CN1882431A - 在注射－拉伸－吹塑模制中具有减少循环时间的聚丙烯的加工 - Google Patents
在注射－拉伸－吹塑模制中具有减少循环时间的聚丙烯的加工 Download PDFInfo
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- CN1882431A CN1882431A CNA2004800335758A CN200480033575A CN1882431A CN 1882431 A CN1882431 A CN 1882431A CN A2004800335758 A CNA2004800335758 A CN A2004800335758A CN 200480033575 A CN200480033575 A CN 200480033575A CN 1882431 A CN1882431 A CN 1882431A
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Abstract
本发明公开了使用茂金属制备的聚丙烯，通过循环时间降低了的注射－拉伸－吹塑－模制工艺来生产单层或多层制品，所述的制品具有优良的光学特性和刚度。
Description
本发明涉及聚丙烯的注射-拉伸-吹塑-模制的加工领域，并公开了使用茂金属制备的聚丙烯以减少循环时间，同时最终制品的光学特性得以改善。
目前，在注射-拉伸-吹塑-模制工艺中，最常用的材料是聚对苯二甲酸乙二醇酯(PET)。它具有获得约1000-1500瓶/空腔(cavity)/小时的非常短的循环时间的优势，而且它提供了具有优异的光学特性的进一步优势。它的较大缺点是成本非常高。
其它可选择的热塑性材料，例如聚氯乙烯(PVC)、聚苯乙烯、丙烯腈、聚丙烯和缩醛，也可以使用。其中，用齐格勒-纳塔催化剂体系制备的聚丙烯在使用中取得较好的效果。它的循环时间虽然值得称道，但仍高于PET树脂的循环时间；它的光学特性虽然不错，但仍达不到PET树脂所取得的水平。
因此需要用不具有用齐格勒-纳塔催化剂体系制备的聚丙烯的缺点的其它树脂替代昂贵的PET树脂。
本发明的一个目的是提供在注射-拉伸-吹塑-模制工艺中循环时间非常短的树脂。
本发明的另一个目的是提供具有优良光学特性的树脂。
本发明的进一步目的是提供具有非常高刚度的树脂。
本发明的再一个目的是提供具有优异耐化学性的树脂。
本发明的另一个目的是提供能够充满热液体的制品。
本发明的进一步目的是提供具有优良冲击和压缩特性的树脂。
本发明的另一目的是制备具有优良抗渗性(barrier property)的制品。
因此，本发明公开了用茂金属制备的聚丙烯，通过注射-拉伸-吹塑-模制，以减少的循环时间来生产单层或多层制品，所述的制品具有优异的光学特性和刚度。
本发明所使用的茂金属制备的聚丙烯优选丙烯的等规均聚体或无规共聚物。其熔体指数为2到100g/10分钟，优选10到20g/10分钟。树脂中的乙烯(ethylene)含量为0到10重量％，优选0到4重量％。
对于聚丙烯树脂，其熔体流动指数MFI采用标准测试ISO1133的过程进行测定，测试温度为230℃，载荷为2.16kg。
用于制备丙烯的等规均聚体或无规共聚物的茂金属组分，可以是本领域已知的任意桥接茂金属，其由通式I表示：
R″s(CpR′k)(C′pRk)MQ2 (I)
式中(CpR′k)为环戊二烯基或取代的环戊二烯基，各R′相同或不同且为氢或烃基，例如具有1到20个碳原子的烷基、烯基、芳基、烷芳基、或芳烷基、或两个碳原子连接在一起形成的C4-C6环，式中(C′pRk)是环戊二烯基、或茚基或芴基，均为取代或未取代的，式中R相同或不同且为氢或烃基，例如具有1到20个碳原子的烷基、烯基、芳基、烷芳基、或芳烷基，对式中Cp环上的取代基进行选择，以使得C1或C2对称于该化合物；R″是Cp和Flu环之间的结构桥以赋予立体刚度(stereorigidity)，其可以是C1-C4烯基、二烷基锗或硅或硅氧烷、或烷基膦或胺基；Q是烃基，例如具有1到20个碳原子的芳基、烷基、烯基、烷芳基或芳烷基、具有1-20个碳原子的烃氧基或卤素，且其彼此可以相同或不同，M是周期表中的IVb族金属。优选的金属是Zr、Ti、Hf。
优选的，(C′pRk)是未取代的芴基。本发明所使用的优选茂金属中，例举它们中的一个如下，异亚丙基-(3-叔-丁基-5-甲基-环戊二烯基)(芴基)二氯化锆，其用于生产丙烯的等规无规共聚物(isotactic random copolymer)。
茂金属可以使用本领域已知的任意方法进行负载。如果其被负载，本发明使用的载体可以是任意有机或无机固体，特别是多孔载体，例如滑石、无机氧化物、和树脂(resinous)载体材料，例如聚烯烃。优选的，载体材料为以其细分散形式的无机氧化物。
与载体反应并具有离子化作用的试剂添加到载体上，产生活性部位。
优选的，在聚合过程中，使用铝氧烷(alumoxane)以使催化剂离子化，本领域所已知的任意铝氧烷都是适用的。
优选的铝氧烷包括由下式表示的低聚线性和/或环状烷基铝氧烷：该式表示低聚、线性铝氧烷，
和该式表示低聚、环状铝氧烷，
式中n为1-40，优选10-20，m为3-40，优选3-20，且R为C1-C8烷基，优选甲基。
优选使用甲基铝氧烷(methylalumoxane)。
在反应器中使用一个或多个作为共催化剂的烷基铝。可以使用式AlRx所示的烷基铝，式中R相同或不同且选自卤化物或具有1到12个碳原子的烷氧基或烷基，x为1到3。尤其适宜的烷基铝是三烷基铝，最优选的是三异丁基铝(TIBAL)。
进一步的，催化剂可以在其引入反应区之前和/或在反应器内反应条件稳定之前进行预聚合。
注射-拉伸-吹塑-模制可以以两步法或以一步法进行。通常优选两步法，其在两个独立的单元(location)中进行。它包括如下步骤：
-通过在多腔模具上注射模塑形成预成型件(preform)；
-冷却该预成型件至室温；
-将该预成型件传送至吹塑机；
-在反射辐射加热炉中，在该吹塑机内重新加热该预成型件；
-将加热后的预成型件通过平衡区，以使热量均匀通过该预成型件的壁散出；
-通过中心杆轴向拉伸该预成型件；
-用高压空气对该拉伸的预成型件进行径向取向(orient)。
在该工艺中，拉伸步骤是决定性的步骤，因为其要求重新加热预成型件：从而使预成型件达到最佳。预成型件被重新加热到的温度比该树脂的熔融温度低大约10℃。
本发明所制备的制品是中空的容器和瓶子，其可用于各种食品和非食品应用。食品应用包括储存水、汁液、油、调味品(flavoured still)和充碳酸气的饮料、等渗饮料(isotonic drink)、干货(dry product)和鲜奶。非食品应用包括储存化妆品和药品、洗碗剂或洗涤剂和干货。
本发明所制备的瓶子和中空容器具有优良的光学特性和非常优良的冲击强度。其耐压强度要远远高于PET树脂制备的瓶子和由齐格勒-纳塔催化剂体系制备的常规聚丙烯树脂制备的瓶子的耐压强度。
本发明制备制品的循环时间基本低于齐格勒-纳塔(ZN)聚丙烯所必需的循环时间：其循环时间比ZN树脂的循环时间至少要少10％，优选15％。其循环时间可以与PET树脂的循环时间相比。茂金属催化剂体系的使用使得聚丙烯树脂产品具有低熔点的同时，保持良好的机械强度特性、耐压强度和冲击强度，同时光学特性也得到改善。该最终制品的刚度，与ZN制备的制品相比提高了至少3％，与PET制备的制品相比提高了至少20％。其光学特性与PET制备的制品相当，且其雾度与ZN催化体系制备的制品相比，改善了至少40％。
实施例
在实施例中采用两个预成型件样式(preform design)：
-样式1是商业聚对苯二甲酸乙二醇酯(PET)预成型件样式，其用于瓶子的制备：它重20g，如图1所示。
-样式2是Bekum PP预成型件样式，其用于瓶子的制备：它重23.8g，如图2所示。
制备三个预成型件：
-P1由商业PET树脂R1制备，采用样式1。
-P2由茂金属生产的聚丙烯树脂R2制备，采用样式2。
-P3用齐格勒-纳塔聚丙烯树脂R3制备，采用样式2。
根据本发明，树脂R2是茂金属制备的丙烯和乙烯的无规共聚物，其采用茂金属催化剂体系制备，该茂金属催化剂体系包括桥接的(3-叔-丁基-5-甲基-环戊二烯基)(芴基)二氯化锆组分和活化剂。其MFI为14g/10分钟。
树脂3是常规的商业齐格勒-纳塔丙烯无规共聚物，其MFI为10g/10分钟，其以商品名PPR7220(以前称为PPR3100MT3)进行销售。
预成型件P1来自外购。
预成型件P2和P3用Synergy 100注塑成型机制造，该注塑成型机具有100吨的合模压力和1750巴的最大注射压力。螺杆的长度L和直径D的比值L/D为20，直径D为45mm，压缩比为1∶2，其装备两个空腔模具。
用于制备预成型件P2和P3的模塑条件概括于表I中。
表I
| 单位 | P2 | P3 | ||
| 增塑 | 螺杆旋转速度 | rpm | 100 | 100 |
| 背压 | 巴 | 50 | 50 | |
| 设定熔融温度 | ℃ | 211 | 211 | |
| 定量给料时间(dosing time) | 秒 | 4.22 | 4.02 | |
| 注射 | 注射时间 | 秒 | 2.12 | 2.69 |
| 最大注射压力 | 巴 | 435 | 435 | |
| 开关(switch-over)压力 | 巴 | 426 | 426 | |
| 保持 | 衬垫 | mm | 2.6 | 3 |
| 开关点(switch-over point) | mm | 4.4 | 4.3 | |
| 保持压力 | 巴 | 359 | 359 | |
| 保持时间 | 秒 | 8.5 | 6.29 |
接着，在两腔线性注射-拉伸-吹塑-模制(ISBM)机ADS G62上，每个预成型件用于制备0.5升瓶子。
检测上述瓶子的循环时间、光学和机械特性，结果记载于表II中。
瓶子B1和B3分别由预成型件P1至P3制备，瓶子B4是商业Vittel瓶。
表II.
| 瓶子 | 循环时间(瓶/小时/空腔) | 刚度(N) | 冲击落差(m) | 光学特性(％) | 目视明晰度(visual transparency) |
| B1 | 1500 | 120 | ＞6m | 9.8 | + |
| B2 | 1375 | 165 | ＞6m | 10.3 | + |
| B3 | 1250 | 160 | ＞6m | 15.7 | - |
| B4 | n.a. | 100 | ＞6m | n.m. | + |
n.a.表示：不能提供，
n.m.表示：未检测。
用于检测刚度的压缩测试按照标准测试ASTM 2659-95的方法，在Zwich张力试验机上以10mm/分钟的速度进行。
冲击降落强度(impact drop strength)的测试按照UN标准和标准测试ASTM 2463-95，在室内通过降落测试进行。用水灌注各个瓶子的95％并调节至室温(约25℃)，放置48小时，然后底部向下从渐增的高度落下。高度逐渐增加，直到发生破裂为止。在该测试中，设备所能测试的最大降落高度为6米，在该高度未检测到任何破裂。
雾度的测试按照标准测试ISO 14782的方法，但必须注意的是瓶子样式不适合可靠记录和反复测试。相同的注释适用于光学特性，其在本实施例中是指示性的(indicative)。
Claims (10)
1.以茂金属催化剂体系生产的等规聚丙烯在制备制品中的应用，所述制品通过注射-拉伸-吹塑-模制工艺并以减少的循环时间进行制备，所述制品具备优良的光学特性和刚度，且其中该茂金属催化剂体系包括式I所示的茂金属组分：
R″s(CpR′k)(C′pRk)MQ2 (I)
式中(CpR′k)为环戊二烯基或取代的环戊二烯基，各R′相同或不同且为氢或烃基，例如具有1到20个碳原子的烷基、烯基、芳基、烷芳基、或芳烷基、或两个碳原子连接在一起形成的C4-C6环，式中(C′pRk)是取代或未取代的芴基，式中R相同或不同且为氢或烃基，例如具有1到20个碳原子的烷基、烯基、芳基、烷芳基、或芳烷基，对式中Cp环上的取代基进行选择，以使得C1或C2对称于该化合物，R″是Cp和Flu环之间的结构桥以赋予立体刚度，其可以是C1-C4烯基、二烷基锗或硅或硅氧烷、或烷基膦或胺基；Q是烃基，例如具有1到20个碳原子的芳基、烷基、烯基、烷芳基或芳烷基、具有1-20个碳原子的烃氧基或卤素，且其彼此可以相同或不同，M是周期表中的IVb族金属，优选的金属是Zr、Ti、Hf。
2.权利要求1的应用，其中该等规聚丙烯是丙烯的等规均聚物或等规无规共聚物，其熔体指数MI2为2到100g/10分钟，且乙烯的量为0到10重量％。
3.权利要求1或2的应用，其中用于制备树脂的茂金属催化剂组分为异亚丙基-(3-叔-丁基-5-甲基-环戊二烯基)(芴基)二氯化锆。
4.权利要求1-3中任一项在制备单层制品中的应用。
5.权利要求1-3中任一项在制备多层制品中的应用。
6.上述权利要求中任一项的应用，其中该最终制品具有非常优良的冲击强度。
7.上述权利要求中任一项的应用，其中该最终制品具有良好的耐化学性。
8.上述权利要求中任一项的应用，其中该最终制品具有热灌装性能。
9.上述权利要求中任一项在食品应用中的用途。
10.上述权利要求中任一项在非食品应用中的用途。
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| US7416766B2 (en) * | 2005-08-16 | 2008-08-26 | S.C. Johnson & Son, Inc. | Bottles made from metallocene polypropylene for delivery of fragrances |
| EP1767334A1 (en) * | 2005-09-22 | 2007-03-28 | Total Petrochemicals Research Feluy | Optimisation of preform preparation in injection-stretch-blow-moulding |
| WO2007046998A1 (en) * | 2005-10-14 | 2007-04-26 | Exxonmobil Chemical Patents Inc. | Methods for stretch blow molding polymeric articles |
| EP1883080B1 (en) * | 2006-07-10 | 2009-01-21 | Borealis Technology Oy | Electrical insulation film |
| EP1884539A1 (en) * | 2006-07-31 | 2008-02-06 | Total Petrochemicals Research Feluy | Polyolefin composition for injection stretch blow moulding |
| US9090000B2 (en) * | 2009-03-26 | 2015-07-28 | Fina Technology, Inc. | Injection stretch blow molded articles and random copolymers for use therein |
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| TWI511859B (zh) * | 2010-11-18 | 2015-12-11 | 道達爾石油化學產品研究弗呂公司 | 擠出吹塑製品及其生產方法 |
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| DE602004027522D1 (de) | 2010-07-15 |
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| US20070246866A1 (en) | 2007-10-25 |
| EP1533102A1 (en) | 2005-05-25 |
| EP1682329B1 (en) | 2010-06-02 |
| DK1682329T3 (da) | 2010-08-30 |
| ATE469750T1 (de) | 2010-06-15 |
| JP2007511630A (ja) | 2007-05-10 |
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