CN107548512B - 聚丙烯膜结构 - Google Patents
聚丙烯膜结构 Download PDFInfo
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- CN107548512B CN107548512B CN201680023072.5A CN201680023072A CN107548512B CN 107548512 B CN107548512 B CN 107548512B CN 201680023072 A CN201680023072 A CN 201680023072A CN 107548512 B CN107548512 B CN 107548512B
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Classifications
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明为包含具有包含丙烯均聚物且与油接触的层的双轴取向膜的结构，特征在于，丙烯均聚物具有从95％到98％的等规立构五单元组含量和不超过30ppm的灰分含量。
Description
技术领域
本发明涉及包含油和双轴取向聚丙烯膜的结构。特别地，本发明涉及具有BOPP膜和铝箔的平卷绕(flat winding)，而该组合被油浸渍的结构。特别地，本发明涉及包括这种结构的电容器。
背景技术
制造电容器的一种方法是将双轴取向PP(BOPP)膜与铝箔一起卷绕。目前，双轴拉伸聚丙烯膜(以下简称为BOPP膜)由于它们优异的电性能主要用作在600V以上的电压下操作的电力电容器的电介质片材。这种类型的电力电容器通常具有几个至几十个单位电容器元件的带束式组件的结构，每个单元电容器元件均为通过轧制由OPP膜和铝箔组成的双层而制备的扁平轧制体的形式。在气密密封之前，将这种单元电容器的带束式组件在金属壳体中以油来浸渍。
EP-A-885918公开了具有99％以上的等规立构五单元组级分和30ppm以下的灰分含量的BOPP的油浸渍膜。
高等规立构级分通常导致加工性问题，例如在纵向上的膜取向期间频繁的膜断裂，更具体的是在横向上在拉幅机烘箱中的膜断裂，或者在双气泡膜技术中太多的泡沫破裂。
此外，等规立构材料的高含量通常具有在膜处理期间该材料更易于降解的结果。不幸的是，已经发现对于普通BOPP膜有效的许多稳定剂和稳定剂组合在油浸渍膜中会出现问题。
次级抗氧化剂，如三(2,4-二叔丁基苯基)亚磷酸酯会增加对电容器有害的消耗。
此外，某些初级抗氧化剂从BOPP膜迁移到油中，从而使油劣化。特别是如果油中含有芳烃类，诸如苄基甲苯衍生物，则更是如此。
因此，本发明的目的是制备与油接触的双轴取向膜，其由具有高结晶度和良好加工性的组合的聚丙烯制成，并且在挤出和膜加工过程中不会降解。此外，包含这种膜和油的电容器具有长工作寿命，并且膜的组分具有减少的向油中迁移的倾向。因此，这些膜可以在多种油的组合中使用。这些薄膜特别用于含有芳烃类，特别是环状芳烃类(诸如甲苯衍生物)的油的组合。
发明内容
从一个方面可以看出，本发明提供了一种包含具有与油接触的包含丙烯均聚物的层的膜的结构，其特征在于，丙烯均聚物具有从95％到98％的等规立构五单元组的含量和不超过30ppm的灰分含量。
具体实施方式
丙烯均聚物
丙烯均聚物通过在聚合催化剂存在下聚合丙烯来制备。聚合催化剂通常包含固体组分，该固体组分包含卤化钛，诸如三氯化钛，其与烷基铝形成催化剂。丙烯均聚物因此通过在60至90℃的温度和5至100巴的压力下使丙烯、聚合催化剂和诸如氢的链转移剂，任选地在惰性稀释剂中接触而制备。
丙烯均聚物具有高结晶度。因此，其具有95至98％、优选为95.5至98％、特别优选为96至97.5％的等规立构五单元组级分的含量。如果等规立构五单元组的含量小于95％，则膜的最终结晶度相当低，并且膜的拉伸性能和模量降低，特别是在双气泡技术上制备的BOPP膜。另一方面，如果等规立构五单元组的含量大于98％，则一方面在纵向上存在膜取向期间频繁的膜断裂，并且另一方面更具体的是在横向上在拉幅机烘箱中存在膜断裂，或者在双气泡膜技术中太多的泡沫破裂。等规立构五单元组级分的含量通常由用于制备丙烯均聚物的聚合催化剂来确定。合适的催化剂是例如在US-A-4534953和EP-A-99026中公开的催化剂。此外，通过使用合适的给体(内部或外部电子给体)来影响等规立构材料的分数是已知的。内部给体是固体催化剂组分的一部分。合适的内部给体的示例包括醚类、酮类、酯类及其组合。外部给体通常与烷基铝接触，其中两种组合形成助催化剂。合适的外部给体包括醚类、酯类、硅醚类、胺类及其组合。
此外，丙烯均聚物具有不大于30ppm、优选不大于20ppm、特别是不大于15ppm的灰分含量。低灰分含量是必要的，因为膜中的金属杂质会导致击穿电压的降低。
典型地，低灰分含量可以通过使用具有足够高活性的催化剂来获得，使得催化剂残余物保持在低水平上。可选地，可使用具有小金属含量的催化剂。可选地，聚合物可以进行一个或多个洗涤步骤，其中催化剂残余物被溶解并从聚合物中除去。
可用于制备丙烯均聚物的合适的催化剂包括基于包含三氯化钛的固体组分的催化剂，该固体组分任选地含有作为内部给体的醚或酯；基于包含负载在二氯化镁上的四氯化钛的固体组分的催化剂，该固体组分含有作为内部给体的醚或酯；基于包含四氯化钛的固体组分的催化剂，其通过使包含四氯化钛和二氯化镁的液滴的乳液固化来制备，并且该固体组分包含作为内部给体的醚或酯；和基于包含四氯化钛的固体组分的催化剂，其通过从溶液中同时沉淀四氯化钛和二氯化镁来制备，并且该固体组分包含作为内部给体的醚或酯。这些固体组分与诸如三乙基铝或二乙基氯化铝的烷基铝化合物或与烷基铝化合物的混合物一起使用，任选与外部给体进行组合。特别优选的是固体组分包含电子给体。当使用这种催化剂时，丙烯均聚物已被发现在规定的限制内。
在EP-A-2543684中公开了适于制备本发明的膜的、在制备丙烯均聚物中特别有效的方法，其中基于包含三氯化钛的固体组分的催化剂与烷基铝、有机醚和甲基丙烯酸烷基酯结合使用。
聚合方便地在淤浆中进行。在这种方法中，催化剂、氢气和丙烯单体在基本上包含一种或多种具有4至15个碳原子、优选为10至14个碳原子的烷烃的稀释剂中接触。“基本上包含”是指稀释剂包含至少90重量％、优选至少95重量％、更优选至少99重量％的一种或多种这样的烷烃。
聚合通常在50至100℃，优选在60至80℃的温度和1至50巴、优选为3至15巴的压力下进行。
优选地，该方法包括一个或多个洗涤步骤。洗涤通常通过使聚合物浆料与烃稀释剂在一个或多个步骤中接触来进行。优选地，聚合物浆料在至少两个步骤中与烃稀释剂接触。当洗涤包括多个步骤时，那么优选的是在至少一个步骤中除了烃稀释剂之外还存在醇或醚。这有助于从聚合物中除去催化剂组分，从而可以获得具有非常低的灰分含量的聚合物。
添加剂
本发明中使用的添加剂优选选自由成核剂、抗氧化剂、除酸剂和稳定剂组成的组。在下文中，抗氧化剂和稳定剂通常称为稳定剂。
根据本发明的丙烯均聚物具有比常规使用的丙烯均聚物更高的等规度。因此，通常在油浸渍膜中使用90至94％的等规度的聚丙烯。然而，已经发现的是，当在油浸渍膜的应用中使用具有95至98％的等规度的丙烯均聚物时，聚合物比具有90至94％的等规度的常规丙烯均聚物更容易降解。因此，聚合物需要更有效的稳定化。
另一个问题是，一些稳定剂倾向于溶解到油中，从而从聚合物迁移到油中。这一方面使油劣化，另一方面使聚合物没有足够的稳定性。因此，优选的是具有稳定剂或稳定剂的组合，从而不具有上述的缺点并且不会不利地影响膜的电性能。
用于本发明的抗氧化剂和稳定剂优选地选自由1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、丁基羟基甲苯和其混合物组成的组。
1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯优选地以基于丙烯均聚物的重量的500至2000ppm的量存在。更优选地，1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯以基于丙烯均聚物的重量的600至1700ppm、特别是600至1500ppm的量存在。1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯可在Irganox 1330、Anox 330、Ethanox 330和Kinox30的商品名下购得。
基于丙烯均聚物的重量，丁基羟基甲苯(BHT)优选地以100至1000ppm的量存在。更优选地，基于丙烯均聚物的重量，丁基羟基甲苯(BHT)以200至900ppm、特别是300至800ppm的量存在。丁基羟基甲苯可在Ionol CP和Vulkanox BHT的商品名下购得。
已经发现，目前BHT作为工艺稳定剂。它可以防止聚合物在挤出过程中降解。因此，从膜测量的聚合物的MFR大体上不大于从颗粒测量的聚合物的MFR。
特别地，抗氧化剂和稳定剂不优选含有含磷的次级抗氧化剂，诸如三(2,4-二叔丁基苯基)亚磷酸酯，因为这样的化合物会增加最终电容器的消耗。
此外，抗氧化剂和稳定剂不优选含有季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)，因为该化合物倾向于从膜迁移到油中。这会导致油的劣化。
成核剂通常选自由一元羧酸和多元羧酸的盐，诸如苯甲酸钠；山梨糖醇化合物，诸如山梨糖醇或木糖醇的二缩醛；诺尼醇(nonitol)基成核剂；磷基化合物，诸如单-、双-或四-苯基磷酸酯；受阻苯胺类，诸如受阻苯基丙酰胺类；滑石；聚合物成核剂，诸如乙烯基环己烷和4-甲基-1-丁烯的均聚物；和两种以上的上述化合物的混合物组成的组。
除酸剂通常是有机酸的盐类，诸如硬脂酸盐类。它们具有中和聚合物中的酸的功能。这些化合物的示例为硬脂酸钙、硬脂酸锌和氧化锌。
其它组分
膜可以含有优选不超过10重量％、更优选不超过5重量％的量的其它聚合物组分。这样的其它聚合物组分可以是其它的丙烯的均聚物或共聚物，乙烯的均聚物或共聚物等。如果存在另外的聚合物组分，它们优选是丙烯的其它均聚物或共聚物，更优选为丙烯均聚物。这样的聚合物可以是例如添加剂母料的载体聚合物等。
其它合适的聚合物组分是长链支化聚丙烯(诸如在EP-A-792894和US-A-6077907中所公开的)、聚乙烯基环己烷、聚-4-甲基-1-丁烯等。这些聚合物通常以不大于5重量％的量存在，更优选以不大于3重量％的量存在。
BOPP膜
双轴取向聚丙烯膜是以本领域已知的任何合适方法由丙烯均聚物制成的。
根据一种合适的方法，将薄膜通过平模头挤出。将挤出物在冷却辊中冷却，使得膜固化。然后通过将膜通过加热辊将温度调节至145至150℃。当膜具有所需的温度时，其通过一组或多组拉伸辊，使得最终拉伸比为4:1至6:1。
之后，将膜传送至一系列退火辊，其中其加热到膜在纵向不收缩的温度。然后将该膜传送至含有夹在膜上的夹子的链条处。将膜加热至160℃，之后链条发散到8:1至10:1的比例(最终宽度：原始宽度)。然后膜在155℃下退火以减少收缩。之后，边缘被修剪掉并且膜被切开和卷绕。
根据可选择的方法，取向线通过所谓的“双气泡法”进行，即聚合物通过圆形模头挤出，并立即在内部冷却心轴上淬火，从而形成厚的主管，然后将主管重新加热至适合的温度，诸如155至160℃，并进行吹塑以形成主要的薄膜的气泡。
由于在启动阶段以空气膨胀，实现了非接触式同步取向。该空气允许横向取向，同时由于拉伸压料辊和塔压料辊之间的速度差异同时进行纵向取向。
气泡被空气冷却，然后变平；在修剪边缘之后，所获得的两个网在两个卷轴中卷起。
电容器
这种类型的电容器通常具有几个至几十个单位电容器元件的带束式组件的结构，每个单元电容器元件均为通过轧制由OPP膜和铝箔组成的双层而制备的扁平轧制体的形式。这种单元电容器的带束式组件在气密密封之前在金属壳体中以油来浸渍。
在结构中使用的合适的油包括矿物油、合成烃油、植物油和硅油。
一组油是那些含有至少20重量％、优选至少50重量％的量的芳烃、优选环状芳烃(诸如甲苯衍生物)的油。这些油由于其出色的耐热老化性通常用于电容器。它们尤其可以在Arkema的JarylecTM的商品名下购得。
根据本发明的结构适用于例如高压功率因数校正。
本发明的益处
包括根据本发明的结构的电容器具有良好的耐热性，并且它们具有良好的电性能。特别是它们的介电性能可长时间保持。此外，可以在高达约105℃的温度使用电容器。此外，膜的组分不会在任何种类的油中迁移，特别是，它们不会迁移至含有至少20重量％的量的环状芳烃的油中。
方法描述
通过NMR光谱对微观结构进行定量化
采用定量核磁共振(NMR)光谱来对丙烯均聚物的等规度和区域规整度进行定量。
采用对1H和13C分别以400.15和100.62兆赫下操作的Bruker Advance III 400NMR光谱仪在溶液状态中记录定量的13C{1H}NMR光谱。对所有气动装置使用氮气，在125℃下采用13C优化的10mm延长温度探头记录所有光谱。
对丙烯均聚物，将约200mg的材料溶解在1,2-四氯乙烷-d2(TCE-d2)中。为了确保均匀的溶液，在加热块中制备初始样品后，将NMR管在旋转炉中进一步加热至少1小时。***磁体时，以10Hz旋转该管。选择该设置主要是为了定量等规度分布所需的高分辨率(BusicoV.,Cipullo R.,Prog.Polym.Sci.26(2001)443；Busico V.；Cipullo R.,Monaco G.,Vacatello M.,Segre A.L.,Macromolecules 30(1997)6251)。利用NOE和双水平WALTZ16解耦算法(Zhou Z.,Kuemmerle R.,Qiu X.,Redwine D.,Cong R.,Taha A.,Baugh D.,Winniford15B.,J.Mag.Reson.187(2007)225；Busico V.,Carbonniere P.,Cipullo R.,Pellecchia R.,Severn J.,Talarico G.,Macromol.Rapid Commun.2007,28,11289)采用了标准单脉冲激发。每个光谱获取共8192(8k)瞬变值。
对定量的13C{1H}NMR光谱进行处理、积分，并且使用专有的计算机程序从积分来确定相关定量性能。
对丙烯均聚物，所有化学位移都是以21.85ppm处的甲基等规立构的五单元组(mmmm)作为内部参考的。
观察到对应于区域缺陷(Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253；Wang,W-J.,Zhu,S.,Macromolecules 33(2000),1157；Cheng,H.N.,Macromolecules17(1984),1950)或共聚单体的特征信号。
等规度分布是通过对校正了与所关注的立体序列不相关的任何位点的在23.6-19.7ppm之间的甲基区域求积分而被定量化的(Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443；Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L.,Macromolecules 30(1997)6251)。
五单元组等规度表示等规立构的五单元组(mmmm)的分数。
流变能力
通过Rheometrics RDA-II QC在230℃、氮气气氛下使用25mm直径的板和板状几何结构对压缩成型样品进行动态流变测试。在0.015至300rad/s的频率下在应变的线性粘弹性范围内完成振荡剪切实验(ISO 6721-10)。
储能模量(G’)、损耗模量(G”)、复数模量(G*)和复数粘度(η*)的值作为频率(ω)的函数被得到。
采用定义为复合粘度的倒数的复合流动性计算零切粘度(η0)。其实部和虚部由此定义为
f’(ω)＝η’(ω)/[η’(ω)2+η”(ω)2]和
f”(ω)＝η”(ω)/[η’(ω)2+η”(ω)2]
从下面等式
η’＝G”/ω和η”＝G’/ω
f’(ω)＝G”(ω)·ω/[G’(ω)2+G”(ω)2]
f”(ω)＝G’(ω)·ω/[G’(ω)2+G”(ω)2]
复数粘度比eta*(0.05rad/sec)/eta*(300rad/sec)，也为剪切稀化指数是0.05rad/sec下的复数粘度(η*)与300rad/sec下的复数粘度(η*)的比值。
多分散指数，PI，PI＝105/Gc，是由G’(ω)和G”(ω)的交叉点计算的，对于该交叉点适用G’(ωc)＝G”(ωc)＝Gc。
熔体流动速率
熔体流动速率(MFR，MFR2)是根据ISO 1133在230℃、2.16kg的负荷下测定的。
膜的熔融温度和结晶度
用TA Instrument Q200差示扫描量热法(DSC)在约5至7mg的膜样品上测量熔融温度。DSC在-30℃至+225℃的温度范围内以10℃/分钟的扫描速率在加热/冷却/加热循环中根据ISO 11357/部分3/方法C2运行。通过将测得的熔融焓(J/g)除以100％结晶聚丙烯的熔融焓(209J/g)获得结晶度。
黄度指数
黄度指数根据ASTM E-313测定。
灰分含量
通过在称重的铂坩埚中燃烧聚合物来测定聚合物的灰分含量。将约100克聚合物称重到坩埚中。然后将坩埚在本生灯火焰中加热，使聚合物慢慢燃烧。聚合物完全燃烧后，将坩埚冷却、干燥并称重。然后，灰分含量是残余物的重量除以聚合物样品的重量。进行至少两次测量，如果测量值之间的差大于7ppm，则进行第三次测量。
实施例
实施例1
对于丙烯的聚合采用根据EP-A-2543684的发明实施例1的聚合方法。将氢和丙烯进料至反应器中，使得在每个聚合反应器中制备具有约3.4g/10min的MFR2的丙烯均聚物。向聚合物中加入1000ppm的量的Irganox 1330和750ppm的量的BHT。丙烯均聚物具有5.5Pa-1的多分散指数，14的剪切稀化指数，8ppm的灰分含量和96.2％的五单元组等规度。
将如上所述的丙烯均聚物挤出成膜，然后逐步双轴取向，得到的膜具有11μm的厚度。该膜具有167℃的熔融温度和44.6％的结晶度。
实施例2
使用Irganox 1010替代Irganox 1330，并且不使用BHT，除此之外按实施例1的步骤进行。丙烯均聚物具有5.5Pa-1的多分散指数，14的剪切稀化指数，8ppm的灰分含量和96.2％的五单元组等规度。
对比例1
聚合方法按照EP-A-2543684的对比例1进行和使用Irganox 1010替代Irganox1330并且不使用BHT，除此之外按照实施例1的步骤进行。丙烯均聚物具有4.5Pa-1的多分散指数，10的剪切稀化指数，9ppm的灰分含量和92.2％的五单元组等规度。
将如上所述的丙烯均聚物挤出成膜，然后逐步双轴取向，得到的膜具有11μm的厚度。该膜具有166℃的熔融温度和42.6％的结晶度。
从实施例1和对比例1可以看出，实施例1的膜比对比例1的膜具有更高的结晶度和熔融温度。
通过对聚合物进行多次挤出试验来评价实施例1和对比例1的聚合物的稳定性。测量聚合物的黄度指数。
表1：多次挤出后的实施例1和2和对比例1的聚合物的黄度指数
| 挤出次数 | E1 | E2 | CE1 |
| 1 | 0.8 | 2.5 | 1.2 |
| 2 | 2.3 | 5.2 | 2.8 |
| 3 | 3.0 | 6.6 | 3.3 |
| 4 | 4.1 | 8.3 | 4.8 |
| 5 | 4.8 | 9.0 | 4.8 |
数据表明，实施例1和对比例1的聚合物具有相同的抗降解性。
实施例3
将实施例1的膜的样品在80℃下在Jarylec C101油中浸渍100天。当分析油时，没有发现Irganox 1330或BHT。
对比例2
用对比例1的膜重复实施例3的步骤。当分析油时，发现含有从膜中迁移到油中的Irganox 1010。
实施例4
为了进一步说明稳定化效果，将根据实施例1的方法制备的但是将MFR2调节至2.8g/10min的聚合物粉末与1000ppm的量的Irganox 1330和750ppm的量的BHT混合。将聚合物挤出成颗粒。测定颗粒的MFR2，且结果为3.3g/10min。
将另一批相同的聚合物仅与1000ppm的量的Irganox 1330混合。测量颗粒的MFR2，且结果为4.8g/10min。
Claims (11)
1.一种结构，包含具有与油接触的包含丙烯均聚物的层的双轴取向膜，其特征在于，所述丙烯均聚物具有从95％到98％的等规立构五单元组含量和不超过30ppm的灰分含量，其中
所述双轴取向膜包含600至5000ppm的选自由稳定剂、除酸剂和成核剂组成的组的添加剂，和
所述稳定剂选自由均基于所述丙烯均聚物的量的500至2000ppm的量的1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、100至1000ppm的量的丁基羟基甲苯和其混合物组成的组。
2.根据权利要求1所述的结构，其中所述油包含至少20重量％的芳烃。
3.根据权利要求2所述的结构，其中所述油包含环状芳烃。
4.根据权利要求3所述的结构，其中所述油包含至少50重量％的环状芳烃。
5.根据权利要求3或4所述的结构，其中所述环状芳烃为甲苯衍生物。
6.包含具有95至98％的等规立构五单元组含量和不超过30ppm的灰分含量的丙烯均聚物的双轴取向膜用于制备包含所述双轴取向膜和油的电容器的用途，其中
所述膜包含600至5000ppm的选自由稳定剂、除酸剂和成核剂组成的组的添加剂，和
所述稳定剂选自由均基于所述丙烯均聚物的量的500至2000ppm的量的1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、100至1000ppm的量的丁基羟基甲苯和其混合物组成的组。
7.根据权利要求6所述的用途，包括将所述膜和铝箔平卷绕以获得卷绕结构，并用油浸渍所述卷绕结构的步骤。
8.根据权利要求6所述的用途，其中所述油包含至少20重量％的芳烃。
9.根据权利要求8所述的用途，其中所述油包含环状芳烃。
10.根据权利要求9所述的用途，其中所述油包含至少50重量％的环状芳烃。
11.根据权利要求9或10所述的用途，其中所述环状芳烃为甲苯衍生物。
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