CN102471577A - 聚苯砜-聚四氟乙烯组合物及其用途 - Google Patents

聚苯砜-聚四氟乙烯组合物及其用途 Download PDF

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CN102471577A
CN102471577A CN2010800315143A CN201080031514A CN102471577A CN 102471577 A CN102471577 A CN 102471577A CN 2010800315143 A CN2010800315143 A CN 2010800315143A CN 201080031514 A CN201080031514 A CN 201080031514A CN 102471577 A CN102471577 A CN 102471577A
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D·布曼
A·德雷克斯勒
R·L·维勒曼
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Roehm GmbH Darmstadt
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06Polysulfones; Polyethersulfones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L57/00Protection of pipes or objects of similar shape against external or internal damage or wear
    • F16L57/06Protection of pipes or objects of similar shape against external or internal damage or wear against wear
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    • C08L27/00Compositions 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18Homopolymers or copolymers or tetrafluoroethene
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    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139Open-ended, self-supporting conduit, cylinder, or tube-type article

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Abstract

本发明涉及制备塑料模制品的方法,其特征在于在挤出机中在340℃-385℃的温度下,将PPSU和PTFE这两种塑料彼此混合,将所得配混料造粒,并在370℃-390℃的螺杆温度下挤出所述粒料而获得塑料模制品。所获得的塑料模制品用作输油管线中的抗磨带。

Description

聚苯砜-聚四氟乙烯组合物及其用途
技术领域
本发明涉及用于制备减摩带的由聚苯砜(PPSU)和聚四氟乙烯(PTFE)形成的混合物,所述减摩带用作柔性流体管线例如输油管线的减摩中间层(抗磨带)。
背景技术
GB 2 441 066(Technip France)描述了用于输送烃的多层构造的柔性管。在所述至少部分地可彼此相对移动的金属带之间设置减摩塑料带,所述塑料带由具有175℃-255℃的玻璃化转变温度的无定形聚合物组成。所述带由聚苯砜(PPSU)和全氟化聚合物和聚醚醚酮(PEEK)组成。在该发明的一个特定的实施方案中,将由85%聚苯砜(PPSU)与15%聚四氟乙烯(PTFE)形成的混合物混合并挤出而获得厚度1.5mm且宽度大约1m的带材。没有提及所使用的塑料的分子量。
US 2005/0229991描述了类似于GB′066中的设置,在这种情况下,中间层的材料是弹性体热塑性聚合物,例如苯乙烯-丁二烯-苯乙烯橡胶(SBS)、苯乙烯-乙烯-丁二烯-苯乙烯共聚物(SEBS)或EPDM(乙烯-丙烯-二烯)共聚物,另外还有聚丁二烯、聚异戊二烯或聚乙烯-丁烯共聚物。
发明内容
目的
鉴于所论述的现有技术,本发明的目的因此是找到用于输油管线中的减摩带的材料和/或材料混合物,其比现有技术中的材料更好地适应那里普遍存在的条件(大约130℃的温度,300-400巴的压力)。
目的的达到
根据本发明的目的通过提供使用由聚苯砜(PPSU)和聚四氟乙烯(PTFE)形成的均匀混合物成功达到,所述聚四氟乙烯具有特别高的分子量和小的粒子尺寸或粒子尺寸分布。所使用的PTFE具有特别高的分子量。然而,它尤其适合于引入工程塑料中,该工程塑料在非常高的熔体温度下加工。
根据本发明的解决方案的整个开发中决定性的是,只有PTFE在整个横截面上在PPSU基体内非常均匀且细分的分布才确保在整个使用期间所希望的效果,其中带的厚度减小,并且确保不但沿挤出方向而且垂直于挤出方向上尤其平衡的机械性能。
聚苯砜(PPSU)
作为PPSU,使用由Solvay Advanced Polymers以商标RADEL
Figure BDA0000130582850000021
R销售的聚苯砜。
所述聚合物的重复单元具有以下通式:
Figure BDA0000130582850000022
在此涉及的是具有极其低的应力开裂敏感性和极高缺口冲击强度(甚至在热老化后)和优异的化学耐性的透明的高性能塑料。所使用的RADEL R 5000nt是不满足所有航空要求的非阻燃PPSU。
它用于制备医疗技术、化学工业和卫生设施安装中的构件。所述聚合物的密度根据ISO 1183测得是1.29g/cm3,屈服应力根据ISO 527测得是70MPa,断裂伸长率根据ISO 527测得是60%,拉伸弹性模量根据ISO 527测得是2340MPa,在23℃下的Izod缺口冲击强度根据ISO 180/1A测得是49.4kJ/m2,在23℃下的Charpy(夏比)缺口冲击强度根据ISO 179/1eA测得是58.3kJ/m2
在50Hz下的介电常数根据IEC 60250测得是3.4,在1MHz下的介电常数根据IEC 60250测得是3.5,在50Hz下的介电损耗因子根据IEC 60250测得是6 1e-4。在1MHz下的介电损耗因子根据IEC60250测得是76 1e-4,击穿强度根据IEC 60243-1,根据ASTM测得是15kV/mm。对于所述击穿强度的厚度是3.2mm,根据IEC 60093的比体积电阻是9e15欧姆米。
沿着流动方向/垂直于流动方向的纵向膨胀根据ISO 11359测得是55 10-6/K,根据ISO 11357测得的熔融温度或玻璃化转变温度是215℃,耐热变形性A根据ISO 75 HDT/A(1.8MPa)测得是207℃,耐热变形性B根据ISO 75 HDT/A(0.45MPa)测得是214℃,最高温度(短期)是180℃,最高温度(长期)是160℃(根据UL 746(RTI)MechanicalW/O Imp.,40 000h的热老化)。最小应用温度是负100℃。
聚四氟乙烯(PTFE)
所使用的高分子量聚四氟乙烯(PTFE)是Zonyl
Figure BDA0000130582850000031
MP 1300型的非常细粒的聚四氟乙烯。这种PTFE特别适合作为基于HT热塑性塑料的聚合物混合物中的添加剂。
具体实施方式
实施例
配混实施例
按以下方式配混由95重量%-60重量%PPSU和40重量%-5重量%PTFE形成的混合物:
在双螺杆挤出机(制造商和型号名称:Werner & Pfleiderer ZSK25WLE(K4))中在345℃-380℃螺杆温度和250rpm下使PPSU熔融并脱气;经由侧向进料口供入PTFE。
将所获得的配混料造粒。
根据本发明的片材可以按本身已知的方式经由挤出从第一步骤中获得的粒料制备。
为此,在简单挤出的情况下经由一个挤出机制备热塑化的熔体,或在共挤出的情况下经由多个挤出机制备热塑化熔体,并将其供给挤出模具。在挤出机和挤出模头之间,可以按本身已知的方式布置附加的设备,例如熔体泵和/或熔体过滤器。然后可以将挤出的幅材供入到平整机组中或校准器中。
使粒料再次熔融并挤出而获得具有以下尺寸的带材:长度1000mm,宽度150mm和厚度1.5mm。熔体温度为大约385℃。
挤出实施例
实施例6涉及具有根据实施例1的组成的带材;在347℃的熔体温度下挤出粒料而获得带材。
实施例7涉及具有根据实施例1的组成的带材;在379℃的熔体温度下挤出粒料而获得带材。
实施例8涉及具有根据实施例1的组成的带材;在380℃的熔体温度下挤出粒料而获得带材。
实施例9涉及具有根据实施例2的组成的带材;在347℃的熔体温度下挤出粒料而获得带材。
实施例10涉及具有根据实施例2的组成的带材;在358℃的熔体温度下挤出粒料而获得带材。
实施例11涉及具有根据实施例1的组成的带材;在350℃的熔体温度下挤出粒料而获得带材。
实施例12涉及具有根据实施例4或5的组成的带材;在352℃的熔体温度下挤出粒料而获得带材。所得带材的机械特性参数如下:
Figure BDA0000130582850000051
方法
根据ISO 527-2/1BA/0.5测定弹性模量,根据ISO 179-1/1eA测定Charpy抗冲击性,根据ASTM D 5420进行Gardner试验,根据ISO8295测量摩擦系数。
所得混合物适合于制备抗磨带,该抗磨带用于制备流体用管线,例如用于柔性输油管线。

Claims (10)

1.用于制备构件的由聚苯砜和聚四氟乙烯形成的混合物,其特征在于所述混合物的PTFE含量是1重量%-15重量%且所述混合物的PPSU含量是99重量%-85重量%。
2.根据权利要求1的混合物,其特征在于所述混合物的PTFE含量是2重量%-10重量%且所述混合物的PPSU含量是98重量%-90重量%。
3.根据权利要求1的混合物,其特征在于所述混合物的PTFE含量是5重量%-10重量%且所述混合物的PPSU含量是95重量%-90重量%。
4.制备塑料模制品的方法,其特征在于将PPSU和PTFE这两种塑料彼此混合并挤出。
5.制备塑料模制品的方法,其特征在于在挤出机中在340℃-385℃的温度下,将PPSU和PTFE这两种塑料彼此混合,将所得配混料造粒,并在370℃-390℃的螺杆温度下挤出所述粒料而获得塑料模制品。
6.制备塑料模制品的方法,其特征在于在挤出机中在345℃-385℃的温度下,将PPSU和PTFE这两种塑料彼此混合,将所得配混料造粒,并在375℃-390℃的螺杆温度下挤出所述粒料而获得塑料模制品。
7.制备塑料模制品的方法,其特征在于在挤出机中在345℃-385℃的温度下将PPSU和PTFE这两种塑料彼此混合,将所得配混料造粒,并在375℃-390℃的螺杆温度下挤出所述粒料而获得塑料模制品。
8.根据上述权利要求中任一项的混合物用于制备抗磨带的用途。
9.可通过挤出根据权利要求1-7的混合物获得的抗磨带。
10.流体用管线,其特征在于它配备有至少一个根据权利要求9的抗磨带。
CN2010800315143A 2009-07-13 2010-05-25 聚苯砜-聚四氟乙烯组合物及其用途 Pending CN102471577A (zh)

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