CN101472726A - 用于注射-拉伸-吹塑-成型的低熔体流动指数树脂 - Google Patents
用于注射-拉伸-吹塑-成型的低熔体流动指数树脂 Download PDFInfo
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Abstract
本发明公开一种用丙烯的无规共聚物通过两步注射－拉伸－吹塑－成型制备瓶、优选医用瓶的方法，该丙烯无规共聚物具有1～3dg/min的熔体指数MI2和基于该树脂重量的2～3.5重量％的乙烯含量，其中预成型件注射温度为至少280℃。
Description
本发明涉及用于两步注射-拉伸-吹塑-成型(ISBM)方法的低熔体流动聚丙烯预成型件的制备。
Mistui的EP-A-151741公开了通过ISBM的制品的一步制造。这些制品由具有4～50dg/min的熔体流动指数并且含有成核剂的丙烯-乙烯无规共聚物制备。注射成型温度为200～260℃且所有实施例在220℃的注射成型温度下进行。
Bekum的WO95/11791涉及通过ISBM制备制品的两步法。优选的树脂是含有大于50重量％丙烯并且具有10～20dg/min的熔体流动指数的乙烯-丙烯共聚物。注射腔充填速率为3～5克/秒且注射温度为约210℃。
Milliken的WO05/074428公开了通过ISBM制备制品的两步法。树脂是通过本领域中已知的任意方法制备的具有6～50dg/min、优选13～35dg/min熔体流动指数的聚丙烯组合物。模具装料速率大于5克/秒且预成型制品的侧壁具有小于3.5mm的最大厚度。实施例中列举的注射温度为230℃和240℃。
BSAF的WO99/41293公开了茂金属生产的丙烯均聚物和共聚物在ISBM中的用途。熔体指数的范围宽泛地限定为0.1～1000dg/min且注射温度为200～280℃。茂金属制备的聚丙烯的多分散指数非常窄。
这些树脂都没有产生具有理想的性质平衡的制品。
本发明的一个目的是通过两步注射-拉伸-吹塑-成型生产医用瓶。
本发明的另一目的是提供一种使用低熔体流动聚丙烯树脂制备用于注射-拉伸-吹塑-成型的预成型件以制备在双轴取向后具有优异光学性质的医用瓶的方法。
本发明的另一目的是生产具有良好厚度分布的医用瓶。
本发明的进一步目的是生产具有良好堆集性质的医用瓶。
本发明的又一目的是生产具有优异的坠落试验尤其在低温下具有优异的坠落试验的医用瓶。
通过本发明至少部分地实现这些目的中的任意一个。
因此，本发明公开了用丙烯和乙烯的无规共聚物通过两步注射-拉伸-吹塑-成型制备的瓶(优选医用瓶)，所述丙烯和乙烯的无规共聚物具有1～3dg/min的熔体指数MI2、基于该聚合物重量的小于3.5重量％的乙烯含量并且其中预成型件注射温度为至少280℃。
本发明还包括制备预成型件的方法、由此获得的预成型件、所述预成型件用于制备医用瓶的用途以及从所述预成型件制备的医用瓶。
熔体流动指数MI2根据标准测试ISO 1133的方法在2.16kg的负载和230℃的温度下测量。
优选地，本发明中使用的聚丙烯树脂用齐格勒-纳塔(ZN)催化剂体系制备。ZN催化剂体系固有地产生具有宽多分散指数的聚合物。多分散指数定义为重均分子量Mw与数均分子量Mn的比Mw/Mn。分子量通过凝胶渗透色谱法(GPC)测得。齐格勒-纳塔催化剂体系通常产生具有至少6的多分散指数的聚合物。为清楚起见，重复的是，茂金属和单位点催化剂不是ZN催化剂。
所述树脂为丙烯的无规共聚物。优选的共聚单体是乙烯并且存在于树脂中的乙烯的量为至多3.5重量％，优选为至多3重量％，且优选的最小值为1重量％。
熔体指数至多为3dg/min。优选的最小MI2为1.5dg/min；优选的最大MI2为2.5dg/min，更优选为2dg/min。
这种类型的低熔体流动树脂一般不用于注射-拉伸-吹塑-成型应用并因此使注射-拉伸-吹塑-成型条件适合于加工该树脂。
所述树脂可额外地含有最高达5000ppm的成核剂。优选地，如果存在成核剂，则成核剂的使用量为200～2500ppm。
可加入本领域中通常采用的其它添加剂，例如抗氧化剂或抗静电剂。
另外，该树脂是被接受用于医疗应用的少数树脂之一。当本发明用于制备医用瓶时，成核剂必须在医疗应用中所接受的那些(例如滑石和苯甲酸钠)中选择。更优选没有成核剂。可加入医疗应用中允许的其它添加剂例如European Pharmacopeia §3.1.6中所描述的那些添加剂。
用于制备预成型件的注射温度为至少280℃，优选为至少320℃且更优选为至少330℃。不存在绝对最大值，只要本领域中公知的添加剂料包是适合于该温度的。然而，通常最大值不超过350℃。
对于较低的熔体指数，优选提高注射温度以避免过高的应力。提高注射温度容许提高注射速率而不增加应力。
在规定的注射温度下，模具装料速率和浇注口直径的比至多为10cc/s/mm，优选8cc/s/mm。其至少为5cc/s/mm。本领域中通常使用的浇注口直径为1.2～4mm，本发明优选使用1.25～3mm的浇注口直径。
预成型件中产生的应力对成品的透明性和冲击性质起重要作用。
注射-拉伸-吹塑-成型可以在两个单独的机器上以两步法(冷循环)进行，或者在单个机器上以一步法(热循环)进行。在本发明中，使用两步法并且其通常在两个单独的场所进行。其包括下列步骤：
-通过在多腔模具上注射成型提供预成型件；
-将该预成型件冷却至室温；
-将该预成型件传送到拉伸-吹塑成型机；
-在该拉伸-吹塑成型机中再加热该预成型件；
-任选地使该经加热的预成型件通过平衡区以容许热量通过预成型件壁均匀地分散；
-任选地，该预成型件进行预吹塑步骤；
-通过中心杆轴向拉伸该预成型件并且同时通过高压空气使该经拉伸的预成型件径向取向。
优选地，该再加热步骤在反射性辐射加热炉中根据适合于该预成型件的预定温度分布进行。
在该过程中，该拉伸步骤是关键步骤且其需要通过优化过程制得的预成型件以获得最终制品的最佳性质。
该预成型件在红外线炉中根据加热分布进行再加热。对于每个腔每小时生产约1500件制品的系统，该再加热步骤中通常必需的能量为28～40kW，优选30～36kW。典型的再加热温度为90～140℃。
预吹塑压力一般为2～8巴，优选4～6巴。然后通常在5～40巴、优选8～30巴且最优选15～20巴的吹塑压力下进行拉伸。拉伸杆速度为1000～2000mm/s，优选为1400～1800mm/s且最优选为约1600mm/s。拉伸杆直径取决于预成型件的尺寸。当杆直径约为预成型件直径的2/3时获得成品中材料分布的最佳结果。例如，对于具有25mm直径的预成型件，优选的杆直径为约16mm。
具有出众的硬度和透明性的改进的冲击强度瓶特别适合于医疗应用。本发明的新瓶子可有利地代替标准玻璃瓶，节约其生产和运输的重量和能量。而且，由于通过本方法生产的容器的玻璃-透明品质，可容易地对医用瓶中所含的溶液应用在线光学控制。另外，该新型瓶比常规聚丙烯吹塑成型的瓶容器更安全，因为它们被制造出来并且在瓶的底部处没有焊线，该焊线在吹塑成型过程中是典型的且可导致泄漏的形成并因此需要额外的品质控制。实际上，聚丙烯树脂由于它们高的熔融温度而具有差的焊接性质。
用本发明的预成型件制备的医用瓶具有优异的光学性质：它们在遍及它们的整个主体或至少遍及它们的主体的大部分上具有优异的透明性。此外，它们具有良好的壁厚分布、优异的坠落试验和非常好的最大负载和堆集性质。它们还具有多种理想的性质例如低的水蒸气渗透性、良好的可压缩性、以及允许如热装料、微波加热或灭菌的优异耐热性。
通过下列实施例说明医用瓶的性质，所述实施例不意图限制本发明的范围。
实施例
已经测试了几种用齐格勒-纳塔催化剂体系制备的丙烯的无规共聚物。R1是通常用在ISBM中的参照树脂。R2是根据本发明的低熔体流动树脂。它们的性质归纳在表1中。
表1.
| 树脂 | R1 | R2 |
| C2(重量％) | 3.3 | 2.8 |
| MI2(dg/min) | 10 | 1.8 |
| 抗氧化剂(ppm) | 1000 | 934 |
| 成核剂(ppm) | 250 | 0 |
| Tm(℃) | 146 | 149 |
| Tc起始(℃) | 132.3 | 109 |
| Tc峰(℃) | 117.3 | 105 |
Tm和Tc分别表示熔融温度和结晶温度。
预成型件是在具有下列单腔模具的Arburg 370机器上从这些树脂制备的：这些预成型件具有16.5g的重量并且这些预成型件用于制备具有约300μm壁厚的500mL瓶。
壁厚分布通过降低熔体指数并通过因此提高注射温度而改善。在沿着瓶高度的三个不同点处并且对于各个高度在沿着瓶圆周周长的彼此成90°的四个不同点处测量壁厚。
现有技术的聚丙烯瓶均显示出不均匀的壁厚分布。厚度沿着瓶的周长相当恒定但随着高度而变化。在本发明的瓶中，显著降低了厚度随高度的变化并且本发明的瓶具有比现有技术的那些瓶好得多的厚度分布，从而使得它们对于堆集或动态压缩具有更好的耐受性。结果示于表2中。
表2.
在相同的空的开口瓶上还使用标准测试ASTM D 2659-95的方法进行了动态压缩试验。结果示于表3中。
坠落试验允许最高达6m的坠落高度。瓶子垂直地坠落在呈15°坡度的金属板上。该试验在室温(23℃)下用装满水并在室温下存放48小时的瓶进行。没有破裂的最大高度H(单位m)也在表3中给出。其表示这样的高度，在该高度处50％的试验样品破裂。
通过雾度量化具有约300＝300μm μm壁厚的瓶的透明性，所述雾度使用标准试验ASTM D 1003的方法测量。
表3.
本发明的从低熔体流动树脂制备的瓶具有比现有技术的那些瓶好得多的壁厚分布，并且具有与现有技术的那些瓶相当的光学和机械性质。
权利要求书(按照条约第19条的修改)
1.一种用丙烯和乙烯的无规共聚物通过两步注射-拉伸-吹塑-成型制备瓶的方法，所述丙烯和乙烯的无规共聚物具有1～3dg/min的熔体指数MI2、基于该树脂重量的2～3.5重量％的乙烯含量并且用齐格勒-纳塔催化剂体系制备，其中预成型件注射温度为至少280℃，并且其中模具装料速率与浇注口直径的比为至多10cc/s/mm。
2.权利要求1的方法，其中所述熔体指数为1.5～2.5dg/min。
3.权利要求1或2的方法，其中所述预成型件注射温度为至少320℃。
4.前述权利要求中任一项的方法，其中，对于1500个瓶/小时的产量，所述预成型件在红外线炉中用28～40kW的能量进行再加热。
5.能够通过权利要求1-4中任一项的方法获得的瓶。
6.丙烯的无规共聚物在通过两步注射-拉伸-吹塑-成型制备医用瓶中的用途，其中所述丙烯的无规共聚物由齐格勒-纳塔催化剂体系制备并且具有1～3dg/min的熔体流动指数MI2和基于该树脂重量的2～3.5重量％的乙烯含量。
Claims (7)
1.一种用丙烯和乙烯的无规共聚物通过两步注射-拉伸-吹塑-成型制备瓶的方法，所述丙烯和乙烯的无规共聚物具有1～3dg/min的熔体指数MI2、基于该树脂重量的2～3.5重量％的乙烯含量并且用齐格勒-纳塔催化剂体系制备，且其中预成型件注射温度为至少280℃。
2.权利要求1的方法，其中所述熔体指数为1.5～2.5dg/min。
3.权利要求1或2的方法，其中所述预成型件注射温度为至少320℃。
4.前述权利要求中任一项的方法，其中模具装料速率与浇注口直径的比为至多10cc/s/mm。
5.前述权利要求中任一项的方法，其中，对于1500个瓶/小时的产量，所述预成型件在红外线炉中用28～40kW的能量进行再加热。
6.能够通过权利要求1-5中任一项的方法获得的瓶。
7.丙烯的无规共聚物在通过两步注射-拉伸-吹塑-成型制备医用瓶中的用途，其中所述丙烯的无规共聚物具有1～3dg/min的熔体流动指数MI2和基于该树脂重量的2～3.5重量％的乙烯含量。
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| PCT/EP2007/056129 WO2007147845A1 (en) | 2006-06-21 | 2007-06-20 | Low melt flow index resins for injections-stretch-blow-moulding |
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| EP2168752B1 (en) * | 2008-09-30 | 2015-01-14 | The Procter & Gamble Company | Stretch blow molding process and container |
| US11292909B2 (en) | 2014-12-19 | 2022-04-05 | Earth Renewable Technologies | Extrudable polymer composition and method of making molded articles utilizing the same |
| JP6555915B2 (ja) * | 2015-03-31 | 2019-08-07 | 株式会社吉野工業所 | 液体ブロー成形装置 |
| EP3909742A1 (en) * | 2020-05-15 | 2021-11-17 | Borealis AG | Injection stretch blow moulded article |
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| DK2032333T3 (da) | 2011-01-03 |
| US8894911B2 (en) | 2014-11-25 |
| JP5261702B2 (ja) | 2013-08-14 |
| JP2009541082A (ja) | 2009-11-26 |
| EP1870223A1 (en) | 2007-12-26 |
| KR20090018943A (ko) | 2009-02-24 |
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