CN101014631A - 聚乙烯树脂的氧气修整 - Google Patents
聚乙烯树脂的氧气修整 Download PDFInfo
- Publication number
- CN101014631A CN101014631A CNA200580027836XA CN200580027836A CN101014631A CN 101014631 A CN101014631 A CN 101014631A CN A200580027836X A CNA200580027836X A CN A200580027836XA CN 200580027836 A CN200580027836 A CN 200580027836A CN 101014631 A CN101014631 A CN 101014631A
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- China
- Prior art keywords
- oxygen
- polyethylene
- resin
- melt conveying
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000001301 oxygen Substances 0.000 title claims abstract description 110
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 110
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- 229920013716 polyethylene resin Polymers 0.000 title description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
本发明提供了使用0.5-7.95vol%的含氧气体对聚乙烯进行修整的方法。修整发生在混合机/挤出机的熔体输送区,而不是在混合机/挤出机的进料区或熔融区。修整的效果是,与在基本上不存在氧气或含氧气体的条件下挤出/混合的类似聚乙烯相比,聚合物的弹性(G’/G”)提高超过10%。
Description
技术领域
本发明的实施方式提供了一种方法,该方法在粒化过程中有意识地改进聚乙烯的流变性的方法,从而改善最终产品的性质,例如对于聚乙烯薄膜应用的膜泡稳定性和厚度均匀性以及对于吹塑和管材应用的胀大和熔塌。
背景技术
修整树脂(例如聚乙烯均聚物或共聚物树脂)是改变分子构造从而改变树脂和由其制成的制品的本体性质的公知方法。修整涉及用能受控地改进树脂的试剂(例如过氧化物或氧气)来处理聚乙烯树脂。与未修整的粒状产品相比,对聚乙烯树脂流变性质进行修整的效果通常体现在已修整颗粒的零剪切粘度增加、弹性(G’/G”)增加和剪切变稀性增加。通过减小吹塑过程中的胀大、减小管材挤出过程中的熔塌、提高膜泡稳定性以及减小薄膜转化过程中的厚度差异,这些变化对将聚乙烯颗粒转化为最终有用制品的过程有利。
在许多应用中,具有多峰分子量分布和/或多峰组成分布的聚烯烃树脂是人们所期望的。多峰聚乙烯包含两个或多个分子量组分或组成分布。包含两个组分的多峰树脂有时被称为双峰树脂。这样的聚烯烃树脂通常至少包括较高分子量聚烯烃与较低分子量聚烯烃的混合物。这样的聚烯烃树脂可以被生产来利用较高分子量树脂和由其制成的制品和薄膜的提高的强度性质以及较低分子量树脂的更好的加工性质。
可以在串联的反应器,例如串联的气相反应器或串联的淤浆反应器中生产多峰树脂。或者,也可以用例如公开在美国专利No.5032562和5525678和欧洲专利EP 0729387中的双金属催化剂在单一反应器中生产多峰聚烯烃树脂。这些催化剂通常包括产生不同平均分子量聚烯烃的非茂金属催化剂组分和茂金属催化剂组分。例如美国专利No.5525678在一种实施方式中公开了一种双金属催化剂,包括产生较高分子量树脂的钛非茂金属组分和产生较低分子量树脂的锆茂金属组分。通过控制反应器内各催化剂的相对量或不同催化剂的相对反应性,可以控制所述多峰产品树脂。
多峰聚乙烯树脂特别适合用在薄膜中。但通常,中密度聚乙烯(MDPE)树脂和高密度聚乙烯(HDPE)树脂的膜泡稳定性和厚度均匀性对于生产薄膜是不足的。已试图修整聚乙烯树脂以改善膜泡稳定性、厚度均匀性和/或以其它方式改善树脂或薄膜性质;参见例如欧洲专利公布EP0457441和美国专利No.5728335、5739266和6147167。其它背景参考文献包括FR 2251576、EP 0180444、美国专利No.5578682、EP 0728796和GB 1201060。
WO 03/047839提出用氧气修整来提高剪切变稀性、增大弹性、提高熔体张力、减少吹塑过程中的胀大和提高薄膜吹塑过程中的膜泡稳定性。该文献提出在挤出机的熔体输送段使用8-40vol%的氧气来实现此目的。该文献并没有建议用较少量的氧气来达到这样的结果。
美国专利No.5739266中提出通过使聚乙烯与氧气或包含氧气的气体混合物接触而在挤出机中对聚乙烯进行改性。该文献提出聚合物在其熔融之前与氧气接触,该文献进一步提出,在聚合物完全熔融之前进行氧气接触。此外,该文献提出,聚合物-氧气接触可以发生在挤出机的任何部分,除了挤出段或熔体输送段。该文献提出的气体混合物包含1-50vol%的氧气(在挤出机的料斗的气氛中测量)。
商业上希望得到修整聚乙烯特别是聚乙烯薄膜树脂的改进方法,以提供在将这种树脂加工成薄膜时膜泡稳定性和厚度均匀性改善的树脂。
发明概述
一种实施方式提供了挤出/造粒聚乙烯的方法,所述方法包括:a)向混合机/挤出机提供聚乙烯;b)将所述聚乙烯输送通过混合机/挤出机,所述混合机/挤出机包括熔体输送区,其中在所述熔体传输区,所述聚乙烯被基本上熔融;c)使基本上熔融的聚乙烯与包含0.5-7.9vol%的氧气的气体混合物接触,以制备经氧气处理的聚乙烯,其中所述接触发生在所述熔体传输区。
另一种实施方式提供了制备用于吹塑薄膜的聚乙烯的方法,该树脂在吹塑薄膜挤出过程中具有改善的膜泡稳定性,所述方法包括:a)将粒状聚乙烯均聚物或共聚物引入混合机/挤出机;b)将所述粒状聚乙烯输送通过混合机/挤出机的进料区、和/或熔融区和熔体输送区;c)将气体混合物引入所述熔体输送区,所述熔体输送区包含气体混合物,所述聚乙烯均聚物或共聚物基本上熔融,所述气体混合物包含2.5-4.5vol%的氧气,所述气体混合物的剩余组分包含非反应性气体或非反应性气体的混合物,所述气体混合物在所述熔体输送区中在与所述基本上熔融的聚乙烯均聚物或共聚物的相同方向或相反方向上流动,以形成经氧气处理的聚乙烯均聚物或共聚物;d)通过以下进一步的操作加工所述经氧气处理的聚乙烯均聚物或共聚物:i)造粒;或ii)形成薄膜;或iii)造粒和形成薄膜,其中所述聚乙烯均聚物或共聚物具有0.930-0.970g/cm3的密度,并且具有比在基本上不存在氧气的条件下混合/挤出的相似的聚乙烯均聚物或共聚物高至少30%的弹性(G’/G”)。
本发明还提供了制备在吹塑薄膜制备过程中具有改善的膜泡稳定性和厚度均匀性的聚乙烯的方法,所述方法包括:a)将粒状聚乙烯均聚物或共聚物引入混合机/挤出机;b)将所述粒状聚乙烯输送通过挤出机的进料区、和/或熔融区和熔体输送区;c)将气体混合物引入所述熔体输送区,所述熔体输送区基本上由挤出机螺杆元件和机筒组成,所述气体混合物和所述聚乙烯均聚物或共聚物基本上熔融;所述气体混合物包含3-4vol%的氧气,所述气体混合物的剩余组分包含非反应性气体或非反应性气体的混合物,所述气体混合物在所述熔体输送区中在与所述基本上熔融的聚乙烯均聚物或共聚物的相同方向或相反方向上流动,以形成经氧气处理的聚乙烯均聚物或共聚物;d)通过以下进一步的操作加工所述经氧气处理的聚乙烯均聚物或共聚物:i)造粒;或ii)形成薄膜;或iii)造粒和形成薄膜,其中所述聚乙烯均聚物或共聚物具有0.930-0.970g/cm3的密度,并且具有比在基本上不存在氧气的条件下混合/挤出的相似的聚乙烯均聚物或共聚物高至少40%的弹性(G’/G”)。
本发明还提供了修整聚乙烯的方法,所述方法包括:a)将粒状聚乙烯引入混合机/挤出机;b)将所述粒状聚乙烯输送通过混合机/挤出机的进料区、和/或熔融区和熔体输送区,其中所述进料区和所述熔融区基本上不含氧气;c)将气体混合物引入所述熔体输送区,所述熔体输送区包含所述气体混合物和基本上熔融的所述聚乙烯;所述气体混合物包含3-4vol%的氧气,所述气体混合物的剩余组分包含非反应性气体或非反应性气体的混合物,所述气体混合物在所述熔体输送区中在与所述基本上熔融的均聚物或共聚物的相同方向或相反方向上流动,以形成经氧气处理的聚乙烯均聚物或共聚物;d)通过以下进一步的操作加工所述经氧气处理的聚乙烯:i)造粒;或ii)形成薄膜;或iii)造粒和形成薄膜;其中所述聚乙烯均聚物或共聚物具有0.930-0.970g/cm3的密度,并且具有比在基本上不存在氧气的条件下混合/挤出的相似的聚乙烯均聚物或共聚物高至少40%的弹性(G’/G”)。
附图说明
图1为Kobe混合机的示意图;
图2为Farrel混合机的示意图;
图3为Werner-Pfleiderer混合机-挤出机的示意图。
发明详述
聚乙烯树脂
在本发明的实施方式中,待修整的聚乙烯树脂可以包括密度为0.900-0.970g/cm3的聚乙烯,包括密度为0.900-0.912g/cm3的极低密度聚乙烯、密度为0.912-0.930g/cm3的线性低密度聚乙烯、密度通常为0.930-0.945g/cm3的中密度聚乙烯(MDPE)或密度大于0.945g/cm3且高达0.970g/cm3的高密度聚乙烯(HDPE)。所述聚乙烯可以为均聚物或共聚物,本文所用术语“共聚物”的范围还包括多于两种共聚单体的聚合物,例如三元聚合物。合适的共聚单体包括α-烯烃,例如C3-C20α-烯烃或C3-C12α-烯烃。所述α-烯烃共聚单体可以是线性或支化的,如果需要可使用两种或多种共聚单体。合适的共聚单体的例子包括线性C3-C12α-烯烃和具有一个或多个C1-C3烷基支链或芳基的α-烯烃。具体例子包括丙烯;3-甲基-1-丁烯;3,3-二甲基-1-丁烯;1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-己烯;具有一个或多个甲基、乙基或丙基取代基的1-庚烯;具有一个或多个甲基、乙基或丙基取代基的1-辛烯;具有一个或多个甲基、乙基或丙基取代基的1-壬烯;乙基、甲基或二甲基取代的1-癸烯;1-十二碳烯和苯乙烯。应当理解,以上所列共聚单体仅为举例而无意于进行限制。
在另一实施方式中,所述聚乙烯树脂具有多峰或单峰分子量分布和/或多峰或单峰组成分布。所述树脂可用任何能制备多峰树脂的催化剂以常规方法制备,例如用单一或串联的气相流化床反应器、或单一或串联的淤浆环管或超临界环管反应器制备。所用催化剂无特殊限制,可包括例如一种或多种Ziegler-Natta催化剂和/或一种或多种茂金属催化剂。还可使用催化剂的混合物。特别地,可在单一反应器内存在两种或多种不同催化剂并且同时活性聚合的条件下进行聚合。所述两种或多种催化剂可以是不同的催化剂类型的,例如非茂金属催化剂和茂金属催化剂,以制备具有所需性质的聚乙烯树脂。催化剂可以分别地、或作为物理混合物被进料至反应器,或每个催化剂颗粒可包含不止一种催化剂化合物。当催化剂包含两种制备不同分子量和/或不同共聚单体含量的聚合物的催化剂时,聚合物产品的分子量、共聚单体或二者可具有多峰分布。这样的多峰产品的物理性质不同于可由单一催化剂得到的或通过将每一催化剂单独获得的各单峰树脂随后在反应器混合而得到的产品的物理性质。
例如,美国专利No.5525678公开了一种催化剂,包括产生较低分子量、高共聚单体含量的聚合物的锆茂金属和产生较高分子量、低共聚单体含量的聚合物的钛非茂金属。通常,乙烯是主要单体,加入少量己烯或其它α-烯烃以降低聚乙烯的密度。所述锆催化剂结合大部分共聚单体和氢,以致在一种典型的实施例中约85%的己烯和92%的氢在低分子量聚合物中。添加水,以通过控制所述锆催化剂的活性来控制总分子量。
合适的催化剂的其它例子包括美国专利No.4554265中公开的Zr/Ti催化剂;美国专利No.5155079和5198399中公开的混合铬催化剂;美国专利No.5395540和5405817中公开的Zr/V和Ti/V催化剂;美国专利No.6271323中公开的铪/大配体茂金属混合催化剂;和美国专利No.6207606中公开的混合茂金属催化剂。
还想到了至少两种聚乙烯的物理混合物,其中每种可以在一个或多个反应器中制备,当混合在一起时,其具有多峰分子量分布和/或多峰组成分布。
多峰树脂可以包含任意数量的组分。通常,多峰树脂包含至少熔融指数I2为100-9000dg/min的组分(称为低分子量组分(LMW))和至少一种流动指数I21.6为0.1-1dg/min的组分(称为高分子量组分(HMW)。多峰树脂包含至少两种组分,其中,HMW与LMW组分的相对重量分数可为1∶9-9∶1。典型的双峰树脂的HMW重量分数为45-70%(其余为LMW重量分数),流动指数(I21.6)为5-15dg/min。
我们还想到了单峰分子量分布和/或单峰组成分布的聚乙烯树脂,以及多峰(双峰或更多峰)分子量分布和/或多峰(双峰或更多峰)组成分布。
本文讨论的任何聚乙烯树脂可以是一种催化剂或聚烯烃催化剂的任意组合的产物。催化剂类型包括部分地由元素周期表中的III、IV、V、VI、VII、VIII、IX、X、XI和XII族的元素组成的任何一种或多种过渡金属催化剂。这些催化剂的例子包括基于锆和铪的茂金属催化剂以及基于镁、铬、钛和钒的常规催化剂。
混合机-挤出机
可以在混合机,例如同向旋转或反向旋转、啮合或非啮合双螺杆混合机或挤出机中加工所述聚乙烯树脂。此类混合机为本领域公知,可从诸如Coperion(Werner-Pfleiderer)、Kobelco和Farrel之类的各种来源商购。通常利用料斗将树脂进料至混合机的进料区,此区中的温度通常低于树脂被压缩和输送至熔融区时的树脂熔融温度。通常,进料区中的温度为20-100℃,并可以通过冷却挤出机壁来保持。在熔融区中,温度升高以使树脂至少部分熔融,通常在此区中,树脂基本上全部熔融。在熔体输送区中,温度足以保持全部熔融树脂保持该状态。这里的“基本上全部”意指大于95wt%,或大于97wt%,或大于99wt%,或100%的聚乙烯被熔融。可以用树脂仅将各个区部分地填充;“部分地填充”意指用树脂和任何添加剂将区体积的10-99%填充。尽管术语“混合机”和“挤出机”通常不严格地可互换使用,但本领域的技术人员应理解混合机(如商购Kobe或Farrel混合机)在较低压力(通常约100psi或更低)下操作,并且混合机内各区通常并不完全充满树脂。在挤出机(例如从Werner-Pfleiderer商购的)中,至少有些区可在较高压力下操作,这依赖于该区的标准螺杆/机筒设计和该区被树脂和/或树脂与添加剂填充的百分比,挤出机内的某些区通常完全充满树脂,这样的区通常在较高压力下操作。
虽然不限于任何具体挤出机,但现在参考示出Kobe混合机10的示意图的图1来说明本发明的方法的一种实施方式。混合机10包括进料区12、熔融区14和熔体输送区16。在进料区12中向混合机10提供树脂和可选的添加剂,并沿下游方向输送树脂通过熔融区14和熔体输送区16。闸门20分隔熔融区14与熔体输送区16。图1示出熔体输送区16中的可选的排气口22。如上所述,树脂在熔融区14中通常至少部分熔融,在熔体输送区16中通常基本上完全熔融。树脂被输送通过混合机出口18,并例如通过造粒进一步加工。
现在参见图2,参考Farrel混合机30。混合机30包括进料区32、熔融区34和熔体输送区36。在进料区32中向混合机30提供树脂和可选的添加剂,并沿下游方向输送树脂通过熔融区34和熔体输送区36。如上所述,树脂在熔融区34中通常至少部分熔融,在熔体输送区36中通常基本上完全熔融。树脂被输送通过混合机出口38,并例如通过造粒进一步加工。Farrel混合机没有例如Kobe混合机的分隔熔融区与熔体输送区的闸门20之类的闸门。但是,通过相应于混合元件44的顶点42的虚线40所示的窄间隙区将熔融区34与熔体输送区36有效地分隔。可在熔融区34与熔体输送区36之间的虚线40的位置插入可选的节流栓(未示出)。
参见图3,参考Werner-Pfleiderer挤出机,其中加工段(1)包含一个或多个机筒(2)和由正向输送元件、非输送元件和反向输送元件构成的一个或多个螺杆(4)。颗粒或切片形式的树脂(聚乙烯)和可选的添加剂被进料至加工段(1)并从进料端(3)输送至出料端(9),由螺杆(4)的捏合元件和反向输送元件形成熔融区,所述加工段被分成熔融区(5)和熔体输送区(7)。要么通过通风排气口(11),要么通过从注入口(10)注入含氧气体流,树脂(聚乙烯)与含氧气体(仅)在熔体输送区中接触,在后一种情况下,气体流(10a)向上游流动,与从左到右输送的熔融聚乙烯逆向流动,这种情况下,气体混合物从通风排气口(11)导出。或者,注入口(10)可被置于通风排气口(11)的上游,气体混合物在注入口(10)被注入,与熔融树脂并流,并从注入口(11)导出。这两种气体流动模式与在排气口简单接触相比的实际效果是停留/接触时间更长。此外,特殊元件(8)可被置于注入口(10)与通风排气口(11)之间,以增大氧气接触的界面生成和增加熔体的局部停留时间。气体也可以通过单个端口与熔融树脂接触,气体的引入和导出由同一个端口进行。可以使用多于一个的“单个端口”。
可在从220(104℃)或240(116℃)或260(127℃)或280(138℃)或300(149℃)或350(176℃)或400(204℃)的下限至低于536(280℃)或518(270℃)或500(260℃)或430(221℃)或低于420(216℃)或低于410(210℃)或低于400(204℃)的上限的熔体温度下加工所述树脂,其中所述熔体温度为熔融区下游端的温度。本文所用的熔体温度是熔融聚合物/聚乙烯的温度。一旦这样的聚合物/聚乙烯从固体(非熔融态)转变后,熔融聚合物/聚乙烯的温度可以继续升高。无论实际温度如何,熔体温度应被理解为聚合物/聚乙烯至少在其熔点下及更高的温度。例如,在图1中,熔体温度是闸门20处的温度;在图2中,熔体温度是顶点42处的温度;在图3中,熔体温度是最后的机筒后的加工段的出料端(9)处的温度。
应当理解,可以使用本文指出和描述之外的混合机和/或挤出机,只要该混合机和/或挤出机具有能够引入氧气或氧气混合物的熔体输送区。
氧化剂
树脂与氧气或氧气混合物在熔体输送区中接触。所述氧气或氧气混合物可例如通过一个或多个气体进口提供。参见图1,例如在某些实施方式中,氧气或氧气混合物可以通过一个或多个进口24提供。参见图2,例如在某些实施方式中,氧气或氧气混合物可以通过一个或多个进口46提供。参见图3,如上所述,例如在某些实施方式中,氧气或氧气混合物可以通过一个或多个进口提供。应当理解,这些具体进口位置仅为示例性的。在本发明的实施方式中,料斗和/或进料区和/或熔融区基本上不含有意添加的氧气或氧气混合物。“基本上不含”意指小于2vol%,或小于1vol%,或小于0.5vol%。
可以以连续气流的形式提供氧气或氧气混合物,也可以间歇地提供氧气。在一种实施方式中,气体流可以在排气口上游位置被注入混合机和/或挤出机机筒。气体可以与熔融聚乙烯树脂逆流,或者气体可与熔融聚乙烯并流。“氧气”意指氧气、过氧化物或其它反应性修整剂。尽管使用氧气或氧气混合物作为修整剂讨论实施方式,但也可使用其它修整剂,例如过氧化物和/或其它自由基引发剂。可以用作自由基引发剂的偶氮混合物为:2,2′-偶氮(2,4-二甲基戊腈)[Vazo52];2,2′-偶氮双异丁腈[Vazo64];2,2′-偶氮双-(2-甲基丁腈)[Vazo 67]和1,1′-偶氮环己烷腈[Vazo 88],其均可从E.I.Dupont获得。其它自由基引发剂包括月桂酰过氧化物;苯甲酰过氧化物;环己酮过氧化物;1,1-双(叔丁基过氧化)-3,3,5-三甲基环己烷;叔丁基过氧化异丙基碳酸酯;过乙酸叔丁基酯;2,2-双(叔丁基过氧化)丁烷;过氧化苯甲酸叔丁基酯;双(1-(叔丁基过氧化)-1-甲基乙基环己烷;二枯基过氧化物;2,5-双(叔丁基过氧化)-2,5-二甲基-3-己炔;叔丁基过氧化物;2,4-戊二酮过氧化物和枯烯过氧化氢。
氧气可以作为基本上纯的气体或作为气体混合物的一部分提供。氧气可以以预混的气体混合物提供,或与稀释气一起进料至挤出机,通过调节氧气/稀释气的相对流率来调节所得混合物中的氧气量。例如,氧气和氮气可以以分别计量的流率进料至挤出机,从而向挤出机提供所需浓度的氧气。可以改变气体流中的氧气含量,以控制对聚乙烯树脂的修整水平或效果。气体流中的氧气水平可为0.1-7.9vol%,或0.25-7.5、或0.5-7.0、或0.75-6.5、或1.0-6.0、或1.5-5.5、或2.0-5.0、或2.5-4.75、或2.75-4.5、或3-4vol%。
气体混合物的剩余组分可以是任何不可燃气体或气体混合物,例如氮、氩、氦、氖、氪、氙、二氧化碳,或其混合物。氧气处理(或“修整”)之后,树脂可通过口模挤出、造粒和冷却,也可在不造粒的条件下直接挤出形成薄膜,例如通过铸塑或吹塑薄膜法。
按照本领域的惯常做法,也可以在挤出机中引入各种添加剂。
修整
修整是修整剂(例如氧气或诸如过氧化物之类的含氧剂)与聚合物之间反应的结果。通过聚合物的温度、修整剂(例如氧气)与聚合物的接触停留时间、修整剂的浓度和抗修整剂(例如抗氧化剂和/或其它稳定添加剂)的浓度或停留时间中的一种或多种,可以影响修整,该修整通过弹性的提高来度量。在修整剂(如氧气)的情况下,此时聚合物熔体中的氧气与气体相比相对溶解度小,大部分修整反应沿着界面发生,因此增大界面的表面积可以提高修整的程度。任何上述变量也可用于控制修整工艺。
在聚乙烯被修整之后,聚乙烯的弹性(G’/G”)将比在类似条件下挤出或混合的未修整聚乙烯的弹性(G’/G”)大至少10、或12、或14、或16、或18、或20、或25、或27、或30、或35、或40、或45、或50、或55%。“类似条件”意指除正常的工艺波动以外,挤出速率、挤出机区温度、螺杆设计和其它参数大体相同。“未修整”意指粒状聚乙烯以其流变性改变最小化的方式被混合或挤出。这样的最小化可以通过以下方法实现:从被挤出/混合的粒状树脂排除修整剂,和/或将聚乙烯与非反应性气体或气体混合物(例如氮气)挤出/混合,和/或将聚乙烯与高浓度的主和/或辅助抗氧化剂挤出/混合,和/或在低于例如200℃的较低融体温度下挤出/混合聚乙烯。或者,“未修整”是指在基本上不存在氧气或氧气混合物的条件下或在氮气或非反应性气氛中挤出/混合。“基本上不存在氧气”意指在给定的工艺或工艺段中存在小于1、或小于0.5、或小于0.25、或小于0.1、或小于0.05vol%的氧气或含氧气体(例如空气)。
修整可受添加剂的影响,所述添加剂例如是抗氧化剂和/或抗臭氧剂,例如亚磷酸酯和/或亚膦酸酯。通常,对于给定的温度、氧气含量和/或停留时间,聚合物中存在的这种添加剂越多,调整的量和效果越小。在聚乙烯树脂中,基于聚乙烯树脂、其它添加剂和可选的填料,这种添加剂的存在量为从0、或2、或5、或10、或20、或30、或40ppm的下限至3000、或2500、或2000、或1500、或1000、或750、或500、或400、或300、或200、或100ppm的上限。
另一种更具体的实施方式涉及制备可用于吹塑薄膜中的聚乙烯树脂的方法,所述树脂在吹塑薄膜挤出过程中具有改善的膜泡稳定性,所述方法包括:
a)将粒状聚乙烯均聚物或共聚物引入混合机/挤出机;
b)将所述粒状聚乙烯输送通过所述混合机/挤出机的进料区、和/或熔融区和熔体输送区;
c)将气体混合物引入所述熔体输送区,所述熔体输送区包含所述气体混合物,所述聚乙烯均聚物或共聚物基本上熔融,所述气体混合物包含2.5-4.5vol%的氧气,所述气体混合物的剩余组分包含非反应性气体或非反应性气体的混合物,所述气体混合物在所述熔体输送区中在与所述基本上熔融的聚乙烯均聚物或共聚物的相同方向或相反方向上流动,以形成经氧气处理的聚乙烯均聚物或共聚物;
d)通过以下进一步的操作加工所述经氧气处理的聚乙烯均聚物或共聚物:i)造粒;或ii)形成薄膜;或iii)造粒和形成薄膜,其中所述聚乙烯均聚物或共聚物具有0.930-0.970g/cm3的密度,并且具有比在基本上不存在氧气的条件下混合/挤出的相似的聚乙烯均聚物或共聚物高至少30%的弹性(G’/G”)。
另一种具体的实施方式涉及制备聚乙烯的方法,所述聚乙烯在吹塑薄膜制备过程中具有改善的膜泡稳定性和改善的厚度均匀性,所述方法包括:
a)将粒状聚乙烯均聚物或共聚物引入混合机/挤出机;
b)将所述粒状聚乙烯输送通过所述混合机/挤出机的进料区、和/或熔融区和熔体输送区;
c)将气体混合物引入所述熔体输送区,所述熔体输送区基本上由挤出机螺杆元件和机筒组成,所述气体混合物和所述聚乙烯均聚物或共聚物基本上熔融;所述气体混合物包含3-4vol%的氧气,所述气体混合物的剩余组分包含非反应性气体或非反应性气体的混合物,所述气体混合物在所述熔体输送区中在与所述基本上熔融的聚乙烯均聚物或共聚物的相同方向或相反方向上流动,以形成经氧气处理的聚乙烯均聚物或共聚物;
d)通过以下进一步的操作加工所述经氧气处理的聚乙烯均聚物或共聚物:i)造粒;或ii)形成薄膜;或iii)造粒和形成薄膜,其中所述聚乙烯均聚物或共聚物具有0.930-0.970g/cm3的密度,并且具有比在基本上不存在氧气的条件下混合/挤出的相似的聚乙烯均聚物或共聚物高至少40%的弹性(G’/G”)。
另一种具体的实施方式涉及修整聚乙烯的方法,所述方法包括:
a)将粒状聚乙烯引入混合机/挤出机;
b)将所述粒状聚乙烯输送通过混合机/挤出机的进料区、和/或熔融区和熔体输送区,其中所述进料区和所述熔融区基本上不含氧气;
c)将气体混合物引入所述熔体输送区,所述熔体输送区包含所述气体混合物和基本上熔融的所述聚乙烯;所述气体混合物包含3-4vol%的氧气,所述气体混合物的剩余组分包含非反应性气体或非反应性气体的混合物,所述气体混合物在所述熔体输送区中在与所述基本上熔融的聚乙烯均聚物或共聚物的相同方向或相反方向上流动,以形成经氧气处理的聚乙烯均聚物或共聚物;
d)通过以下进一步的操作加工所述经氧气处理的聚乙烯:i)造粒;或ii)形成薄膜;或iii)造粒和形成薄膜;其中所述聚乙烯均聚物或共聚物具有0.930-0.970g/cm3的密度,并且具有比在基本上不存在氧气的条件下混合/挤出的相似的聚乙烯高至少40%的弹性(G’/G”)。
实施例
术语“熔融指数”是指按照ASTM D-1238条件E(190℃,2.16kg载荷)测量的树脂的熔体流动速率,通常表示为I2.16。术语“流动指数”是指按照ASTM D-1238条件F(190℃,21.6kg载荷)测量的树脂的熔体流动速率,通常表示为I21.6。熔融指数和流动指数的单位为g/10min,或等同于dg/min。术语“MFR”意指比值I21.6/I2.16,是无量纲的。
比能输入(SEI)意指对于每单位重量的熔融加工树脂向挤出机主驱动机构输入的能量,用单位hp·hr/lb或kW·hr/kg表示。
本文所用“弹性”是在0.1S-1的频率下G’与G”之比,其中G’和G”分别为储能(或弹性)模量和损耗(或粘性)模量。G’和G”按照ASTMD-4440-84测量。在200℃下用装有25mm平行板和约1.5mm间隙的Rheometrics DSR500动态应力振动流变仪进行测量。
密度(g/cm3)用从板中切出的碎片测定,按照ASTM D-1928-96方法C模压、按照ASTM D618方法A老化、并按照ASTM D1505-96测量。
将氧气供给至氧气-氮气混合物。通过改变氧气与氮气的相对流率来控制氧气水平。数据表中列出的氧气水平根据空气和氮气的体积流率计算。
实施例A
所使用的基体树脂是用双金属催化剂在单一气相流化床反应器中(在商业化反应器中)制备的双峰HDPE树脂。双金属催化剂为美国专利No.6403181所述的Ziegler-Natta/茂金属催化剂。未修整的树脂的密度为0.953g/cm3,熔融指数I2.16为0.07dg/min,流动指数I21.6为7.8dg/min,弹性(G’/G”)为0.53。混合过程中加入的添加剂为800ppm的Irganox-1010和200ppm的Irgafos-168以及1500ppm的硬脂酸锌。
所用设备为Coperion(Werner-Pfleiderer)ZSK-57同向旋转双螺杆挤出机。示意图见图3,该图示出了机器的加工段(1)。此加工段包括机筒(2)和由正向输送元件、非输送元件和反向输送元件构成的螺杆(4)。颗粒或切片形式的树脂和可选的添加剂被进料至加工段(1)并从进料端(3)输送至出料端(9)。所述加工段被分成由捏合和反向输送螺杆元件形成的熔融区(5)和熔体输送区(7)。可选的添加剂的例子为抗氧化剂和聚合物加工助剂(PPA)。在此实施例中,总浓度为0.1%的两种抗氧化剂(Irganox-1010和Irgafos-168)的组合与0.15%的作为PPA(聚合物加工助剂)的硬脂酸锌一起使用。添加剂的总量为0.25%。
通过将氧气、氧气混合物或氮气(如表1所示)注入通风排气口(11),或者更有效地从注入口(10)注入氧气或氧气混合物,使该树脂与氧气在熔体输送区中接触。在后一种情况下,气体流向上游与熔融树脂的熔体输送逆流流动,然后气体流从排气口(11)导出。停留时间远大于在排气口接触的情形。而且,中性捏合元件被置于(10)与(11)之间,以增加氧气接触的界面生成和增大熔融树脂的局部停留时间。
改变气体流中氧气含量来控制修整水平。表1所示的试验/实验表明,当氧气含量从0%(氮气氛)变为3%以及6%时,弹性分别从0.54变为0.64和0.69。这些变化说明,与未修整的基体树脂相比,弹性提高21-30%。
表1
试验 | 注入气体流中的氧气含量 | I2 | I21 | MFR | G′/G″ | G′/G″增量(%) |
1 | 0%(氮气) | 0.07 | 8.6 | 119.2 | 0.54 | 1 |
2 | 3% | 0.069 | 7.8 | 113.3 | 0.64 | 21 |
3 | 6% | 0.06 | 8.6 | 146.1 | 0.69 | 30 |
实施例B
此实施例所用的聚合物基本上与实施例A中所用的聚合物相同。在装有EL-2马达的Kobe Steel LCM-320上进行混合。在粒状树脂进料被引入混合机之前,向其中添加200ppm Irganox-168、800ppm Irganox-1010、500ppm硬脂酸锌和1000ppm硬脂酸钙。氧气(以纯化空气并用氮气稀释以获得4%的氧气)被引入熔融区(闸门的下游)。总气体流量被保持在3Nm#/hr。调整闸门位置及SEI,以对每个修整对象在闸门处保持恒定范围的温度。
通过直接从反应器中提取粒状样品来确定未修整的数据。用1500ppmIrganox-1010、1500ppm Irganox-168和500ppm硬脂酸锌与样品干燥混合。然后将混合样品引入氮气氛下的单螺杆挤出机并进行熔融均化。评价由熔融均化的样品得到的切片,计算2个样品(间隔1小时取样,相当于20吨反应器生产区间)的平均值。
当来自所述20吨的生产区间的相同反应器树脂被引入Kobe LCM-320时,每小时采集样品,对其进行评价并取平均值,以确定表2所列的性质。同样,修整平均值通常涉及间隔1小时取样的两个样品。混合机加工数据(例如SEI和氧气%)是对相同的20吨区间取平均。
表2
生产吨数RXN计时开始RXN计时结束 | 2005/2/2004 15:065/2/2004 18:12A | 3005/3/2004 05:005/3/2004 07:18B | 4005/3/2004 17:005/3/2004 18:12C |
未修整FIMFR弹性 | 12.461240.545 | 6.00890.532 | 7.931140.530 |
修整条件SEI氧气% | 1934% | 1974% | 2064% |
修整后的性质FIMFR弹性弹性变化%MFR变化% | 15.271510.61011.9%21.7% | 6.581120.65122.4%25.2% | 8.881390.67326.9%22.6% |
Lot | 4EA14 | 4EA16 | 4EA18 |
Claims (11)
1.挤出/造粒聚乙烯的方法,包括:
a)向混合机/挤出机提供聚乙烯;
b)将所述聚乙烯输送通过混合机/挤出机,所述混合机/挤出机包括熔体输送区,其中在所述熔体输送区,所述聚乙烯基本上熔融;和
c)使所述基本上熔融的聚乙烯与包含0.5-7.9vol%氧气的气体混合物接触,以制备经氧气处理的聚乙烯,其中所述接触发生在所述熔体输送区。
2.如权利要求1的方法,其中所述气体混合物包含下限为0.5vol%、或0.75vol%、或1.0vol%、或1.5vol%、或2.0vol%、或2.5vol%、或2.75vol%、或3.0vol%之一的氧气和/或上限为7.9vol%、或7.5vol%、或7.0vol%、或6.5vol%、或6.0vol%、或5.5vol%、或5.0vol%、或4.75vol%、或4.5vol%、或4.0vol%的氧气。
3.如权利要求1或2的方法,其中所述混合机/挤出机还包括进料区和/或熔融区。
4.如权利要求3的方法,其中所述气体混合物以单个端口、与所述基本上熔融的聚乙烯逆流或并流中的一种方式被引入所述熔体输送区。
5.如权利要求4的方法,其中所述聚乙烯包含乙烯和下列中的一种或多种:丙烯;3-甲基-1-丁烯;3,3-二甲基-1-丁烯;1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-戊烯;1-己烯;具有一个或多个甲基、乙基或丙基取代基的1-己烯;1-庚烯;具有一个或多个甲基、乙基或丙基取代基的1-庚烯;1-辛烯;具有一个或多个甲基、乙基或丙基取代基的1-辛烯;1-壬烯;具有一个或多个甲基、乙基或丙基取代基的1-壬烯;乙基、甲基或二甲基取代的1-癸烯;1-十二碳烯或苯乙烯。
6.如权利要求5的方法,其中所述聚乙烯的弹性G’/G”较在基本上不存在氧气的类似条件下混合/挤出的相似的聚乙烯高至少10%、或20%、或30%、或40%、或50%。
7.如权利要求7的方法,其中所述聚乙烯具有多峰分子量分布和/或多峰组成分布。
8.如权利要求7的方法,其中所述聚乙烯为物理混合物,或用两种或多种催化剂在单一或多个反应器中制备。
9.如权利要求1的方法,其中所述聚乙烯是单峰的。
10.如权利要求3的方法,其中所述基本上熔融的聚乙烯与所述气体混合物在所述混合机/挤出机的基本上由所述熔体输送区构成的一部分中接触。
15.如权利要求1-10中任何一项的方法,还包括将所述经氧气处理的聚乙烯造粒。
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CN104936993A (zh) * | 2012-12-12 | 2015-09-23 | 汉高股份有限及两合公司 | 在挤出机中降解(共)聚合物的方法及用于实施所述方法的挤出机 |
CN105085725A (zh) * | 2015-08-24 | 2015-11-25 | 华南理工大学 | 一种臭氧氧化工艺制备氧化聚丙烯的装置及方法 |
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- 2005-07-25 MX MX2007001862A patent/MX2007001862A/es active IP Right Grant
- 2005-07-25 CN CNA200580027836XA patent/CN101014631A/zh active Pending
- 2005-07-25 BR BRPI0514491-4A patent/BRPI0514491A/pt not_active Application Discontinuation
- 2005-07-25 WO PCT/US2005/026352 patent/WO2006023213A1/en active Application Filing
- 2005-07-25 EP EP05778036A patent/EP1778745A4/en not_active Withdrawn
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102892790A (zh) * | 2010-01-19 | 2013-01-23 | 陶氏环球技术有限责任公司 | 改善适用于吹制膜挤出工艺的聚乙烯组合物的膜泡稳定性的方法 |
CN102892790B (zh) * | 2010-01-19 | 2015-02-25 | 陶氏环球技术有限责任公司 | 改善适用于吹制膜挤出工艺的聚乙烯组合物的膜泡稳定性的方法 |
CN104936993A (zh) * | 2012-12-12 | 2015-09-23 | 汉高股份有限及两合公司 | 在挤出机中降解(共)聚合物的方法及用于实施所述方法的挤出机 |
CN104936993B (zh) * | 2012-12-12 | 2018-06-01 | 汉高股份有限及两合公司 | 在挤出机中降解(共)聚合物的方法及用于实施所述方法的挤出机 |
CN105085725A (zh) * | 2015-08-24 | 2015-11-25 | 华南理工大学 | 一种臭氧氧化工艺制备氧化聚丙烯的装置及方法 |
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EP1778745A1 (en) | 2007-05-02 |
MX2007001862A (es) | 2008-10-24 |
AU2005277807A1 (en) | 2006-03-02 |
CA2577548A1 (en) | 2006-03-02 |
EP1778745A4 (en) | 2010-02-03 |
WO2006023213A1 (en) | 2006-03-02 |
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US20060038315A1 (en) | 2006-02-23 |
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