TWI523898B - 用於可撓性輸油管內之抗磨損帶的聚苯碸─聚四氟乙烯摻合物 - Google Patents
用於可撓性輸油管內之抗磨損帶的聚苯碸─聚四氟乙烯摻合物 Download PDFInfo
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Description
本發明有關一種用於製造減少摩擦力帶之由聚苯碸(PPSU)與聚四氟乙烯(PTFE)製成的經改良混合物,該等減少摩擦力帶係用作可撓性流體管之減少摩擦力中間層,其實例為輸油管(抗磨損帶)。
GB 2 441 066(Technip France)描述一種用於輸送烴類之多層結構的撓性管。該配置在介於可至少某種程度地相對於彼此移動的金屬條帶之間具有減少摩擦力之塑膠像帶,且該塑膠條帶係由玻璃轉化溫度為175℃至255℃之非晶形聚合物所構成。該條帶係由聚苯碸(PPSU)及全氟化之聚合物和聚醚醚酮(PEEK)所構成。在本發明一特定具體實例中,將85%之聚苯碸(PPSU)製成之混合物與15%之聚四氟乙烯(PTFE)混合且擠出產生厚度為1.5 mm且寬度為約1 m之條帶。未提及所使用之塑膠的分子量。
US 2005/0229991描述與GB '066相似之配置,但該實例之中間層的材料為彈性熱塑性聚合物,例如苯乙烯-丁二烯-苯乙烯橡膠(SBS)、苯乙烯-乙烯-丁二烯-苯乙烯共聚物(SEES)或EPDM(乙烯-丙烯-二烯)共聚物,或者為聚丁二烯、聚異戊二烯或聚乙烯-丁烯共聚物。
德國專利申請案DE102009027659.9揭示含PTFE之
PPSU,其比例為1至15重量%之PTFE,特佳為5至10重量%。然而,已發現在所述範圍中之該類型組成物的機械性質非常多變。此外,DE102009027659.9未指示最佳化擠出程序以改善機械性質的方式。
根據所討論之先前技術,本發明目的因而為發現可用於輸油管內之減少摩擦力帶且對於該狀態中普遍的條件(溫度為約130℃,壓力為300至400 bar)之適用性優於先前技術之材料的材料及/或材料混合物。
特定目的係提出用於製造減少摩擦力帶之經改良方法,該減少摩擦力帶包含由聚苯碸(PPSU)及聚四氟乙烯(PTFE)製成之塑膠模製物,其中該等模製物具有良好且平衡之機械性質,特別是在擠出方向,但與擠出方向垂直之方向亦如此。
該等目的係經由用於製造由聚苯碸(PPSU)及聚四氟乙烯(PTFE)製成之塑膠產物的經改良方法所獲致。此處已發現,若特別地確保PPSU基質中之PTFE粒子的精細分散,可提供不只在擠出方向且亦垂直於擠出方向的特別平衡之機械性質。已發展意外簡單之方法,其產生該不與PPSU混溶之PTFE的精細分散。
令人意外地,特別是鑒DE102009027659.9之教示,
已發現PTFE在PPSU中之精細分散對於機械性質且對於呈在輸油管內之減少摩擦力帶形式的摻合物之耐用性特別重要。若分散不良,形成相對較大之PTFE相,且該帶內特別是該等PTFE邊界處的內聚力受損。
根據本發明,下文中,術語帶意指該等塑膠模製物的較佳具體實例。
藉此,已發現只有非常細微粒子PTFE在PPSU基質內之整體橫斷面非常均勻分散提供在使用期間的所希望效果(舉例來說,該帶之厚度縮減),及提供不只在擠出方向且亦垂直於擠出方向的特別平衡之機械性質。
本發明方法的特徵特別在於混合物之PTFE含量為4.0重量%至6.0重量%,較佳為4.5重量%至5.5重量%。該PPSU含量對應地從94.0重量%至96.0重量%,較佳為95.5重量%至94.5重量%。
另外重要的是使用非常細微之粒狀PTFE。然而,基於擠出技術之因素,粉塵含量必須不過量。特別適用於本發明方法的PTFE係在擠出程序之前粒度小於3 μm的比例小於12體積%,較佳為8至11體積%,及粒度小於25 μm的比例至少88體積%,較佳至少90體積%者。特別適用之PTFE為亦具有1.5至3.0 m2/g之比表面積者。
該等粒度係使用得自Microtrac之設備,利用雷射散射所測定。該比表面積係利用氮吸附測定。
本發明之方法另外之特別特徵係於第一擠出機中,在340至390℃,較佳為345℃至385℃之溫度下混合該PTFE
及該PPSU,且在第二擠出機中,在345至390℃,較佳為375至390℃之溫度下處理從該第一擠出程序獲得之丸粒,以產生塑膠模製物。較佳係該產生提供PTFE在PPSU中之特別精細分散的丸粒之第一擠出程序係在500至700 mbar之周圍壓力下,以220至270 min-1之旋轉速率,在340至390℃,較佳為375至390℃之熔融溫度,及50%至80%,較佳為60%至75%之轉矩,較佳係在雙螺桿擠出機中進行。
令人意外的,已發現可在該等於PPSU之熔融範圍的高溫下不分解的情況下擠出PTFE。
該進一步處理以產生塑膠模製物的第二擠出步驟通常涉及在單螺桿擠出機中以40至60 min-1之速率的擠出程序。
本發明進一步提出該混合物或該等塑膠模製物用於製造抗磨損帶的用途,其中該混合物或該等塑膠模製物係根據本發明方法製造。
本發明亦特別提出該抗磨損帶在用於供流體用之管內的用途。該等管的特徵為特別之耐用性及機械強度。
所使用之PPSU包含由Solvay Advanced Polymers所售,商標為RADEL® R(例如RADEL R 5000 nt.)之聚苯碸。
該聚合物的重複單元具有下式:
此處涉及的材料為透明且高性能塑膠,其即使在熱老化之後亦具有極高之抗應力龜裂性及極高之凹口抗衝擊性,以及具有優異之化學抗性。
其用於製造醫學技術、化學產業及管路系統中之組件。該聚合物的密度為1.29 g/cm3(根據ISO 1183測量)、屈伏應力為70 MPa(根據ISO 527測量)、斷裂伸長率為60%(根據ISO 527測量)、彈性之張力模數為2340 MPa(根據ISO 527測量)、於23℃下之艾氏(Izod)凹口抗衝擊性為49.4 kJ/m2(根據ISO 180/1A測量),及於23℃下之查皮(Charpy)凹口抗衝擊性為58.3 kJ/m2(根據ISO 179/1eA測量)。
於50 Hz下之介電常數為3.4(根據IEC 60250測量)、於1 MHz下之介電常數為3.5(根據IEC 60250測量),及於50 Hz下之介電損失因數為6*10-4(根據IEC 60250測量)。於1 MHz下之介電損失因數為76*10-4(根據IEC 60250測量),及介電強度為15 kV/mm(根據IEC 60243-1測量,根據ASTM測量)。介電強度的厚度為3.2 mm,及根據IEC 60093之比體積電阻率為9*1015 ohm m。
沿著/垂直於流動方向之縱向膨脹為55*10-6/K(根據ISO 11359測量,根據ISO 11357測量之熔點或玻璃轉
化溫度為215℃,熱變形溫度A為207℃(根據ISO 75 HDT/A(1.8 MPa)測量),熱變形溫度B為214℃(根據ISO 75 HDT/A(0.45 Mpa)測量),最高溫度(短期)為180℃,最高溫度(長期)為160℃(熱陳化係根據UL 746(RTI)Mechanical W/O Imp.,40 000小時)。最低使用溫度為負100℃。
根據本發明,較佳係必須使用具有中等分子量且具有小顆粒大小,以及特別是具有窄顆粒大小分布的聚四氟乙烯(PTFE)。該等PTFE特別適於結合至工程塑膠,其中該等工程塑膠係在非常高之熔融溫度下加山且具有良好機械性質,以及具有高度對於化學物質(諸如礦油)之抗性。
所使用之高分子量聚四氟乙烯(PTFE)的實例為非常細微之粒狀Zonyl® MP 1300聚四氟乙烯。該PTFE特別適於作為以HT熱塑性塑膠為底質之聚合物混合物中的添加劑。
以下列方式將從95重量%至60重量%之PPSU及從40重量%至5重量%之PTFE所製成之混合物預以混合:
在雙螺桿擠出機(製造商及型號:Werner & Pfleiderer ZSK25 WLE(K4))中將該PPSU熔融及去揮發,且經由橫向進料孔導入該PTFE。所使用之PPSU包含Radel R-5000且所使用之PTFE包含Zonyl MP 1300。
將所獲得之混合材料予以粒化。
本發明之薄片可以本身已為人習知之方式,經由擠出在第一步驟中所獲得之丸粒來製造。
為此,在單一擠出程序之情況下,熱塑化熔體係經由一部擠出機所產生,或在共擠出程序之情況下,熱塑化熔體係經由複數部擠出機且進料至一擠出模所產生。其中可有額外裝置,例如熔體泵及/或熔體過濾器,其係以本身為人習知之方式配置在該擠出機及擠出模之間。然後將擠出之片(web)導入拋光研磨器或導入校正器。
將該等丸粒再熔融且擠出以產生具有下列尺寸之帶:長度1 000 mm,寬度150 mm,厚度1.5 mm。熔融溫度為
約385℃。
對照實例3:如發明實例1,旋轉速率為200 min-1。此處之轉矩高到使得不可能均勻擠出。
對照實例4:如發明實例1,擠出溫度為320℃。在所得之丸粒中,即使肉眼亦可辨別出相分離。
從發明實例1以及從對照實例1及2所形成之丸粒係在380℃下擠出以產生帶。在圖式(圖1至4)中,根據本發明所製造之摻合物與非根據本發明所製造之摻合物之間的相分離方面的差異明顯。
以顯微鏡研究從第一擠出程序所得之摻合物,以測定存在之個別微相分離。為此,各例中係藉由SEM/EDS進行測量。SEM為掃描電子顯微術。EDS為能量色散X射線光譜術。二者測量均在丸粒的表面上進行。各例中,SEM測量係描繪於右側。
當根據本發明之圖1與非根據本發明之圖2及圖3比較時,明顯看出PTFE相(淺色)明顯較小。藉此,已獲致較佳均質化,形成較高之機械強度。反之,根據對照實例1及2之材料展現出長而相對較大之PTFE相,尤其是在擠出方向上,且此等PTFE相導致該等帶於進一步處理之後的不安定性提高。
圖1:來自發明實例1之粒化材料的SEM影像(右側)及EDS影像(左側)。
圖2:來自對照實例1之粒化材料的SEM及EDS影像。
圖3:來自對照實例2之粒化材料的SEM及EDS影像。
Claims (7)
- 一種用於製造由聚苯碸(PPSU)與聚四氟乙烯(PTFE)製成之塑膠產物的方法,其特徵在於將PPSU及PTFE所製成之混合物予以摻合,該混合物的PTFE含量為4.0重量%至6.0重量%,該混合物的PPSU含量為94.0重量%至96.0重量%,在擠出程序之前,粒度小於3μm之PTFE的比例為8至12體積%,及粒度小於25μm之PTFE的比例為至少88體積%,該PTFE與該PPSU係在擠出機中於340℃至390℃之溫度下混合,且係在第二擠出機中處理以產生塑膠模製物。
- 如申請專利範圍第1項之方法,其中該PTFE的比表面積為1.5至3.0m2/g。
- 如申請專利範圍第1或2項之方法,其中該混合物的PTFE含量為4.5重量%至5.5重量%,及該混合物的PPSU含量為95.5重量%至94.5重量%。
- 如申請專利範圍第1或2項之方法,其中這兩種塑膠PPSU與PTFE係在345至385℃之溫度下於第一擠出機中在500至700mbar之周圍壓力下,以220至270min-1之旋轉速率,在自340至390℃之螺桿溫度及 50%至80%之轉矩下彼此混合,且在該第一擠出程序之後所獲得的丸粒係在單螺桿擠出機中擠出以產生塑膠模製物。
- 如申請專利範圍第1或2項之方法,其中該等丸粒係在345至390℃之螺桿溫度下擠出以產生塑膠模製物。
- 一種藉由如申請專利範圍第1項之方法所製造之塑膠模製物的用途,其用於製造抗磨損帶。
- 一種如申請專利範圍第6項之抗磨損帶的用途,其用於供流體用之管。
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CN103249764B (zh) | 2016-06-29 |
EP2663591B1 (de) | 2018-07-11 |
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JP2014502661A (ja) | 2014-02-03 |
ZA201305289B (en) | 2014-03-26 |
US20130230677A1 (en) | 2013-09-05 |
JP5905027B2 (ja) | 2016-04-20 |
SG191720A1 (en) | 2013-08-30 |
WO2012095214A1 (de) | 2012-07-19 |
EP2663591A1 (de) | 2013-11-20 |
HK1184483A1 (zh) | 2014-01-24 |
AU2011355261A1 (en) | 2013-06-06 |
MY161963A (en) | 2017-05-15 |
CN103249764A (zh) | 2013-08-14 |
CA2824834A1 (en) | 2012-07-19 |
MY163932A (en) | 2017-11-15 |
DK2663591T3 (en) | 2018-10-29 |
BR112013017560A2 (pt) | 2016-10-11 |
RU2013137505A (ru) | 2015-02-20 |
RU2595666C2 (ru) | 2016-08-27 |
US9040135B2 (en) | 2015-05-26 |
TW201245290A (en) | 2012-11-16 |
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