CN1246136A - 具有反相形态的聚乙烯与聚(环氧乙烷)的共混物及其制法 - Google Patents

具有反相形态的聚乙烯与聚(环氧乙烷)的共混物及其制法 Download PDF

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CN1246136A
CN1246136A CN97181805A CN97181805A CN1246136A CN 1246136 A CN1246136 A CN 1246136A CN 97181805 A CN97181805 A CN 97181805A CN 97181805 A CN97181805 A CN 97181805A CN 1246136 A CN1246136 A CN 1246136A
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J·H·X·王
D·M·舒尔茨
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Abstract

一种热塑性薄膜,它包含:聚烯烃,如聚乙烯,作为主要成分;聚(环氧乙烷)作为次要成分;以及总共约0.1wt%～约30wt%接枝到聚烯烃和聚(环氧乙烷)上的单体。该薄膜呈现一种反相形态,致使聚(环氧乙烷)形成薄膜中的连续相,而聚烯烃形成分散或不连续相。该薄膜最好用于用即弃个人卫生用品。

Description

具有反相形态的聚乙烯与 聚(环氧乙烷)的共混物及其制法
本申请要求1996-12-31提交的美国临时申请号60/034，235的优先权，该公开内容收作本文的参考。
发明领域
本发明涉及一种包含聚乙烯和聚(环氧乙烷)的组合物热塑性薄膜，它表现为反相形态。
发明背景
当今，人们使用着多种多样的用即弃塑料制品。由于成本低、使用方便，它们受到广泛的欢迎并具有很大的消费需求。然而，这些制品中许多属不可降解或不易处置的。因此，它们已经并将继续造成废弃物处置方面的问题。
个人护理用品，如尿布、卫生巾、成人失禁服装类等等，通常由多种不同的成分和材料构成。典型的此类制品总是有某部分，通常是背面包覆层、衬里或阻挡层，由防液材料构成的薄膜制成。此种防液材料经过恰当的制作，可大大较少或防止已被吸收的液体从制品中流出并从而使制品的吸收能力得到更大限度的利用。通常所使用的防液薄膜包含塑料，如聚乙烯薄膜之类。
虽然此种制品相对便宜、卫生和使用方便，但是，制品在脏了之后的处置上并非不存在问题。一种理想的处置此类制品的方法，要算利用市政污水处理及私人住宅化粪池系统。适合丢弃到污水系统中的产品可以顺着马桶冲下去，故而称作“可冲入(马桶)的”。虽然将此种制品冲走可能是方便的，但是，防液材料在水中通常不解体，结果往往堵塞马桶和下水管。于是，冲入之前就不得不，尽管不情愿，把阻隔膜材料与吸收制品分开。
为了克服防水薄膜造成的可冲入问题，先有技术对其防水聚合物做了改性。较为有用的聚合物改性方法之一是将它们与一些结构和性质不同的其他聚合物掺混。在少数情况下，聚合物共混物的组合在热力学上为互相溶混的并表现出机械相容性。然而，绝大多数共混物会出现相分离并通常表现出很差的机械相容性。相分离的共混物在某些情况下也可表现出机械相容性，这些情况是：聚合物在组成上相近，例如，一种聚烯烃与其他类似的聚烯烃相掺混，或者加入界面活性剂，以改善聚合物共混物中不同成分之间在界面处的相容性。
聚烯烃与聚(环氧乙烷)的聚合物共混物虽然是可熔融加工的，但却表现出很差的机械相容性。这种不良的机械相容性尤其表现在聚烯烃的比例超过50wt％的共混物上。这种薄膜通常不受水的影响，因为，就典型情况而言，多数相，即聚烯烃，将包围并包封着少数相，即聚(环氧乙烷)。聚(环氧乙烷)的被包封就实际上阻止了因使用聚(环氧乙烷)本来可能获得的可降解性和/或可冲入优点的发挥。
鉴于先有技术存在的问题，人们仍然十分渴望获得一种呈现反相的形态的约50wt％以上聚烯烃与聚(环氧乙烷)的共混物。用此种共混物制成的薄膜来作个人护理用品的阻隔薄膜，则制品将是可冲入的。此种薄膜还可用于制作过滤膜。
发明概述
扼要地说，本发明提供一种热塑性薄膜，它包含聚烯烃、聚(环氧乙烷)及一定数量接枝到聚烯烃和聚(环氧乙烷)以便使薄膜呈现反相形态的单体。本文所使用的术语“反相形态”是指，体积占多数的成分，即，通常预期将构成薄膜中的连续相的，实际上成了分散相。相应地，体积占少数的成分则形成连续相，在它内部分散着体积占多数的成分。
本发明的目的是提供一种具有反相形态的热塑性薄膜。更具体地说，本发明的目的是提供一种热塑性薄膜，它包含约55wt％～约85wt％聚烯烃、约45wt％～约15wt％聚(环氧乙烷)以及一定数量接枝到聚烯烃和聚(环氧乙烷)以便使薄膜呈现反相形态的单体。这里所使用的聚烯烃和聚(环氧乙烷)的“重量百分数(wt％)”是采用构成热塑性组合物的聚烯烃与聚(环氧乙烷)的总量(为基准)确定的，不考虑所加入的单体数量。
附图简述
图1是一种4密耳(0.004英寸)薄膜断面的反向散射电子图像扫描电子显微镜照片，薄膜组成中包含60wt％聚乙烯和40wt％聚(环氧乙烷)。
图2一种4密耳薄膜断面的反向散射电子图像扫描电子显微镜照片，薄膜组成中包含60wt％聚乙烯和40wt％聚(环氧乙烷)，其中在聚乙烯和聚(环氧乙烷)中又加入了约3wt％的某种单体。
图3一种4密耳薄膜断面的反向散射电子图像扫描电子显微镜照片，薄膜组成中包含60wt％聚乙烯和40wt％聚(环氧乙烷)，其中在聚乙烯和聚(环氧乙烷)中又加入了约5.5wt％的某种单体。
图4一种4密耳薄膜断面的反向散射电子图像扫描电子显微镜照片，薄膜组成中包含60wt％聚乙烯和40wt％聚(环氧乙烷)，其中在聚乙烯和聚(环氧乙烷)中又加入了约9wt％的某种单体。
发明详述
虽然本发明是结合热塑性薄膜描述的，但是，本领域技术人员懂得本发明对其他可挤塑或注塑热塑性制品的实用价值。本发明的薄膜组合物包含约55wt％～约85wt％聚烯烃、约45wt％～约15wt％聚(环氧乙烷)以及一定数量接枝到聚烯烃和聚(环氧乙烷)以便使薄膜呈现反相形态的单体。已出乎意料地发现，这种由亲水部分构成连续相的反相形态可通过在薄膜中使用一种少量成分来达到，从而大大提高了薄膜的水敏感性和可降解性。优选的是，共混物包含约60wt％～约85wt％聚乙烯、约40wt％～约15wt％聚(环氧乙烷)以及使热塑性塑料呈现反相形态的有效数量的、接枝到聚烯烃和聚(环氧乙烷)上的单体。
可用于实施本发明的饱和乙烯聚合物是乙烯均聚物或共聚物，并且是基本线型结构的。这里所使用的术语“饱和(的)”是指完全饱和的聚合物，然而也涵盖含有最高约5％不饱和部分的聚合物。乙烯均聚物包括，或者在低压下制备的均聚物，即线型低密度或高密度聚乙烯，或者在高压下制备的，即支链或低密度聚乙烯。高密度聚乙烯通常用密度约等于或大于0.94克每立方厘米(g/cc)来表征。一般地，可用作本发明基础树脂的高密度聚乙烯的密度范围在约0.94g/cc～约0.97g/cc。该聚乙烯在2.16kg和190℃条件下测定的熔融指数在约0.005dg/min(分克/分)～100dg/min的范围。希望的是，该聚乙烯的熔融指数为0.01dg/min～约50dg/min，更希望在0.05dg/min～约25dg/min。替代地，聚乙烯的混合物也可用作生产该接枝共聚物组合物的基础树脂，而此种混合物的熔融指数应在大于0.005dg/min到小于约100dg/min的范围。
低密度聚乙烯的密度小于0.94g/cc，一般在0.91g/cc～约0.93g/cc。低密度聚乙烯的熔融指数为约0.05dg/min～约100dg/min，希望在0.05dg/min～约20dg/min。超低密度聚乙烯也可用于本发明。一般而言，超低密度聚乙烯的密度小于0.90g/cc。
以上的聚烯烃也可采用众所周知的多部位齐格勒-纳塔催化剂，或者采用较新的单部位金属茂催化剂来制备。与采用齐格勒-纳塔催化剂制备的聚烯烃相比，金属茂催化的聚烯烃具有控制得更好的聚合物微结构，包括更窄的分子量分布、控制得很好的化学组成分布、共聚单体序列长度分布以及立体规整性。已知，金属茂催化剂可使丙烯聚合成为无规立构、全同立构、间同立构、全同立构-无规立构的立构嵌段共聚物。
可用于本发明的乙烯共聚物包括乙烯与1种或多种另外的可聚合不饱和单体的共聚物。此种共聚物的例子包括但不限于：乙烯与α-烯烃(如丙烯、丁烯、己烯或辛烯)的共聚物，包括线型低密度聚乙烯；乙烯与1～24个碳原子的线型或支链羧酸的乙烯基酯的共聚物，如乙烯-醋酸乙烯共聚物；以及乙烯与1～28个碳原子线型、支链或环烷醇的丙烯酸或甲基丙烯酸酯的共聚物。后一种共聚物的例子包括乙烯-(甲基)丙烯酸烷基酯共聚物，如乙烯-丙烯酸甲酯共聚物。
适用于本发明的聚(环氧乙烷)聚合物的分子量在200,000～8,000,000的范围，优选约200,000～约6,000,000。聚(环氧乙烷)可由联合碳化物公司按商品名POLY0X购得。就典型而言，聚(环氧乙烷)为干燥、自由流动的白色粉末，结晶熔点在约65℃之谱，高于熔点时聚(环氧乙烷)树脂转变为热塑性的，并可通过模塑、挤塑和其他技术上已知的方法成形。
构成薄膜的聚烯烃和聚(环氧乙烷)具有接枝到其上的有效数量单体，即，一种聚乙二醇乙基醚的甲基丙烯酸酯(Aldrich化学公司出品，威斯康星州，密尔沃基)，它出乎意料地在薄膜中产生一种反相形态。参见图1，本领域技术人员很可能会预料，聚乙烯，由于是主要成分，会形成连续相，在连续相中分散着聚(环氧乙烷)作为非连续相。然而，参见图2～4，本发明的薄膜包含的聚(环氧乙烷)却是以连续相出现的，而聚乙烯分散于其中构成非连续相，尽管聚乙烯的含量更大些。接枝到聚烯烃和聚(环氧乙烷)上去的单体数量，以聚烯烃与聚(环氧乙烷)重量为基准，为总共约0.1wt％～约30wt％。希望的是，聚烯烃和聚(环氧乙烷)包含总共约1wt％～约20wt％接枝在其上的单体。更希望的是，聚烯烃和聚(环氧乙烷)包含总共约1wt％～约10wt％接枝在其上的单体。
为制备本发明薄膜的接枝聚乙烯和聚(环氧乙烷)成分，聚烯烃与聚(环氧乙烷)在自由基引发剂的存在下与该单体进行反应。引发剂起着引发该单体的自由基接枝反应的作用。在聚合物共混物上接枝的过程包括：将要求重量比的聚烯烃、聚(环氧乙烷)、所述单体以及自由基引发剂的混合物置于挤塑机中，并在使聚烯烃和聚(环氧乙烷)转变为熔融状态的反应温度下进行熔融掺混。据此，优选的方法包括：将聚烯烃、聚(环氧乙烷)、单体及自由基引发剂同时加入到挤塑机中，然后，各聚合物成分，即聚烯烃和聚(环氧乙烷)，发生熔融。希望的是，用于熔融掺混的熔融挤塑机能够沿螺杆长度的不同部位向共混物中引入各种成分。例如，自由基引发剂、交联剂或其他活性添加剂，可在1种或多种聚合物成分熔融或彻底混合之前或之后，注入到共混物中。更优选的是，聚烯烃及聚(环氧乙烷)在挤塑机开始的一端加入。(聚合物)熔融之后，将单体加入到熔融的聚合物中，并在沿挤塑机机筒更靠下游的地方，将自由基引发剂加入到熔融共混物中。该方法更详细地描述在1996年12月31日提交的共同未决美国专利申请序列号08/777，226中题为“聚烯烃与聚(环氧乙烷)的共混物及其制法”，在此将全文收作本文的参考。
可用来使单体接枝到聚烯烃上去的自由基引发剂包括酰基过氧化物，如过氧苯甲酰；二烷基、二芳基或二芳烷基的过氧化物，如过氧二叔丁基、过氧二枯基、过氧枯基丁基、1，1-二叔丁基过氧-3，5，5-三甲基环己烷、2，5-二甲基-2，5-二(叔丁基过氧)己烷、2，5-二甲基-2，5-双(叔丁基过氧)己炔-3以及双(a-叔丁基-过氧异丙基苯)；过氧酯，如过新戊酸叔丁酯、过辛酸叔丁酯、过苯甲酸叔丁酯、2，5-二甲基己基-2，5-二(过苯甲酸酯)、二(过邻苯二甲酸)叔丁酯、二烷基的过氧单碳酸酯以及过氧二碳酸酯；氢过氧化物，如叔丁基过氧化氢、对甲烷(methane)过氧化氢、蒎烷过氧化氢及枯烯过氧化氢；以及酮过氧化物，如过氧环己酮和过氧甲乙酮。偶氮化合物，如偶氮二异丁腈，也可使用。
自由基引发剂向挤塑机中的加入量应当是足以使单体的约1％～约100％接枝到聚烯烃和聚(环氧乙烷)上的数量。该用量为约0.1wt％～约10wt％的引发剂，优选在约0.1wt％～约5wt％的范围，其中所有这些范围均以加入到熔融共混物中的单体数量为基准。
本发明热塑性薄膜的的特征是，当采用扫描电子显微镜并利用反向散射电子检测器图像检验时，该薄膜显示，聚(环氧乙烷)形成连续相，其中有聚烯烃不连续相，即分散在整个聚(环氧乙烷)相中。在反向散射电子检测器成象所产生的图像中，成分的平均原子数越高，产生的反向散射电子强度就越高，照片上的图像看上去就越亮。原子数越低的成分，产生的反向散射电子强度就越低，在照片上显示的图像就越暗。反向散射电子显微镜成象技术更详细地描述在Linda C.Sawyer和David T.Grubb的《聚合物显微术》，Chapman & Hall，伦敦，1987年，第25页。希望的是，热塑性薄膜聚烯烃部分的平均断面直径在约0.1μm～约50μm，优选在约0.5μm～约30μm，更优选约0.5μm～约25μm的范围。此种“聚烯烃部分”可以是固化的聚烯烃囊、纤维或二者的组合。
下面，将通过具体实施例更详细地说明本发明。要知道，这些实施例是举例说明用的实施方案，不拟用以界定本发明，相反，概括地说，认为其在所附权利要求的范围和内容之内。
对比例
低密度聚乙烯(PE)与聚(环氧乙烷)(PEO)按60/40重量比的树脂共混物，在挤塑机中进行熔融混炼。PE的熔融指数为1.9dg/min，密度为0.917g/cc(Dow 5031，陶氏化学公司(Dow Chemical Company)，Midland，MI)。PEO的分子量为200,000g/mol(POLYOXWSRN-80，联合碳化物公司).用于加工共混物的挤塑机为Werner & PfleidererZSK-30挤塑机(制造商：Werner & Pfleiderer公司，Ramsey，新泽西)。该树脂共混物以34 lb/h的速率喂入到挤塑机中。挤塑机包括一对平行布置并同向旋转的螺杆。二轴的中心距为26.2mm。螺杆名义直径为30mm。螺杆的实际外径为30mm。螺杆的内直径为21.3mm。螺纹深度为4.7mm。挤塑机包括14段加工机筒，其中13段加热的机筒分成7个加热区。总加工长度是1340mm。7个加热区均设定在180℃。螺杆速度设定在300rpm。
对比例和实施例1～9的熔融共混物的所有薄膜均是采用Haake反向旋转双螺杆挤塑机(制造商：Haake公司，West Century Road，Paramus，新泽西，07652)，装上4英寸的缝型模头，制成的。该挤塑机的长度为300mm。该锥形螺杆在进料口处的直径是30mm，模头处的直径是20mm。挤塑机包括4个加热区，分别设定在170、180、180和190℃。螺杆速度为30rpm。采用骤冷卷取辊收集薄膜。该骤冷辊操作在足以成形厚度约4密耳(约0.004英寸)的薄膜的速度，并维持在15～20℃的温度。
参见图1，其中聚乙烯形成了连续相，而聚(环氧乙烷)形成非连续相。
实施例1～3
根据本发明，低密度聚乙烯与聚(环氧乙烷)按60/40重量比的树脂共混物，如上面对比例那样，以34 lb/h的速率被喂入到ZSK-30挤塑机中。7个加热区全部设定在180℃。螺杆速度为300rpm。在挤塑机的机筒(段)4处，单体--聚(乙二醇)乙基醚的甲基丙烯酸酯(PEG-MA，Aldrich化学公司出品，Milwaukee，WI)，按规定速率喂入其中。在挤塑机的机筒5处，自由基引发剂(2，5-二甲基-2，5-二(叔丁基过氧)己烷，供应商Atochem，2000 Market St.，费城，宾夕法尼亚州，商品名Lupersol 101，按规定的速率喂入。
在实施例1中，PEG-MA的进料速率为1.0 lb/h，引发剂速率为0.068 lb/h。
在实施例2中，PEG-MA的进料速率为1.9 lb/h，引发剂速率为0.068 lb/h。
在实施例3中，PEG-MA的进料速率为3.1 lb/h，引发剂速率为0.17 lb/h。
参见图2～4，本发明的热塑性薄膜显示出反相形态，其中聚(环氧乙烷)是连续相，而聚乙烯是非连续相。
实施例4
低密度聚乙烯(Dow5031)与分子量100，000g/mol的聚(环氧乙烷)(POLYOXWSRN-10)按60/40重量比的树脂共混物，以35 lb/h的速率喂入到ZSK-30挤塑机中。7个加热区全部设定在180℃。螺杆速度为300rpm。熔融共混树脂的薄膜显示出反相形态，其中聚(环氧乙烷)是连续相，而聚乙烯是非连续相。
实施例5～9
低密度聚乙烯(Dow 5031)与聚(环氧乙烷)(POLYOXWSRN-80)按规定比例的树脂共混物，以5.0 lb/h的速率喂入到Haake挤塑机中。Haake挤塑机与上面对比例中所描述的挤塑机类似，只是，该挤塑机包括2孔线材模头，而不是4英寸缝型模头。与聚合物喂入挤塑机同时，规定数量的单体、PEG-MA以及自由基引发剂(Lupersol 101)从进料口加入。挤塑机包括4个加热区，分别设定在170、180、180和190℃。挤塑机螺杆的速度为150rpm。线材在空气中经冷却，继而造粒。
在实施例5中，共混物为60/40的PE/PEO；PEG-MA的进料速率为0.50 lb/h；引发剂速率为0.025 lb/h。
在实施例6中，共混物为65/35的PE/PEO；PEG-MA的进料速率为0.50 lb/h；引发剂速率为0.025 lb/h。
在实施例7中，共混物为70/30的PE/PEO；PEG-MA的进料速率为0.50 lb/h；引发剂速率为0.025 lb/h。
在实施例8中，共混物为75/25的PE/PEO；PEG-MA的进料速率为0.50 lb/h；引发剂速率为O.025 lb/h。
在实施例9中，共混物为80/20的PE/PEO；PEG-MA的进料速率为0.50 lb/h；引发剂速率为0.025 lb/h。
实施例5～9的薄膜显示出反相形态，其中聚(环氧乙烷)是连续相，而聚乙烯是非连续相。
在实施例5中，单体接枝到聚(环氧乙烷)上去的量，按质子NMR谱术在重水中测定，结果为共混物中聚(环氧乙烷)量的9.52wt％。未反应的单体量按质子核磁共振(NMR)谱术在重水中测定，结果为共混物中聚乙烯与聚(环氧乙烷)总和的2.02wt％。单体接枝到聚乙烯上的量，按傅里叶-变换红外(FT-IR)及氧含量分析，测定值为0.51wt％，该测定方法可见诸于共同未决美国专利申请08/733,410中，1996年10月18日提交，在此全文收作本文的参考。
虽然已就优选的实施方案对本发明做了描述，但是，仍可在不偏离本发明精神的前提下作出各种各样的替换、简化、修改及改进。因此，上述实施例只不过作为本发明的示范例给出，而不应视为对本发明的限定。

Claims (21)

1.一种热塑性制品，它包含：
a)聚烯烃，作为主要成分；
b)聚(环氧乙烷)，作为次要成分；以及
c)一定数量接枝到所述聚烯烃和所述聚(环氧乙烷)上的单体，由于接枝上该数量的单体，所述制品呈现一种反相形态，致使所述次要成分形成所述热塑性制品中的连续相，而所述主要成分形成分散相。
2.权利要求1的热塑性制品，它包含55wt％～约85wt％所述聚烯烃以及约45wt％～约15wt％所述聚(环氧乙烷)。
3.权利要求1的热塑性制品，它包含60wt％～约85wt％所述聚烯烃以及约40wt％～约15wt％所述聚(环氧乙烷)。
4.权利要求1的热塑性制品，其中所述聚烯烃是聚乙烯。
5.权利要求1的热塑性制品，其中所述聚烯烃是聚丙烯。
6.权利要求1的热塑性制品，其中所述单体是聚乙二醇乙基醚的甲基丙烯酸酯。
7.权利要求1的热塑性制品，其中以聚烯烃与聚(环氧乙烷)的总量为基准，总共约0.1wt％～约30wt％的所述单体被接枝到所述聚烯烃和所述聚(环氧乙烷)上。
8.权利要求1的热塑性制品，其中以聚烯烃与聚(环氧乙烷)的总量为基准，总共约1wt％～约20wt％的所述单体被接枝到所述聚烯烃和所述聚(环氧乙烷)上。
9.权利要求1的热塑性制品，其中以聚烯烃与聚(环氧乙烷)的总量为基准，总共约1wt％～约10wt％的所述单体被接枝到所述聚烯烃和所述聚(环氧乙烷)上。
10.权利要求1的热塑性制品，其中所述制品是薄膜。
11.权利要求10的热塑性薄膜，其中分散相中的聚烯烃具有约0.1μm～约50μm的平均断面直径。
12.权利要求10的热塑性薄膜，其中分散相中的聚烯烃具有约0.5μm～约30μm的平均断面直径。
13.权利要求10的热塑性薄膜，其中分散相中的聚烯烃具有约0.5μm～约25μm的平均断面直径。
14.一种热塑性薄膜，它包含：
a)聚乙烯，作为主要成分；
b)聚(环氧乙烷)，作为次要成分；以及
c)一定数量接枝到所述聚乙烯和所述聚(环氧乙烷)上的聚乙二醇乙基醚的甲基丙烯酸酯，由于这种接枝，所述薄膜呈现一种反相形态，致使所述聚(环氧乙烷)形成所述热塑性薄膜中的连续相，而所述聚乙烯形成分散相或不连续相。
15.权利要求14的热塑性薄膜，它包含55wt％～约85wt％所述聚烯烃以及约45wt％～约15wt％所述聚(环氧乙烷)。
16.权利要求14的热塑性薄膜，它包含60wt％～约85wt％所述聚烯烃以及约40wt％～约15wt％所述聚(环氧乙烷)。
17.权利要求14的热塑性薄膜，其中以聚烯烃与聚(环氧乙烷)的总量为基准，总共约0.1wt％～约30wt％的所述单体被接枝到所述聚烯烃和所述聚(环氧乙烷)上。
18.权利要求14的热塑性薄膜，其中以聚烯烃与聚(环氧乙烷)的总量为基准，总共约1wt％～约20wt％的所述单体被接枝到所述聚烯烃和所述聚(环氧乙烷)上。
19.权利要求14的热塑性薄膜，其中以聚烯烃与聚(环氧乙烷)的总量为基准，总共约1wt％～约10wt％的所述单体被接枝到所述聚烯烃和所述聚(环氧乙烷)上。
20.一种热塑性薄膜，它包含：
a)55wt％～约85wt％的聚乙烯；
b)约45wt％～约15wt％的聚(环氧乙烷)；以及
c)以聚烯烃与聚(环氧乙烷)的总量为基准，总共约0.1wt％～约30wt％接枝到所述聚乙烯和所述聚(环氧乙烷)上的聚乙二醇乙基醚的甲基丙烯酸酯，由于这种接枝，所述薄膜呈现一种反相形态，致使所述聚(环氧乙烷)形成所述热塑性薄膜中的连续相，而所述聚乙烯形成分散相或不连续相。
21.权利要求20的热塑性薄膜，其中分散相中的聚乙烯具有约0.1μm～约50μm的平均断面直径。
CNB971818053A 1996-12-31 1997-12-19 具有反相形态的聚乙烯与聚(环氧乙烷)的共混物及其制法 Expired - Fee Related CN1137207C (zh)

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CN102597029A (zh) * 2009-09-14 2012-07-18 陶氏环球技术有限责任公司 包含源自乙烯和聚(烷氧基化物)的单元的聚合物
CN102597029B (zh) * 2009-09-14 2014-09-17 陶氏环球技术有限责任公司 包含源自乙烯和聚(烷氧基化物)的单元的聚合物
CN104130484A (zh) * 2014-06-27 2014-11-05 苏州市盛百威包装设备有限公司 一种pe薄膜包装材料及其制备方法
CN104130484B (zh) * 2014-06-27 2016-08-24 佛山市顺德区众锐塑料机械制造有限公司 一种pe薄膜包装材料及其制备方法

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CN1137207C (zh) 2004-02-04
WO1998029508A1 (en) 1998-07-09
EP0951508B1 (en) 2003-11-05
AU5624598A (en) 1998-07-31
JP2001507744A (ja) 2001-06-12
AU728926B2 (en) 2001-01-18
CA2275386A1 (en) 1998-07-09
US6214933B1 (en) 2001-04-10
US6225406B1 (en) 2001-05-01
IL130514A0 (en) 2001-04-30
EP0951508A1 (en) 1999-10-27
DE69726011T2 (de) 2004-04-22
KR20000069775A (ko) 2000-11-25
KR100468345B1 (ko) 2005-01-27
US5912076A (en) 1999-06-15

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