CN1863860B - 用于热恢复发泡管的组合物 - Google Patents

用于热恢复发泡管的组合物 Download PDF

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Publication number
CN1863860B
CN1863860B CN2004800290920A CN200480029092A CN1863860B CN 1863860 B CN1863860 B CN 1863860B CN 2004800290920 A CN2004800290920 A CN 2004800290920A CN 200480029092 A CN200480029092 A CN 200480029092A CN 1863860 B CN1863860 B CN 1863860B
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polymer
pipe
thermal contraction
layer
temperature
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CN1863860A (zh
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A·梅汉
R·J·雷沃伊尔塔斯
J·J·因佩里亚勒
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TE Connectivity Corp
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Tyco Electronics Corp
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    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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Abstract

本发明提供了用于热收缩发泡结构的熔体组合物，所述熔体组合物包含至少一种基础聚合物和由至少一种热激活性化合物密封在多个聚合物壳中制成的发泡剂。所述熔体组合物也可包含交联促进剂或其它添加剂。本发明还提供制备热收缩聚合物发泡管的方法。本发明提供了含有至少一种具有熔融温度的基础聚合物材料和具有活化温度的发泡剂的熔体组合物。所述熔体组合物在升高的温度下混合。所述熔体组合物随后在高温下挤出通过模具。挤出发泡管随后进行处理，通常为热处理。此外，本发明还提供了含有挤出发泡聚合物管的内层和外层的热收缩发泡聚合物管，其中每层由至少一种基础聚合物和发泡剂制成，所述发泡剂包括密封在多个聚合物壳中的热激活性化合物。

Description

用于热恢复发泡管的组合物
发明背景
发明领域
本申请涉及可热恢复(如热收缩)的聚合物发泡管。更具体地讲，它涉及含有分散的胶囊密封的发泡剂的挤出聚合物发泡管。
发明介绍
对工具、用具到服装的广泛应用中的各种基材如金属线、棒、管道或其它伸长的无规形状(如把手和柄)而言，绝缘、垫料或防护层经常是必需的。发泡聚合物涂层是提供这种绝缘或垫料的有效而廉价的方法。特别是管状泡沫结构可挤出并制成热收缩管。当基材插入发泡管且随后将该管加热至用于该管的聚合物组合物的聚合物熔点以上时，热收缩聚合物发泡管会在基材上紧密恢复。
挤出是经常用于聚合物材料的连续成型方法。在挤出过程中，聚合物材料连续受热并受到机械作用成为均匀的熔融态粘性流体料。或者，可引入已为熔融态的聚合物到挤出装置。接着受热料经推动通过末端开口的模具。聚合物从模具中以模具的普通形状挤出，通常它为环形的。再通过空气冷却或水骤冷挤出材料使挤出熔体凝固。凝固的材料通常经过交联、随后机械膨胀以制备热恢复物品。加热膨胀物品使之恢复(通常通过收缩)到接近其最初未膨胀的形状。
当需要发泡挤出物时，聚合物熔体经常与发泡剂混合。化学发泡剂一般为热激活性细粉的形式，如碳酸氢钠或偶氮二酰胺。当含有发泡剂粉末的聚合物材料受热和熔融时，大部分粉末分解并在聚合物熔体结构中形成气泡或气球。气体立即溶于聚合物熔体，由于挤出机中挤出方法条件下普遍的高压，大部分保持溶于熔体中。然而，在形成发泡聚合物材料管的常规管挤出方法中，当熔融聚合物材料离开模具时，一些溶解的气体释放到了挤出聚合物发泡管的内部空穴中。这能导致最终成品形状和尺寸的缺陷。
或者，在挤出方法后期(即加热聚合物后但在将聚合物熔体最终泵送通过挤出模具之前)将物理发泡剂加入聚合物熔体中。这种方法也有与上述常规方法同样的缺点，且仍然存在无法接受的聚合物发泡管形状和尺寸上的变化。此外，成品产物的泡沫室尺寸均匀性差，这可能对交联步骤后管直径膨胀能力产生负面影响。
从而，需要用于管挤出的聚合物熔体组合物，所述组合物形成发泡聚合物材料，所述聚合物材料能制成实用的热收缩泡沫结构，优选在例如管挤出或型坯吹模方法的连续方法中，但不允许气体逃逸并使管状结构变形。
发明概述
本发明的实施方案提供了用于热收缩泡沫结构的熔体组合物。所述组合物包含至少一种基础聚合物和发泡剂。该发泡剂本身包含至少一种热激活性化合物及密封所述热激活性化合物的聚合物壳。
本发明的另一个实施方案提供了用于热收缩泡沫结构的熔体组合物。所述组合物包含约80-约99.9％重量的乙烯/乙酸乙烯酯共聚物基础聚合物、约0.1-约10％重量的发泡剂和任选约0-约19.9％重量的任选填充剂。
本发明的还一个实施方案提供了制备热收缩聚合物发泡管的方法。首先提供熔体组合物，所述组合物包含至少一种具有熔融温度的基础聚合物材料和具有活化温度的发泡剂。所述熔体组合物在升高的温度下混合。随后在高温下将所述熔体组合物从模具中挤出。该挤出发泡管随后经过后处理。
本发明的再一个实施方案提供包含挤出发泡聚合物管的至少一个内层和一个外层的热收缩发泡聚合物管。每层由至少一种基础聚合物和发泡剂制成，其中所述发泡剂包含密封在聚合物壳中的热激活性化合物。
通过以下本发明的描述，本发明的其它方面将变得显而易见。
附图简述
图1是具有内表面和外表面的本发明的实施方案的发泡聚合物管的透视图。
图2是具有内层和外层以及置于两层之间的中间层的本发明的实施方案的发泡聚合物管的透视图。
优选实施方案详述
用于本发明的发泡聚合物的组合物包含至少一种基础聚合物组合物和发泡剂。此外，所述组合物(在此也称为熔体组合物)可包含任选填充剂，如抗氧剂、交联促进剂、热稳定剂、着色剂、阻燃剂等。
选择组合物的基础聚合物材料使得其容易熔融、承受挤出热量和压力而不降解并与发泡剂均匀混合。热塑性聚合物满足基础聚合物的所有要求。优选的基础聚合物组合物包括但不限于聚乙烯(包括极低密度聚乙烯、低密度聚乙烯、中密度聚乙烯、高密度聚乙烯和茂金属聚合乙烯)；含C4-C10烯烃的乙烯共聚物；聚乙烯和乙酸乙烯酯、乙酸烷基酯、丙烯酸、马来酸酐或羧酸的共聚物和三元共聚物；聚丙烯；三元乙丙橡胶(EPDM)；丁苯橡胶；与聚烯烃的橡胶共混物；聚氨酯；聚酰胺；聚酯；聚硅氧烷；含氟聚合物；其它热塑性聚合物及其中两种或多种的混合物。经常希望结晶度比较高的聚合物与结晶度比较低的聚合物混合以获得特殊的热恢复性能。一种优选基础聚合物可得自DuPont，以商品名ElvaxTM 460出售的乙烯/乙酸乙烯酯共聚物(EVA)。
如本领域技术人员所知，基础聚合物材料的选择取决于产品的最终用途以及所涉及的任何其它材料或方法。例如，用于能在低热收缩温度下容易安装并具有舒适把手的管的基础聚合物(如乙酸乙烯酯含量高(即至少15％重量)的EVA聚合物或EVA-EPDM聚合物共混物)可用于制备室外用具(例如剪草机)上的防护装置，而能承受腐蚀性化学品侵蚀的基础聚合物(如聚偏氟乙烯/六氟丙烯共聚物)可用于制备管道的绝缘层。
基础聚合物一般占熔体组合物的约80％重量至约99.9％重量，优选占熔体组合物的约90％重量至约99.9％重量。
本发明使用多个聚合物壳密封热激活性化合物的形式的发泡剂。这些胶囊经常称为微球。所选择的化合物优选在室温下为液体，具有相对低的沸点(即低于50℃)。选择具体的化合物和聚合物壳材料使得聚合物壳在整个挤出的严格条件中保持完整；更具体地讲，选择聚合物壳材料使得壳在混合方法所用热和压力下不会降解或熔融，且在挤出方法所施加的力下不会破裂。
微球还具有活化温度，在此温度下胶囊密封的液体开始沸腾并变成气体。在此活化温度下，聚合物壳足够柔软以开始膨胀来允许化合物进入气态时体积增加同时仍然有效地密封化合物。微球的这种膨胀在基础聚合物中形成了空穴以形成发泡材料。通常活化温度包括一个范围以适应具体批产物中微球尺寸的差异。此外，胶囊密封的发泡剂经常通过最低膨胀温度(或温度范围)，即密封剂开始膨胀的温度和最高膨胀温度(或温度范围)，即密封剂完成膨胀的温度进行定义。活化温度一般略低于最高膨胀温度。
聚合物壳可包含但不限于氯乙烯、偏氯乙烯、丙烯腈、甲基丙烯腈、苯乙烯的聚合物和共聚物或其组合。优选聚合物壳密封烃基液体(如异戊烷或异丁烷)。
本发明的优选实施方案中，未膨胀的聚合物壳优选直径为约3μm至约60μm，更优选约6μm至约40μm。未膨胀的胶囊密封发泡剂的密度一般小于25kg/m3。所用的未膨胀的胶囊密封发泡剂优选占熔体组合物的约0.1％重量至约10％重量，更优选占熔体组合物的约1％重量至约7％重量，最优选占熔体组合物的约2.5％重量至约6％重量，尽管所用发泡剂的量是聚合物类型、发泡剂类型和任选填充剂的存在的函数。
一种优选的胶囊密封发泡剂为得自Expancel，Inc.的ExpancelTM聚合物微球。通常这种微球的未膨胀直径为约6μm至约40μm，膨胀直径为约20μm至约150μm。更优选胶囊密封的热激活性发泡剂为ExpancelTM 091-DU-80或ExpancelTM 092-DU-120，两者的聚合物壳都包含丙烯腈和甲基丙烯腈的共聚物，两者都密封异戊烷。
发泡剂的选择部分取决于应用选择的基础聚合物和用于挤出方法的加工温度。在挤出或吹模方法中存在两个重要的温度区，混合或熔体共混温度区(在此基础聚合物熔融)和挤出模具温度区。选择混合温度区高于基础聚合物的熔融温度。熔融温度定义为示差扫描量热计(DSC)曲线的吸热峰。当熔体组合物包含一种以上聚合物，DSC曲线上的峰超过一个时，熔融温度定义为最高温度峰。
然而为了制备均匀稳定的泡沫体，优选直到或仅稍微早于聚合物混合物挤出模具，发泡剂微球才开始膨胀而不过早膨胀。优选选择发泡剂使得其活化温度高于混合温度区，但低于挤出模具温度区。因此优选选择最低膨胀温度高于基础聚合物熔融温度的发泡剂，从而当基础聚合物材料熔融时发泡剂不会产生膨胀。更优选选择的发泡剂的最低膨胀温度高于挤出方法的熔融步骤的所要求混合温度。
为了制备热恢复管，聚合物材料经常交联。交联赋予聚合物其现有形状的“记忆”且赋予成品聚合物管受热时收缩或其它改变形状的能力。交联还提高了发泡聚合物的结构刚度，确保泡沫在膨胀或热收缩时不会减压或“变平”。可通过辐射或化学方法实现交联，聚合物混合物可包含交联剂或促进剂以提高离散的聚合物链之间的交联量。现有两种一般类型的交联促进剂-化学交联促进剂和辐射交联促进剂。可使用这两类交联促进剂的一种或两种，尽管对于某些优选实施方案而言，优选只使用辐射交联促进剂。
当暴露于辐射(例如来自高能电子束)时，辐射交联促进剂用作聚合物交联的催化剂。辐射交联促进剂可选自通常用于促进聚合物交联的那些，包括氰尿酸三烯丙酯(TAC)、异氰尿酸三烯丙酯(TAIC)、偏苯三酸三烯丙酯、苯三酸三烯丙酯(triallyl trimesate)、均苯四酸四烯丙酯、1，1，3-三甲基-5-羧基-3-(4-羧基苯基)茚的二烯丙基酯、三羟甲基丙烷偏苯三酸酯(TMPTM)、季戊四醇三甲基丙烯酸酯、三(2-丙烯酰氧乙基)异氰尿酸酯、三(2-甲基丙烯酰氧乙基)偏苯三酸酯等及其组合。特别优选的辐射交联促进剂为TMPTM，以SartomerTM SR350市售得自Sartomer Company。
也可加入阻燃剂，所加入的量为能提供发泡管有效的阻燃性。合适的阻燃剂一般包括多溴化的芳族化合物如十溴联苯，结合无机材料如三氧化锑。也可使用常规量的其它填充剂，如抗氧剂、增粘剂、紫外光屏蔽剂、增塑剂、着色剂、热稳定剂及其它添加剂。如本领域技术人员所知，可根据产品的最终用途选择这些添加剂。
熔体组合物中任选填充剂的量(在本发明说明书中包括交联促进剂和阻燃剂及其它上述填充剂和添加剂)取决于基础聚合物和胶囊密封的发泡剂的种类和数量及所要求的物理性能。通常，任选填充剂的量至多为熔体组合物的约35％重量，优选至多为熔体组合物的约20％重量，特别是至多为熔体组合物的约10％重量，例如熔体组合物的约0-约19.9％重量。
本发明的发泡聚合物的挤出方法类似于本领域技术人员所知的那些。基础聚合物首先与发泡剂和其它发泡聚合物组合物成分混合。采用本领域技术人员所知的任何方法进行混合；优选在班伯里型混合机中进行混合。也可成功地采用双螺杆混合装置。在升高的温度下进行混合，所选温度足够高使得基础聚合物在混合过程中会熔融，但不应高到活化聚合物混合物中其它组分，例如发泡剂或任何交联促进剂(存在的情况下)。因此，优选混合步骤在高于所选基础聚合物的熔融温度，但低于发泡剂的最低活化温度的温度下进行。
如本领域已知，熔融态的混合聚合物共混物随后挤出通过模具。对本申请而言，模具优选为环状或环形模具；然而，模具可为本领域已知的任何形状，优选用于选定最终结果。熔融和混合后但在挤出前的聚合物共混物的温度可独立于挤出时间和点的温度进行设定。优选混合后挤出前的温度设定为等于或高于混合温度，但低于聚合物共混物中各组分的活化温度。更优选混合后挤出前温度设定为高于混合温度，但低于聚合物共混物的各组分的最低活化温度。挤出点的温度优选设定为适当超出至少发泡剂的最低活化温度，即至少超出10℃。通过等待直到恰在挤出前达到活化发泡剂的温度，发现形成了更稳定均匀的泡沫。活化时，发泡剂的聚合物胶囊中的液体变为气态，胶囊膨胀产生气泡。因此熔体组合物优选加工成所要求的形状(例如通过挤出)，并几乎同时发泡。熔体组合物离开挤出加工时为尺寸还没有膨胀的发泡聚合物管。
一旦管经过挤出和发泡，发泡剂微球为完全膨胀的状态，基础聚合物为熔体，即高粘性类液态。当挤出的发泡管恰在挤出后开始冷却时，聚合物开始在膨胀的微球周围凝固。随后微球冻结于膨胀的状态，在泡沫体中产生空穴。
挤出后，对发泡聚合物管进行后处理，一般包括一个涉及受热的步骤。优选的第一步骤中，发泡聚合物管可进行交联。根据所用交联方法的种类，管经辐射或加热至合适的温度以活化化学交联促进剂。采用本领域已知的任何方法进行辐射，例如高能电子束辐射。交联泡沫体中的聚合物线料的目的是赋予管现有管形状和直径的“记忆”以及在超过基础树脂熔点的温度下的结构稳定性。
接下来，采用本领域已知的任何方法(例如在心轴上成形或使用真空设备)使得管膨胀。优选通过压差式膨胀方法使得管膨胀。在压差式膨胀中，发泡聚合物管首先加热至足以熔融发泡聚合物管的结晶聚合物区的温度。在保持升高的温度的同时，加热管再沿着管壁受到压差。压差优选管内空气压力高于管外空气压力。施加这种空气压差的方法对本领域技术人员而言是已知的。空气压差使得管的直径膨胀。压差与发泡聚合物管的最终膨胀的直径直接相关；通过调整压差和/或其它变量(例如定型模内径)可获得所需膨胀直径。
管膨胀后，同时保持压差，将发泡聚合物管迅速冷却(如果在膨胀过程已经加热)。这种快速冷却将物理聚合物泡沫位置冻结在膨胀状态的位置。这种冷却也用于凝固发泡聚合物管。冷却后，发泡聚合物管保持其膨胀状态直到再次受热。一旦膨胀管再次受热或“恢复”，它会收缩到接近其初始尺寸。
在优选实施方案中可使用多层方法，其中聚合物管由第一层(内层)和第二层(外层)组成，两者都按照上述方法制成。这两层可共挤出。在这种实施方案中，内层和外层材料可包含相同或不同的基础聚合物和相同或不同的发泡剂。内层和外层可具有明显不同的机械性能或已发泡成不同水平的空穴含量以调整特定最终用户所需的产品的整体性能。例如，当内层由半结晶基础聚合物材料制备且发泡成较低水平的空穴含量，而外层由较柔软的无定形或弹性基础聚合物材料共混物制备且发泡成较高水平的空穴含量时可实现柔软度、手感、防振特性、机械坚固性和热收缩性能特征的极佳平衡。(空穴含量可通过对比未膨胀固态熔体组合物的比重和膨胀后组合物的比重来确定。)同样地，增粘填充剂，如线形酚醛树脂、部分聚合的树脂、妥尔油树脂酯或低分子量芳族热塑性树脂可加入内层。增粘剂提高了泡沫体表面的粘合质量并增强了泡沫体表面与基材(热收缩聚合物泡沫体在其上安置)的粘附。对于许多应用，当一个层包含具有显著水平的结晶度(如至少10％)的基础聚合物时，热恢复性能得到提高。
聚合物管中还可有其它层。例如非发泡的粘合层(优选在管发泡后加入)可存在于管的内表面以增强与基材的结合。或者，可存在发泡的或未发泡的中间层以提供结构支撑。
通过附图对本发明进行说明，其中图1为本发明的发泡管1的透视图，其中管形式的熔体组合物3具有内表面5和外表面7。
图2是本发明的另一种发泡管1的透视图。在该实施方案中，中间层13位于内层11和外层15之间。
实施例
采用胶囊密封的发泡剂的可发泡组合物的示例性制剂列于下表1中。
表1
示例性可发泡聚合物管组合物
  成分描述   成分产品   供应商   重量
  基础树脂(EVA)   Elvax<sup>TM</sup> 460   Du Pont   90.5
  胶囊密封的发泡剂   Expancel<sup>TM</sup> 092DU-120   Expancel Inc.   3.0
  辐射交联促进剂   TMPTM   Sartomer   2.0
  抗氧剂   Irganox<sup>TM</sup> 1010   Ciba Specialty Chemicals   2.0
  成分描述   成分产品   供应商   重量
  热稳定剂   Cyanox<sup>TM</sup> 1212   Cytec Industries   1.0
  着色剂(TiO<sub>2</sub>)   TiPure<sup>TM</sup> 101   DuPont   1.0
  金属减活化剂   Irganox<sup>TM</sup> 1024   Ciba Specialty Chemicals   0.5
  总计   100.0
根据供应商的产品说明，所选发泡剂ExpancelTM 092 DU-120的粒度为28-38μm(根据重均直径)，最低膨胀温度为116-126℃，最高膨胀温度为190-202℃，密度小于14kg/m3(根据热机械分析)。
在制备挤出用示例性聚合物混合物时，双螺杆混合装置安装有直径为约3.2mm(0.125英寸)的三孔线材挤出模头。在约95℃至约110℃以喂入速率为约6.8kg/hr(15磅/小时)，同时螺杆转速为约72转/分钟进行熔融和混合。当用30X显微镜检查时，在挤出线料中没有观察到发泡现象。
随后将复合物切粒，挤出通过51mm(2英寸)，24∶1 L/D的单螺杆挤出机(采用标准市售模具)。用于本实施方案的挤出方法参数列于下表2中。在发泡剂通过挤出机的最后阶段小心加热发泡剂至高于其最低膨胀温度使得发泡剂的微球膨胀。这通过提高挤出机筒和含模具的十字头的温度至接近但不高于发泡剂的最高推荐膨胀温度来实现。如上所述，本示例性实施方案中的发泡剂的最高推荐膨胀温度为约190℃至约202℃。
表2
挤出方法参数
保持约9.7mm(0.380英寸)模具内径的挤出发泡管接着经过膨胀方法。首先用1.5MeV电子束照射挤出发泡管约6.1Mrad以在基础树脂中获得交联聚合物网络。
随后通过管内表面和外表面之间所施加的压差使得发泡管膨胀。在本示例性实施方案中，在约130℃的温度下进行预膨胀加热。接下来，穿过管壁赋予压差使得管膨胀至内径为约20mm(0.8英寸)。在承受差示压力时，管以约7.6m/分钟(25英尺/分钟)的速度通过冷却区。用于本示例性实施方案的膨胀方法的进一步的参数列于下表3中。
表3
膨胀详情
  甘油浴温度   107℃(225°F)
  罐塞模具类型   12.1mm(0.475英寸)
  罐压力   72.4kPa(10.5psi)
  管压力   89.6kPa(13psi)
  线速度   9.93m/分钟(32.6英尺/分钟)
  罐至定型模间隙设定   2.54mm(0.100英寸)
如下表4给出了本示例性方法制得的最终产品的详细机械特性。当加热膨胀发泡聚合物管时，管恢复到大约初始挤出内径。
表4
产品特性
  膨胀的内径   18.3±0.5mm(0.720±0.020英寸)
  膨胀的壁厚   0.64-0.74mm(0.025-0.029英寸)
  挤出的内径   8.26mm(0.325英寸)
  挤出的壁厚   1.60-1.75mm(0.063-0.069英寸)
  恢复的内径(150℃下3分钟)   9.1mm(0.357英寸)
  恢复的壁厚(150℃下3分钟)   1.78-1.96mm(0.070-0.077英寸)
  纵向长度变化(150℃下3分钟)   -4.0％
  挤出的比重   0.42g/cm<sup>3</sup>
  挤出的空气穴百分数   56％
  膨胀的内径   18.3±0.5mm(0.720±0.020英寸)
  膨胀的比重   0.47g/cm<sup>3</sup>
  膨胀的空气穴百分数   52％
  恢复的比重   0.35g/cm<sup>3</sup>
  恢复的空气穴百分数   66％
因此上述详细说明被看作是对本发明进行说明而不是限定，应该理解正是如下权利要求(包括所有的等同物)将对本发明的精神和范围进行定义。

Claims (9)

1.一种热收缩发泡聚合物管，包含：
(A)挤出发泡聚合物的第一层，其中所述第一层为所述管的内层，含有空穴，并且包含：
(1)至少一种基础聚合物，选自聚乙烯、含C4-C10烯烃的乙烯共聚物、聚丙烯、三元乙丙橡胶、丁苯橡胶、聚烯烃与橡胶的共混物、聚氨酯、聚酰胺、聚酯、聚硅氧烷、含氟聚合物、及其混合物；和
(2)发泡剂，所述发泡剂包含：
(a)多个聚合物壳，选自氯乙烯、偏氯乙烯、丙烯腈、甲基丙烯腈或苯乙烯的聚合物，或其组合；和
(b)至少一种热激活性化合物，所述热激活性化合物密封在所述聚合物壳中，在室温下为液体，并且具有低于50℃的沸点，
和
(B)挤出发泡聚合物的第二层，其中所述第二层为所述管的外层，含有空穴，并且包含：
(1)至少一种基础聚合物，选自聚乙烯、含C4-C10烯烃的乙烯共聚物、聚丙烯、三元乙丙橡胶、丁苯橡胶、聚烯烃与橡胶的共混物、聚氨酯、聚酰胺、聚酯、聚硅氧烷、含氟聚合物、及其混合物；和
(2)发泡剂，所述发泡剂包含：
(a)多个聚合物壳，选自氯乙烯、偏氯乙烯、丙烯腈、甲基丙烯腈或苯乙烯的聚合物，或其组合；和
(b)至少一种热激活性化合物，所述热激活性化合物密封在所述聚合物壳中，在室温下为液体，并且具有低于50℃的沸点。
2.权利要求1的热收缩发泡聚合物管，其中所述内层的所述基础聚合物是半结晶性的。
3.权利要求1的热收缩发泡聚合物管，其中所述外层的所述基础聚合物是弹性的。
4.权利要求1的热收缩发泡聚合物管，其中所述外层的空穴含量大于所述内层的空穴含量。
5.权利要求1的热收缩发泡聚合物管，其中所述内层还包含选自线形酚醛树脂、妥尔油树脂酯和低分子量芳族热塑性树脂中的一种或多种的增粘填充剂材料。
6.权利要求1的热收缩发泡聚合物管，其中所述内层和外层共挤出。
7.权利要求1的热收缩发泡聚合物管，其中所述热收缩发泡聚合物管还包含至少一个位于所述内层和所述外层之间的中间层。
8.权利要求7的热收缩发泡聚合物管，其中所述至少一个中间层是发泡的或未发泡的。
9.权利要求1的热收缩发泡聚合物管，其中所述多个聚合物壳选自氯乙烯、偏氯乙烯、丙烯腈、甲基丙烯腈或苯乙烯的共聚物，或其组合。
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EP1656419B1 (en) 2008-06-04
KR20060130544A (ko) 2006-12-19
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US20050031811A1 (en) 2005-02-10
US7413785B2 (en) 2008-08-19
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