CN1685006A - 用于挤出涂布的聚合物组合物 - Google Patents

用于挤出涂布的聚合物组合物 Download PDF

Info

Publication number
CN1685006A
CN1685006A CNA038226928A CN03822692A CN1685006A CN 1685006 A CN1685006 A CN 1685006A CN A038226928 A CNA038226928 A CN A038226928A CN 03822692 A CN03822692 A CN 03822692A CN 1685006 A CN1685006 A CN 1685006A
Authority
CN
China
Prior art keywords
mixture
branched polyethylene
thin film
film layer
inhomogeneous
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.)
Granted
Application number
CNA038226928A
Other languages
English (en)
Other versions
CN100537649C (zh
Inventor
R·J·威克斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of CN1685006A publication Critical patent/CN1685006A/zh
Application granted granted Critical
Publication of CN100537649C publication Critical patent/CN100537649C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

本发明涉及适用于挤出涂布的组合物。所述组合物包括均匀乙烯聚合物和不均匀乙烯聚合物连同高熔融强度聚烯烃一起的混合物。由该组合物制得的薄膜层具有改良的“向内弯曲”和极好的热封引发性。

Description

用于挤出涂布的聚合物组合物
本发明大体涉及可用于挤出涂布用途的薄膜组合物，更具体而言，涉及提供用于包装用途的密封层。
有许多用于挤出涂布用途的聚合物组合物的例子，包括线型低密度聚乙烯(LLDPE)与高压(自由基)低密度聚乙烯(LDPE)的混合物。挤出涂布是一种用特殊的聚合物涂布衬底，由此令衬底具有如对另一块衬底或对其本身具有如密封能力的功能性的方法。例子包括汁液包装袋，典型地其具有通过挤出涂布到金属箔衬底上的内部聚合物，随后在金属箔上聚合物涂层与自身密封(粘接)。挤出涂布是一种非常特别的方法，其中“向内弯曲”对形成涂层是重要的。“向内弯曲”指的是聚合物配方在挤压后保持其宽度或其原始尺寸的能力。最小化“向内弯曲”使聚合物配方更为有效以及均匀地涂布到衬底上。
例如，美国专利5,587,247公开用于挤压成形的树脂组合物，其包括吸热峰在80℃到120℃之间的高压乙烯聚合物、吸热峰在118℃到130℃之间的乙烯共聚物，和在其它性质中，在高于110℃没有吸热峰的乙烯共聚物，其公开内容经此引用并入本文。
然而，仍然需要一种能够在保持良好密封能力的同时降低“向内弯曲”的聚合物配方。
现在，本发明公开特别适于具有最小“向内弯曲”、极佳密封性能(例如，低热封装引发温度)和坚韧性的挤出涂布的聚合物组合物。这种组合物包括：
(A) 60到80wt％至少一种均匀支链聚乙烯和至少一种不均匀的支链聚乙烯的混合物；和
(B) 20到40wt％至少一种熔融强度至少为混合物(A)两倍的聚合物。一种由这些组合物制得的薄膜层也在本发明的范围内。
在本发明的另一个具体实施方案中，制造一种包括至少两层的薄膜，
(A) 一层是由一种聚合物组合物制成的，该组合物包括至少一种均匀支链聚乙烯和至少一种不均匀的支链聚乙烯的混合物，以及
(B) 另一层是包括至少一种熔融强度至少为(A)的混合物两倍的其它聚合物。
图1显示的是本发明的(A)的混合物的示差扫描量热图。值得注意的是，有三个明显的熔融峰。
可用于本发明的聚合物树脂是聚乙烯，对于组分(B)，可以额外使用聚丙烯无规共聚物(PPRCP)、苯乙烯/丁二烯共聚物(SBC)、聚苯乙烯、乙烯-乙酸乙烯酯共聚物(EVA)和环/烯烃共聚物(COC)。
可用于本发明的聚乙烯属于两大类别：一些在高温和高压下采用自由基引发剂制备的聚乙烯，和一些在高温和相对低压下采用配位催化剂制备的聚乙烯。形成物通常被称作LDPE，其特征在于从聚合物骨架侧面垂下的聚合单体单元的支链。LDPE聚合物的密度通常在0.910到0.940g/cm3之间。在本文中除非另行说明，均按照ASTM D-792的程序测量聚合物的密度。
由于基本上不存在从聚合物骨架侧面垂下的聚合单体单元的支链，所以通过使用如齐格勒—纳塔催化剂或菲利普催化剂的配位催化剂来制备的乙烯聚合物和共聚物通常被称作线型聚合物。乙烯和至少一种3到12个碳原子、优选为4到8个碳原子的-烯烃的线型共聚物是众所周知且可市售的。如本领域内所熟知的，线型乙烯/-烯烃共聚物的密度是-烯烃长度和相对于乙烯数量的烯烃单体在共聚物中数量的函数，-烯烃越长，以及所含-烯烃的量越大，共聚物的密度越低。LLDPE是一种不均匀的聚合物，指的是共聚单体并非均匀地沿聚合物骨架分布。由于支链的非均匀性，不均匀乙烯聚合物的支链分布是显著的。
典型地，LLDPE是乙烯和3到20个碳原子、优选为4到8个碳原子的-烯烃(例如，1-丁烯、1-辛烯等等)的共聚物，其具有相对于LDPE(例如，0.910g/cm3到0.940g/cm3)的来说足以降低共聚物密度的-烯烃含量。当该共聚物含有更多-烯烃时，其密度将会降至低于大约0.91g/cm3，并且这些共聚物可以交换地称为超低密度聚乙烯(ULDPE)或VLDPE。VLDPE或ULDPE的密度通常在0.87到0.91g/cm3之间。LLDPE和VLDPE或ULDPE在本领域内均如其制备过程那样为人所熟知。例如，如美国专利4,076,698中所述，可以采用齐格勒—纳塔催化剂，在浆料、气相、溶液或高压工艺中制得不均匀的LLDPE，同时，可以如美国专利3,645,992中所述制得均匀的线型乙烯聚合物。均匀乙烯聚合物具有均匀的支链分布，也就是说，基本上所有的聚合物分子均具有相同数量的并入每个分子的共聚单体。已经使用组成分布分支指数(CDBI)来描述支链分布(或均一性或非均一性)的特征，并且其可以采用美国专利5,008,204中所述的装置，按照美国专利5,246,783来进行测定，各项专利公开的内容经此引用并入本文。不均匀聚合物的CDBI在30到70之间，而均匀聚合物的CDBI则在80到最高可为100之间。
聚合物混合物(A)可以是干燥材料的物理混合物，随后熔融混合，或者如美国专利5,844,045中所述且要求权利的那样，聚合物混合物(A)可以原位制得，其公开的内容经此引用并入本文。
通常密度在0.941到0.965g/cm3之间的高密度聚乙烯(HDPE)典型地是乙烯的均聚物，相对于各种乙烯和-烯烃的线型共聚物，其几乎不含支链。HDPE是众所周知的，可以以各种级别市售的，而且可以用于本发明中。
本发明的聚丙烯共聚物是包括由丙烯和乙烯和/或一种或多种不饱和共聚单体获得的单元。术语“共聚物”包括三聚物、四聚物等等。“无规共聚物”指的是单体随机分布在整个聚合物链上的共聚物。典型地，聚丙烯共聚物包括占共聚物至少60wt％、优选为至少70wt％和更优选为至少80wt％的得自丙烯的单元。乙烯和/或一种或多种共聚物的不饱和共聚单体含有至少0.1、优选为至少1和更优选为至少3wt％，而且不饱和共聚单体的典型最大量不超过共聚物的40wt％，优选不超过30wt％。此类聚丙烯的无规共聚物是可以市售的，例如，可以从陶氏化学公司获得的陶氏聚丙烯树脂(DOW Polypropylene RESINSTM)。
苯乙烯/丁二烯共聚物(SBC)是本领域内已知的透明树脂。SBC树脂既可以提供高透明性，又可以提供良好的薄膜劲度。适宜SBC树脂的例子为可以从雪佛龙菲利浦化学公司获得的SBC的K-树脂系列(K-Resinfamily)。
环-烯烃共聚物(COC)是通过金属茂催化剂制造的无定形玻璃透明的乙烯和降冰片烯共聚物。COC可以市售，例如，可以从Ticona公司获得的TopasCOC共聚物。
聚苯乙烯是在本领域内为人熟知的透明树脂，并且可以市售。聚苯乙烯既可以提供高透明性，又可以提供良好的薄膜劲度。适宜的市售聚苯乙烯的例子是可以从陶氏化学公司获得的StyronTM663聚苯乙烯。
乙烯-乙酸乙烯酯共聚物是广为人知且可市售的弹性体。
优选地，(A)的混合物包括大约40到大约75wt％均匀支化聚乙烯，和大约25wt％到大约60wt％不均匀支化聚乙烯。不均匀支化聚乙烯的分子量分布Mw/Mn在大约3到大约6之间，而均匀支化聚乙烯的分子量分布Mw/Mn在大约1.5到大约3之间。(A)的混合物的熔融指数I2在大约6克/10分钟到大约20克/10分钟之间。按照ASTM D1238，条件190℃/2.16千克，测量熔融指数(I2)。(A)的混合物的密度在大约0.88克/立方厘米到大约0.92克/立方厘米之间。在示差扫描量热曲线上，(A)的混合物具有至少3个熔融峰。优选地，(A)的混合物包括大约50到大约60wt％均匀支化聚乙烯和大约40到大约50wt％不均匀支化聚乙烯。
组分(B)可以选自低密度聚乙烯、乙烯/羧酸共聚物、乙烯/羧酸共聚物的离聚物、乙烯乙酸乙烯酯共聚物、高熔融强度聚丙烯均聚物或高熔融强度聚丙烯共聚物。组分(B)应具有至少两倍于混合物(A)的熔融强度，和甚至更高的熔融强度，例如，大约为混合物(A)熔融强度的2.5倍，大约为混合物(A)熔融强度的3倍或更高，同样是可以预期的。
不受任何特定理论的束缚，值得相信的是，三相聚合物(三个熔融峰)的好处在于，由于第一峰(也就是说，出现在最低温度下的主峰)的高百分比，能够以低热密封引发温度进行密封。同时可以用维卡软化温度表示第二和第三峰提供的全面抗热性。
优选地，组分(A)构成大约60到大约80wt％所述组合物，组分(B)构成大约20到大约40wt％所述组合物。在本发明的组合物中可以有利地使用通常用于本领域中，例如抗氧化剂的添加剂。
在另一个具体实施方案中，由聚合物组合物制造一种薄膜层，该组合物包括：
(A) 大约60到大约80wt％至少一种均匀支化聚乙烯和至少一种不均匀支化聚乙烯的混合物，以及
(B) 大约20到大约40wt％至少一种熔融强度至少为混合物(A)的两倍的聚合物。
本发明的薄膜层适用于汁液包装袋、快餐包装，和除此之外的垂直/成形/填充/密封用途。
实施例
在实施例的薄膜生产中使用下列树脂。
熔融指数I2为2.3克/10分钟(由ASTM D-1238，条件190℃/2.16千克测得的)，密度为0.918克/立方厘米(由ASTM D-792测得的)，按照前面本发明的详细说明中所述方法测得的熔融张力为8克，并含有300ppm的受阻碍酚性抗氧剂(在此实施例中，可以从汽巴嘉基(CibaGeigy)获得的Irganox 1010)的LDPE。
混合物(A)  一种56wt％熔融指数I2为20克/10分钟(由ASTMD-1238，条件190℃/2.16千克测得的)、密度为0.903克/立方厘米(由ASTM D-792测得的)的均匀乙烯聚合物，和44wt％不均匀乙烯聚合物的混合物，由此合成的混合物具有20克/10分钟的最终熔融指数和0.907克/立方厘米的密度。
在装配有按照如下区域温度运行的3.5”挤出机(9厘米)(32L/D)的挤出涂布生产线上实施本配方：
桶1 200  桶2  250  桶3  280  桶4  290
桶5 290    桶6  290  边缘         290
管子区域1到3    290  供料区1-3    290
模具区1到10     290
向内弯曲(毫米)
收缩(米/分钟)
在氮气气氛下，采用TA Q-1000示差扫描量热计进行示差扫描量热(DSC)测量。通过大约100℃/分钟的快速加热至180℃将每个样品熔融，令其在180℃保持3分钟，以10℃/分钟的速率冷却到零下40℃，并通过以10℃/分钟的速率从零下40℃扫描到150℃记录其常规DSC吸热。可以在ASTM D-3417和ASTM D-3418中找到适于除LLDPE以外的聚合物温度循环设置。
可以根据ASTM D1525或ISO 306测量维卡软化点。
采用Goettfert Rheotens毛细管流变仪，将温度为190℃的熔融聚合物以30.26立方毫米/秒的速率加入到内径为2.1毫米、模长41.9厘米且流入角为90度的模具中，来测量熔融强度。活塞直径为9.54毫米，活塞速率为0.423毫米/秒，剪切速率为33秒-1，收缩为100毫米。随即用具有10厘米的气隙和2.4平方毫米/秒的加速度变化率的GoettfertRheotens Model 71.97拉伸流变仪的轮子拉伸熔化物。熔融强度是以百分之一牛顿(cN)测量的、在纺线(spinline)中的力的平顶值，或在缺少平顶值情况下的峰值，如采用高强度材料所经常遭受到的熔融强度。
用ISO 527-3或相当标准的测试方法测量聚合物的拉伸性能。拉伸性能包括2％割线模量、最大拉伸强度、和最大拉伸强度处的延伸率。按照ASTM D-3706使用A J & B Topwave测定热粘性引发温度，并可同样使用A J & B Topwave确定热封性。热封机装有5毫米宽的特氟纶涂装热封棒，采用0.5牛顿/平方毫米的密封棒压力和0.5秒的停留时间进行密封。在随即制得热封的2秒滞留后，根据ASTM D-88，用一台Instron多功能试验仪测量热封强度。可以用Sentinel或Lioyd K装置(instrument with)测量热封引发温度。
收缩是聚合物可拉伸性(表#？)的量度标准，由此可以起到在稳定的织物结构中聚合物可以拉伸多薄的指示器的作用。通过首先设定稳定涂布量和等价于如表中所示、在既定工艺条件下的恒定压出量的线速度来测定收缩。通过在保持恒定压出量的同时提高线速度，直到发生分级织物缺损，来测量收缩速度。将织物缺损分为包括边缘撕裂、织物撕裂和织物一面超过+/-3毫米离子的边缘波纹化的熔融拉伸限制。

Claims (25)

1.一种聚合物组合物，包括：
(A)    60到80wt％的由至少一种均匀支化聚乙烯和至少一种不均匀支化聚乙烯组成的混合物，以及
(B)    20到40wt％至少一种熔融强度至少为混合物(A)两倍的聚合物。
2.根据权利要求1所述的组合物，其中(A)的混合物包括40到75wt％均匀支化聚乙烯和25到60wt％不均匀支化聚乙烯。
3.根据权利要求1所述的组合物，其中均匀支化聚乙烯是乙烯和至少C3-C20α-烯烃的共聚体。
4.根据权利要求1所述的组合物，其中不均匀支化聚乙烯具有3到6之间的分子量分布Mw/Mn。
5.根据权利要求1所述的组合物，其中(A)混合物具有10克/10分钟到30克/10分钟之间的熔融指数I2。
6.根据权利要求1所述的组合物，其中(A)混合物具有0.88克/立方厘米到0.92克/立方厘米之间的密度。
7.根据权利要求1所述的组合物，其中(A)混合物在示差扫描量热曲线上具有至少三个熔融峰。
8.根据权利要求1所述的组合物，其中均匀支化聚乙烯具有1.5到3之间的分子量分布Mw/Mn。
9.根据权利要求1所述的组合物，其中(A)混合物包括50到60wt％均匀支化聚乙烯和40到50wt％不均匀支化聚乙烯。
10.根据权利要求1所述的组合物，其中(B)选自低密度聚乙烯、乙烯/羧酸共聚物、乙烯/羧酸共聚物的离聚物、乙烯乙酸乙烯酯共聚物、高熔融强度聚丙烯均聚物或高熔融强度聚丙烯共聚物。
11.一种用聚合物组合物制得的薄膜层，所述组合物包括
(C)    60到80wt％的由至少一种均匀支化聚乙烯和至少一种不均匀支化聚乙烯组成的混合物，以及
(D)    20到40wt％至少一种熔融强度至少为混合物(A)两倍的聚合物。
12.根据权利要求10所述的薄膜层，其中(A)混合物包括40到75wt％均匀支化聚乙烯和25到60wt％不均匀支化聚乙烯。
13.根据权利要求10所述的薄膜层，其中均匀支化聚乙烯是乙烯和至少C3-C20α-烯烃的共聚体。
14.根据权利要求10所述的薄膜层，其中不均匀支化聚乙烯具有3到6之间的分子量分布Mw/Mn。
15.根据权利要求10所述的薄膜层，其中(A)混合物具有10克/10分钟到30克/10分钟之间的熔融指数I2。
16.根据权利要求10所述的薄膜层，其中(A)混合物具有0.88克/立方厘米到0.92克/立方厘米之间的密度。
17.根据权利要求10所述的薄膜层，其中(A)混合物在示差扫描量热曲线上具有至少三个熔融峰。
18.根据权利要求10所述的薄膜层，其中均匀支化聚乙烯具有1.5到3之间的分子量分布Mw/Mn。
19.根据权利要求10所述的薄膜层，其中(A)的混合物包括50到60wt％均匀支化聚乙烯和40到50wt％不均匀支化聚乙烯。
20.一种含有权利要求10所述薄膜层的装配品。
21.根据权利要求1所述的组合物，进一步包括至少一种选自低密度聚乙烯、线型低密度聚乙烯、高密度聚乙烯、其混合物、聚丙烯均聚物、聚丙烯无规共聚物、苯乙烯/丁二烯共聚物、聚苯乙烯、乙烯-乙酸乙烯酯共聚物或环-烯烃共聚物的聚合物。
22.根据权利要求10所述的薄膜层，进一步包括至少一种其它层。
23.根据权利要求10所述的薄膜层，其中(B)选自低密度聚乙烯、乙烯/羧酸共聚物、乙烯/羧酸共聚物的离聚物、乙烯乙酸乙烯酯共聚物、高熔融强度聚丙烯均聚物或高熔融强度聚丙烯共聚物。
24.一种包括至少两层的薄膜，其一层是由一种聚合物组合物制成的，所述组合物包括
(A)    至少一种均匀支化聚乙烯和至少一种不均匀支化聚乙烯的混合物，以及另一层包括
(B)    至少一种熔融强度至少为(A)的混合物两倍的其它聚合物。
25.一种聚合物组合物，包括
(A)    60到80wt％的具有至少三个熔融峰的乙烯聚合物，以及
(B)    20到40wt％的至少一种熔融强度至少为(A)两倍的聚合物。
CNB038226928A 2002-09-23 2003-09-22 用于挤出涂布的聚合物组合物 Expired - Lifetime CN100537649C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41284302P 2002-09-23 2002-09-23
US60/412,843 2002-09-23

Publications (2)

Publication Number Publication Date
CN1685006A true CN1685006A (zh) 2005-10-19
CN100537649C CN100537649C (zh) 2009-09-09

Family

ID=32030934

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB038226928A Expired - Lifetime CN100537649C (zh) 2002-09-23 2003-09-22 用于挤出涂布的聚合物组合物

Country Status (13)

Country Link
US (1) US7846552B2 (zh)
EP (1) EP1546254B1 (zh)
JP (1) JP2006500443A (zh)
KR (1) KR101043187B1 (zh)
CN (1) CN100537649C (zh)
AU (1) AU2003275062A1 (zh)
BR (1) BRPI0314479B1 (zh)
CA (1) CA2499517C (zh)
DE (1) DE60317692T2 (zh)
DK (1) DK1546254T3 (zh)
ES (1) ES2293022T3 (zh)
MX (1) MXPA05003160A (zh)
WO (1) WO2004026955A2 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103987740A (zh) * 2011-12-09 2014-08-13 北欧化工股份公司 一种新型的聚乙烯

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723398B1 (en) * 1999-11-01 2004-04-20 Dow Global Technologies Inc. Polymer blend and fabricated article made from diverse ethylene interpolymers
AU2005307750B2 (en) * 2004-11-16 2011-09-01 Dow Global Technologies Llc Elastomeric compositions with improved resistance to necking for high speed sheet extrusion applications
WO2006124369A1 (en) * 2005-05-12 2006-11-23 Dow Global Technologies Inc. Thermoformed, extruded sheeting with reduced gloss
US20070010626A1 (en) * 2005-07-11 2007-01-11 Shankernarayanan Manivakkam J Polyethylene compositions
US9018310B2 (en) * 2009-04-06 2015-04-28 Polyone Designed Structures And Solutions Llc Polymer blend composition for automotive flooring applications
US9885149B2 (en) * 2009-07-08 2018-02-06 Dow Global Technologies Llc Carpet and carpet backing
WO2012004422A1 (es) 2010-07-06 2012-01-12 Dow Global Technologies Llc Mezclas de polímeros de etileno y artículos orientados con resistencia mejorada a la contracción
US9287563B2 (en) 2011-01-20 2016-03-15 Samsung Sdi Co., Ltd. Electrode for lithium secondary battery and lithium secondary battery including the same
CN102610789B (zh) * 2011-01-20 2016-03-02 三星Sdi株式会社 用于锂可充电电池的电极和包括该电极的锂可充电电池
WO2013006409A1 (en) * 2011-07-06 2013-01-10 Dow Global Technologies Llc Polyethylene with high melt strength for use in extrusion coating
US10065404B2 (en) * 2011-07-29 2018-09-04 Eastman Chemical Company In-line lamination of heavy-gauge polymer sheet with a pre-formed polymer film
CA2868640C (en) 2014-10-21 2021-10-26 Nova Chemicals Corporation Solution polymerization process
WO2016063205A2 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Dilution index
KR101786313B1 (ko) 2016-03-17 2017-10-17 현대자동차주식회사 자동차 발포에어덕트에 사용되는 폴리올레핀 복합재 조성물
US10329412B2 (en) 2017-02-16 2019-06-25 Nova Chemicals (International) S.A. Caps and closures
US10442920B2 (en) 2017-04-19 2019-10-15 Nova Chemicals (International) S.A. Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations
US10882987B2 (en) 2019-01-09 2021-01-05 Nova Chemicals (International) S.A. Ethylene interpolymer products having intermediate branching
US11046843B2 (en) 2019-07-29 2021-06-29 Nova Chemicals (International) S.A. Ethylene copolymers and films with excellent sealing properties

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076698A (en) 1956-03-01 1978-02-28 E. I. Du Pont De Nemours And Company Hydrocarbon interpolymer compositions
CA849081A (en) 1967-03-02 1970-08-11 Du Pont Of Canada Limited PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES
JPS57128729A (en) * 1981-02-02 1982-08-10 Sekisui Chem Co Ltd Olefinic resin composition
JPS60123544A (ja) * 1983-12-07 1985-07-02 Showa Denko Kk ラミネ−ト用エチレン系重合体組成物
US4950541A (en) * 1984-08-15 1990-08-21 The Dow Chemical Company Maleic anhydride grafts of olefin polymers
JPS61194247A (ja) * 1985-02-18 1986-08-28 株式会社クラレ 複合繊維布帛
US5133917A (en) * 1986-09-19 1992-07-28 The Dow Chemical Company Biconstituent polypropylene/polyethylene fibers
US5008204A (en) 1988-02-02 1991-04-16 Exxon Chemical Patents Inc. Method for determining the compositional distribution of a crystalline copolymer
US5082899A (en) * 1988-11-02 1992-01-21 The Dow Chemical Company Maleic anhydride-grafted polyolefin fibers
US5108827A (en) * 1989-04-28 1992-04-28 Fiberweb North America, Inc. Strong nonwoven fabrics from engineered multiconstituent fibers
WO1993001622A1 (en) * 1991-07-09 1993-01-21 Scimat Limited Polymeric sheet
EP0594777A1 (en) 1991-07-18 1994-05-04 Exxon Chemical Patents Inc. Heat sealed article
US5246783A (en) 1991-08-15 1993-09-21 Exxon Chemical Patents Inc. Electrical devices comprising polymeric insulating or semiconducting members
US5677383A (en) * 1991-10-15 1997-10-14 The Dow Chemical Company Fabricated articles made from ethylene polymer blends
US6448355B1 (en) * 1991-10-15 2002-09-10 The Dow Chemical Company Elastic fibers, fabrics and articles fabricated therefrom
US5582923A (en) * 1991-10-15 1996-12-10 The Dow Chemical Company Extrusion compositions having high drawdown and substantially reduced neck-in
US6143854A (en) * 1993-08-06 2000-11-07 Exxon Chemical Patents, Inc. Polymerization catalysts, their production and use
PT681592E (pt) 1993-01-29 2001-01-31 Dow Chemical Co Interpolimerizacoes de etileno
US5929128A (en) 1993-08-18 1999-07-27 The Dow Chemical Company Gaskets made from olefin polymers
DE69410948T2 (de) 1993-11-29 1999-02-11 Sumitomo Chemical Co., Ltd., Osaka Harzzusammensetzung für Strangpressen
IL115911A0 (en) * 1994-11-14 1996-01-31 Dow Chemical Co Extrusion compositions having high drawdown and substantially reduced neck-in
US5879768A (en) * 1995-10-06 1999-03-09 The Dow Chemical Company Pouches for packaging flowable materials
US5616408A (en) * 1995-12-22 1997-04-01 Fiberweb North America, Inc. Meltblown polyethylene fabrics and processes of making same
JPH1077374A (ja) 1996-09-04 1998-03-24 Kanegafuchi Chem Ind Co Ltd プロピレン系樹脂組成物、改質プロピレン系樹脂組成物および前記組成物の製法
JPH10120841A (ja) * 1996-10-18 1998-05-12 Asahi Chem Ind Co Ltd 押出しラミネート用ポリエチレン系樹脂組成物及びその押出しラミネート品
ATE218599T1 (de) 1996-11-13 2002-06-15 Dow Chemical Co Schrumpffolie mit ausgeglichenen eigenschaften oder verbesserter zähigkeit und verfahren zu ihrer herstellung
NZ335732A (en) * 1996-11-13 2000-12-22 Dow Chemical Co Polyolefin compounds with balanced sealant properties and improved modulus and method for same
JPH10168245A (ja) * 1996-12-12 1998-06-23 Asahi Chem Ind Co Ltd 押出しラミネート用ポリエチレン系樹脂組成物及びその押出しラミネート品
AR018359A1 (es) * 1998-05-18 2001-11-14 Dow Global Technologies Inc Articulo resistente al calor , configurado, irradiado y reticulado, libre de un agente de reticulacion de silano
US6339134B1 (en) * 1999-05-06 2002-01-15 Univation Technologies, Llc Polymerization process for producing easier processing polymers
US6423421B1 (en) * 1999-08-11 2002-07-23 Sealed Air Corporation Heat shrinkable film with multicomponent interpenetrating network resin
US6977287B2 (en) 1999-12-10 2005-12-20 Exxonmobil Chemical Patents Inc. Propylene diene copolymers
AU2001263457A1 (en) * 2000-05-26 2001-12-11 The Dow Global Technologies Inc. Polyethylene rich/polypropylene blends and their uses
US6734265B1 (en) * 2000-10-06 2004-05-11 Univation Technologies, Llc. Linear low density polyethylenes with high melt strength and high melt index ratio
JP4288157B2 (ja) * 2001-07-17 2009-07-01 ダウ グローバル テクノロジーズ インコーポレイティド 二構成要素弾性繊維及び二組成成分弾性繊維、及びそれらからセルロース系構造物を製造する方法
US7052636B2 (en) * 2002-01-15 2006-05-30 3M Innovative Properties Company Heat treated profile extruded hook
WO2003082971A2 (en) 2002-03-22 2003-10-09 Dow Global Technologies Inc. Thermoplastic vulcanizate composition and method of making same
WO2003089501A1 (en) * 2002-04-19 2003-10-30 Gammatron (Pty) Ltd Method of increasing the hydrostatic stress strength of a polymer
CA2536292C (en) 2003-09-05 2012-05-08 Dow Global Technologies Inc. Improved resin compositions for extrusion coating
AU2005224261B2 (en) 2004-03-19 2010-04-01 Dow Global Technologies, Inc. Film layers made from polymer formulations

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103987740A (zh) * 2011-12-09 2014-08-13 北欧化工股份公司 一种新型的聚乙烯
CN103987740B (zh) * 2011-12-09 2016-08-24 北欧化工股份公司 一种聚乙烯

Also Published As

Publication number Publication date
AU2003275062A1 (en) 2004-04-08
EP1546254A2 (en) 2005-06-29
US20050256270A1 (en) 2005-11-17
MXPA05003160A (es) 2005-07-05
CN100537649C (zh) 2009-09-09
CA2499517A1 (en) 2004-04-01
WO2004026955A2 (en) 2004-04-01
BR0314479A (pt) 2005-07-26
WO2004026955A3 (en) 2004-06-24
DE60317692D1 (de) 2008-01-03
BRPI0314479B1 (pt) 2015-10-13
EP1546254B1 (en) 2007-11-21
ES2293022T3 (es) 2008-03-16
CA2499517C (en) 2009-01-20
DE60317692T2 (de) 2008-10-30
DK1546254T3 (da) 2008-04-14
KR20050047543A (ko) 2005-05-20
US7846552B2 (en) 2010-12-07
KR101043187B1 (ko) 2011-06-20
JP2006500443A (ja) 2006-01-05

Similar Documents

Publication Publication Date Title
CN100537649C (zh) 用于挤出涂布的聚合物组合物
EP0971980B1 (en) Lldpe blends with an ethylene-norbornene copolymer for resins of improved toughness and processibility for film production
US6969741B2 (en) Polyethylene compositions for rotational molding
EP0721967B1 (en) Thermoplastic seal and wrapping film
EP0052555B2 (fr) Compositions de polyéthylène améliorées pour extrusion, notamment pour extrusion-soufflage
CN100351304C (zh) 树脂组合物及由此获得的薄膜
JP6482081B2 (ja) ポリオレフィン組成物およびポリオレフィン延伸フィルムとその製法
CN1823106A (zh) 注塑聚合物
US11174356B2 (en) Polymer compositions for injection stretch blow molded articles
EP2891680B1 (en) Polymer blend: HDPE with ethylene-norbornene or propylene-norbornene copolymer
US20120064269A1 (en) Multilayered Composite Plastic Material Containing an Adhesion Promoter Interlayer
EP1216824B1 (en) Sealant for polypropylene and easily openable hermetically sealed package including the same
CA2585376C (en) Elastomeric compositions with improved resistance to necking for high speed sheet extrusion applications
WO1999033913A1 (en) Easy-open packaging
US6428901B1 (en) Films formed from blends of polyethylene and polypropylene
CN1668688A (zh) 收缩薄膜
JPH0665448A (ja) 樹脂組成物
JP3324975B2 (ja) ストレッチ包装用フィルム
EP0777702A1 (en) Polyketone linear low density polyethylene blends
JP2004231919A (ja) プロピレン・α−オレフィン共重合体組成物、成形体およびその用途
KR20230165538A (ko) 이축배향 필름용 폴리에틸렌 수지 조성물
JP2023134193A (ja) エチレン系樹脂組成物およびその用途
JPH09327889A (ja) シーラントフィルム
MXPA99008934A (en) Lldpe blends with an ethylene-norbornene copolymer for resins of improved toughness and processibility for film production

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20090909

CX01 Expiry of patent term