到，把熔体指数提高到超过2g/10分钟这个值，会导致用基于金属茂的聚乙烯树脂所生产瓶子的厚度分布差。
这些结果清楚表明了由用金属茂生产的聚乙烯所获得的空心包装物在光泽度、循环时间、尺寸稳定性和冲击强度的质量方面有了改进。

Claims (8)

1.一种单层中空包装物，其主要含有用金属茂生产的聚乙烯，并用注坯吹塑法生产，其特征在于该中空包装物的外光泽度和内光泽度至少为30，该金属茂生产的聚乙烯的密度为0.910至0.966g/cm3或高至均聚物的密度，熔体指数MI2为0.5至2.5g/10分钟。
2.根据权利要求1的中空包装物，其中金属茂生产的聚乙烯的熔体指数MI2为0.5至2.0g/10分钟。
3.根据权利要求1或权利要求2的中空包装物，其中金属茂生产的聚乙烯的分子量分布为2～7。
4.根据前述权利要求任一项的中空包装物，其中金属茂催化剂是亚乙基双-(四氢茚基)二氯化锆、亚乙基双-(茚基)二氯化锆或双-(正丁基环戊二烯基)二氯化锆。
5.根据前述权利要求生产任一项的食品包装物。
6.根据权利要求1至3中的任一项生产的化妆品或药品包装物。
7.根据权利要求1至3中的任一项生产的家用包装物。
8.金属茂生产的聚乙烯在制备内光泽度和外光泽度至少为30的中空包装物方面的用途。
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JP2005500220A (ja) 2005-01-06
KR100898940B1 (ko) 2009-05-25
CN100404236C (zh) 2008-07-23
AU2002331183A1 (en) 2003-03-10
EP1287969A1 (en) 2003-03-05
WO2003018290A1 (en) 2003-03-06
ATE344126T1 (de) 2006-11-15
EP1427579A1 (en) 2004-06-16
ES2274089T3 (es) 2007-05-16
US20060269709A1 (en) 2006-11-30
DE60215828D1 (de) 2006-12-14
EP1427579B1 (en) 2006-11-02
US20050037166A1 (en) 2005-02-17
DE60215828T2 (de) 2007-03-15

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