CN1274366A - 适合透明流延薄膜用的丙烯聚合物 - Google Patents

适合透明流延薄膜用的丙烯聚合物 Download PDF

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CN1274366A
CN1274366A CN99801294A CN99801294A CN1274366A CN 1274366 A CN1274366 A CN 1274366A CN 99801294 A CN99801294 A CN 99801294A CN 99801294 A CN99801294 A CN 99801294A CN 1274366 A CN1274366 A CN 1274366A
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polymkeric substance
laminated thing
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viscosity breaking
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CN1151181C (zh
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E·贝卡里尼
G·帕西
F·萨托里
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Basell North America Inc
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Abstract

由具有如下特征的高结晶丙烯聚合物制备的流延层合物:MFR介于5～15g/10min;重均分子量与数均分子量之间的比值在4.5～9;密度等于或大于0.9020g/cm3;以及在常温二甲苯中的溶解度不大于2.5wt%。

Description

适合透明流延薄膜用的丙烯聚合物
发明领域
本发明涉及高结晶丙烯聚合物以及由其制成的流延层合物。本发明还涉及由所述聚合物生产所述层合物的方法。
本发明的聚合物使得有可能按照本发明的方法生产出具有良好光学性质，特别是透明度和光泽的层合物，但是它即使在高温下仍保持诸如挺度之类为高结晶聚丙烯所特有的高机械性能。凭借上述特性以及由所用聚合物高结晶度带来的在二甲苯中的低溶解百分数，本发明的层合物特别适合用来包装食品。
用于生产透明度好、机械性能高的薄膜所使用的丙烯聚合物是已知的。所述薄膜例如描述在欧洲专利EP 497590中。按照所述专利，上述特性是采用熔体流动速率(MFR)在1～10dg/min、重均分子量( Mw)与数均分子量( Mn)之间的比值，即， Mw/ Mn，在2.5～4范围的高结晶聚丙烯获得的。
现已惊奇地发现，既有良好透明度又有良好机械性能的流延层合物，即使采用各项参数不在上述专利所规定的范围的丙烯聚合物，也可以获得。
凭借本发明的聚合物，可以做到使生产出的层合物，与采用已知技术聚合物获得的相比，在相同厚度条件下具有良好机械性能和更高的透明度。
正如上面提到的，所述层合物还表现出优异的光泽。
因此，本发明提供具有如下特征的丙烯结晶聚合物：
(a)MFR介于5～15g/10min，优选6～13，更优选9～12；
(b)重均分子量(Mw)与数均分子量( Mn)之间的比值，即，Mw/ Mn，在4.5～9，优选5～8，更优选6～8的范围；
(c)多分散性指数(PI)，按下面将描述的方法测定，在2～6的范围，优选在3～5；
(d)密度等于或大于0.9020g/cm3；以及
(e)在常温，即在约25℃二甲苯中的溶解度不大于2.5wt％，优选不大于2％；
所述聚合物可通过多分散性指数为5～8，优选6～7的聚合物的化学减粘裂化(chemical visbreaking)获得。
本发明的聚合物选自丙烯均聚物，这是优选的，还有丙烯与乙烯或C4～C8α-烯烃的共聚物或其混合物；均聚聚丙烯与上述共聚物的混合物也可使用。上述α-烯烃，可为线型或支链的，优选选自1-丁烯、1-己烯及3-甲基-1-戊烯。乙烯在共聚物中的含量不超过1mol％，而C4～C8α-烯烃的含量，例如可在0.2～5mol％，更优选在0.2～1％的范围内变化。
本发明的聚合物是采用选自已知齐格勒-纳塔催化剂当中高度立构有规的那些催化剂，在1个或多个聚合阶段中制备的。具体地说，所使用的催化剂体系包含：(a)固体催化剂组分，其中包含钛化合物和电子给体化合物，二者均载于氯化镁载体上；以及(b)三烷基铝化合物及电子给体化合物。
可使用的催化剂及聚合方法的实例描述在公开的欧洲专利申请EP-A-45977中。
由该聚合方法生产的聚合物具有1～4.5g/10min，优选1.5～4的MFR。然后，所生成的聚合物按照技术上熟知的方法接受聚合物链的化学减粘裂化处理，以便获得要求的MFR、PI和 Mw/ Mn数值；例如，聚合物的化学减粘裂化在诸如过氧化物之类自由基引发剂存在下进行。可用于此目的的自由基引发剂实例是2，5-二甲基-2，5-二(叔丁基过氧)-己烷以及过氧化二枯基。减粘裂化是采用恰当用量的自由基引发剂实施的，且优选在诸如氮气的惰性气氛中进行。可采用技术上已知的方法、设备和操作条件来实施本方法。
常用的添加剂，如稳定剂和颜料，可加入到本发明的聚合物中。在层合物的制备中，所加入的常用添加剂是针对所述领域的那些，即，抗粘连剂(如二氧化硅)，以及滑爽剂如芥酰胺。本发明的另一个目的是由上述聚合物制备的具有上面提到的光学及机械性能的流延层合物。所述层合物，在该术语用于描述薄膜和片材的情况下，具有0.01mm～0.5mm，典型地0.01～0.4mm的厚度。
本发明的层合物可以是单层或多层的。在后一种情况下，至少1层由本发明的聚合物构成。
一般而言，本发明的层合物不呈现，按下面所描述的方法测定，尺寸大于1.5mm的鱼眼。就典型而言，每平方米范围内，尺寸在0.7mm～1.5mm之间的鱼眼数目不大于3，且每平方米，尺寸在0.2～0.7mm以下的鱼眼不超过300个。
为了获得具有上述性质的层合物，聚合物所接受的层合处理方法包括：将刚刚生产出来的层合物趁热在例如模头出口处立即冷却到室温或更低，譬如等于或小于20℃，优选低于15℃。所述冷却发生在不超过2s之内，优选1.9s之内。
按照本发明的典型层合方法包括：
1)将上述丙烯聚合物挤出并层合；以及随即
2)将从挤塑机模头出来的层合物在不超过2min时间内迅速冷却(骤冷)至层合物表面不超过70℃的状态。
层合物的骤冷可按各种各样的方式进行：例如，让层合物处于与诸如旋转滚筒表面接触的状态，该滚筒维持在低于20℃，优选不超过15℃的温度。
作为本发明方法的例子，0.05mm厚的薄膜在离开模头之后的0.07～0.13s便开始骤冷。
聚合物的挤出采用传统挤塑技术和设备(如，Bandera挤塑机)以及操作条件来实施。一般而言，从挤塑机模头出来的层合物被引导到表面温度维持在上述范围内的滚筒上。
下面给出实例，其目的在于说明而不是限制本发明。对本发明的聚合物及薄膜进行了测试以评估其特征和性能；所述测试使用的方法为如下所述。
溶解度：关于可溶于25℃二甲苯中的残余百分数，按下列方式测定：通过将样品放在135℃的二甲苯中搅拌1h制备成浓度为1wt％样品的二甲苯溶液。还在搅拌下，让溶液冷却至95℃，然后，倒入到25℃的浴中，在浴中保持20min不加搅拌，然后恢复搅拌并持续另外的10min。然后，溶液经过滤，在一部分滤液中加入丙酮，以便获得溶解聚合物的沉淀。回收如此获得的聚合物，洗涤、干燥，最后称重以确定可溶于二甲苯中的百分数。
熔体流动速率(MFR)：按照方法ASTM-D 1238，条件L。
多分散性指数(PI)：根据以RMS-800流变学力谱仪实施的动态试验结果计算获得。PI由等式PI＝105/Gc来定义，其中Gc(交叉模量)值是G’(储能模量)与G”(损耗模量)相重合处的数值。样品由1g聚合物制备，所述样品厚3mm，直径25mm；随后将其放在上述设备中，然后逐步升温，直至90min后达到200℃。在此温度下进行试验，在试验中测定G’和G”随频率变化的情况。
弹性挠曲模量：ASTM D-790
凝胶含量：采用Sistemi Intelligenti sipar设备由光学计数器自动计数来测定每平方米0.05mm厚薄膜上的鱼眼数目。
雾度：ASTM D-1003
光泽：ASTM D-2457
摩擦系数：ASTM D-1894，条件D。试验是在挤出后24h，在23℃对层合物进行的。按照该方法，为确定摩擦系数(FC)，使层合物在按照DIN 4768方法制备的金属导板上滑动。
实例1
如下组成(重量份)的掺混料在Bandera挤塑机(L/D＝30)中进行挤塑：
-(a)99.642份在常温二甲苯中的溶解度等于1.7％、MFR等于3.5g/10min、PI为7.2的聚丙烯；
-(b)0.34份含50wt％二氧化硅和50wt％芥酰胺的组合物，由Grace公司按商品名Syloblock 250H出售；
-(c)0.018份含10份2，5-二甲基-2，5-二(叔丁基过氧)己烷和90份聚丙烯碎片的组合物。
挤塑机的操作条件如下：
-区1温度：190～250℃；
-熔体温度：248℃；
-流率：600kg/h；
-螺杆转速：150rpm；
-压缩比：3.5。
以250℃离开挤塑机模头(其尺寸为150×03mm)的熔融聚合物被引导到距离模头15mm的直径15.4cm的滚筒(骤冷辊)上。滚筒温度为10℃，它以7m/min的速度转动。薄膜表面通过与上述滚筒进行2s的接触被冷却到68℃。如此生产的薄膜具有0.05mm的厚度。
对比例1c
重复实例1，不同之处在于，所使用的聚合物的特征如表1所示。聚合物在化学减粘裂化之前的MFR为1.8g/10min。
对比例2c
重复实例1，不同之处在于，所使用的聚合物的特征如表1所示，但未经减粘裂化处理。
对比例3c
重复实例1，不同之处在于，成膜期间薄膜表面冷却到68℃的过程超过了2s的时间。
实例2
重复实例1，不同之处在于，薄膜的厚度为0.025mm。
表1和2给出了按照本发明的实例及对比例中所用聚合物的性能，以及挤出薄膜的机械及光学性能。
                                表1
实例及对比例     1     1c     2c
  化学减粘裂化前的聚合物性能
MFRL      g/10min     3.5     1.8     10.1
PI     7.2     3.9     4.3
化学减粘裂化后的聚合物性能
MFRL      g/10min     10.9     9.8     10.1
PI     4.01     3.0     4.3
密度g/cm3     0.9067     0.9005     0.9053
二甲苯中溶解度wt％     1.8     3.8     1.9
特性粘度dl/g     1.51     1.62     1.55
Mw/ Mn     7.1     6.2     7.3
                                          表2
实例及对比例   1     1c     2c     3c   2
厚度             mm   0.05     0.05     0.05     0.05   0.025
鱼眼     D＞1.5mm   n/m2   0     0     0     0   0
鱼眼     D＞0.7-1.5mmn/m2   1     0     0     2   1
鱼眼     D＞0.2mm   n/m2   55     60     73     80   55
雾度             ％   2.4     2.2     10.3     6.8   1.5
光泽(45°)       ‰   82.7     83.9     68.0     60.7   98.7
光泽(60°)       ‰   139.4     133.1     109.0     105.0   149.0
正切拉伸模量MPa   MD 907TD 807     MD 658TD 660     MD 830TD 750     MD 751TD 783   MD 898TD 866
屈服拉伸强度MPa   MD 22.5TD 22.1     MD 17.9TD 17.7     MD 19.8TD 19.4     MD 21.2TD 21.4   MD 22.1TD 21.9
屈服伸长％   MD 7.0TD 6.7     MD 9.7TD 9.0     MD 6.3TD 7.1     MD 8.4TD 8.0   MD 7.6TD 7.6
断裂拉伸强度MPa   MD 40.9TD 33.0     MD 40.7TD 33.9     MD 40.7TD 33.2     MD 56.1TD 30.2   MD 48.2TD 34.2
断裂伸长％   MD 792TD 769     MD 793TD 762     MD 750TD 770     MD 590TD 614   MD 652.8TD 609.7
埃尔曼多夫试验   N   MD 0.51TD 1.24     MD 0.50TD 0.82     MD 0.52TD 1.02     MD 0.19TD 3.43   MD 0.27TD 3.23
静摩擦系数＞24h   0.37     0.42     0.40     0.15   0.40
MD＝纵向TD＝横向

Claims (9)

1.具有如下特征的结晶丙烯聚合物：
(a)MFR介于5～15g/10min；
(b)重均分子量( Mw)与数均分子量( Mn)之间的比值，即 Mw/ Mn，在4.5～9；
(c)多分散性指数(PI)，按下面将描述的方法测定，在2～6的范围，优选在3～5；
(d)密度等于或大于0.9020g/cm3；以及
(e)在常温，即在约25℃二甲苯中的溶解度不大于2.5wt％，优选不大于2％；
所述聚合物可通过多分散性指数为5～8的聚合物的化学减粘裂化获得。
2.权利要求1的聚合物，其中化学减粘裂化是在自由基引发剂存在下进行的。
3.权利要求1和2的聚合物，选自均聚聚丙烯。
4.生产权利要求1的聚合物的方法，包括：在齐格勒-纳塔催化剂存在下多分散性指数在5～8范围内的聚合物的聚合制备，以及如此获得的聚合物的化学减粘裂化。
5.权利要求1的聚合物在生产层合物中的应用。
6.生产流延层合物的方法，包括：
1)将权利要求1～3的丙烯聚合物挤出并层合；以及随即
2)将从挤塑机模头出来的层合物在不超过2s的时间内迅速冷却直至层合物表面达到不超过70℃的温度为止。
7.可由权利要求6和7的方法获得的层合物。
8.权利要求8的层合物，其厚度在0.01mm～0.5mm范围内。
9.权利要求8的层合物用于食品包装的应用。
CNB998012947A 1998-06-01 1999-05-27 适合透明流延薄膜用的丙烯聚合物 Expired - Fee Related CN1151181C (zh)

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IT98MI001213A ITMI981213A1 (it) 1998-06-01 1998-06-01 Polimeri propilenici adatti per film cast trasparenti

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US4282076A (en) * 1979-09-17 1981-08-04 Hercules Incorporated Method of visbreaking polypropylene
JPS587329A (ja) * 1981-07-07 1983-01-17 Chisso Corp ポリオレフインフイルムの製造方法
US4567089A (en) * 1984-07-23 1986-01-28 Mitsubishi Petrochemical Co., Ltd. Thermoforming propylene polymer laminated sheet
CA1280543C (en) 1985-01-31 1991-02-19 B. Joseph Scheve Polypropylene with free-end long chain branching, process for making it, and use thereof
JP3016880B2 (ja) 1991-02-01 2000-03-06 三菱化学株式会社 フィルム成形用高結晶性ポリプロピレン
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JP2819996B2 (ja) * 1993-07-08 1998-11-05 住友化学工業株式会社 ポリプロピレン積層フィルム
JP3258830B2 (ja) * 1994-09-29 2002-02-18 株式会社興人 ポリオレフィン系熱収縮性積層フィルム
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KR100595334B1 (ko) 2006-07-03
EP1000095B1 (en) 2004-02-11
CA2297665A1 (en) 1999-12-09
ES2214033T3 (es) 2004-09-01
ATE259383T1 (de) 2004-02-15
CN1151181C (zh) 2004-05-26
DE69914701T2 (de) 2004-10-07
BR9911038A (pt) 2001-01-16
BR9911038B1 (pt) 2009-01-13
AR018421A1 (es) 2001-11-14
US6440577B1 (en) 2002-08-27
DE69914701D1 (de) 2004-03-18
JP2002517525A (ja) 2002-06-18
ITMI981213A1 (it) 1999-12-01
EP1000095A1 (en) 2000-05-17
WO1999062966A1 (en) 1999-12-09

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