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TW201925347A - 用於發泡體之ｐｅｓ－ｐｐｓｕ摻合物 - Google Patents

用於發泡體之ｐｅｓ－ｐｐｓｕ摻合物 Download PDF

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TW201925347A
TW201925347A TW107141637A TW107141637A TW201925347A TW 201925347 A TW201925347 A TW 201925347A TW 107141637 A TW107141637 A TW 107141637A TW 107141637 A TW107141637 A TW 107141637A TW 201925347 A TW201925347 A TW 201925347A
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composition
pes
foaming
ppsu
blowing agent
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克利斯汀 特瑞瑟
凱 柏恩哈德
路易斯 阿勞霍
伊娜 雷柏
德克 羅森
沃 朗
湯瑪斯 理查特
馬里昂 哈克斯
朗 弘
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德商贏創羅恩有限責任公司
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Abstract

本發明係關於一種用於製備新型發泡體的組成物，其具有較佳的阻燃性質和良好的斷裂伸長率。這些新型發泡體係由聚醚碸(PES)和聚伸苯碸(PPSU)的摻合物所製成。

Description

用於發泡體之ＰＥＳ﹘ＰＰＳＵ摻合物
本發明係關於一種用於製備新型發泡體的組成物，其結合了較佳的阻燃性質和良好的斷裂伸長率。這些新型發泡體係由聚醚碸(PES)和聚伸苯碸(PPSU)的摻合物所製成。
PES和PPSU摻合物用於其它技術應用係已知的。EP 1 497 376描述了這種用於熔融製造、注塑成型(injection moulding)、壓縮模製、擠出或吹塑成型(blow moulding)之加工的摻合物。然而，使用這種組成物製備發泡體係未知的。
例如，在EP 0 764 461中也描述了來自這種摻合物的多孔膜。這種類型的膜藉由鑄製法由聚合物的含水組成物製備而成。
許多工業上使用的發泡體在高溫下使用時具有缺點或整體上具有不太理想的機械性能，但特別是在這些高溫下。此外，只有極少數現有的發泡體不易燃，因此有資格安裝在例如公路、鐵路或航空載具的內部。例如，PES發泡體具有較差的阻燃效果，而PPSU發泡體則具有不太理想的斷裂強度。
PPSU或PES的發泡體在原則上是已知的，儘管它們彼此並不互相混合。在L. Sorrentino所撰寫的“高性能熱塑性塑膠的聚合發泡體”，Advances in Polymer Technology, Vol. 30, No. 3, pp. 234-243, 2011 (DOI 10.1002/adv)中報導了用於鑑定發泡PPSU和/或PES的理想條件的工作。
包含PPSU或PES的摻合物係類似地已知，儘管在先前技藝中提供了相當少的細節。更特別地，兩種聚合物都已用作定量地微量組分，例如在PS發泡體中，為了影響這些商品材料的性質。相反地，包含PPSU或PES作為主要組分的發泡體僅在極少數的描述中找到，例如以下內容：
US 4,940,733揭示了一種基於聚碳酸酯與包含PES或PPSU的第二聚合物的摻合物的發泡體，以及多種其它實施例。雖然這種類型的發泡體具有高水平的熱穩定性，但其阻燃效果不是特別好。關於機械性能也沒有提供任何細節。
WO 2015/097058描述了基於PPSU或PES的發泡體，其包含不少於10重量%的聚烯烴。相分離聚烯烴可能主要作為成核劑。雖然獲得了更均勻的微孔(cell)，但不利於阻燃性質或機械性能(例如，斷裂伸長率)。事實上，相分離可能對斷裂伸長率產生不利影響。混合的聚烯烴組分也可能對阻燃性產生不利影響。
有鑑於先前技藝，本發明所解決的問題是提供用於製備新型發泡體的組成物。所得到的發泡體將表現出在高溫下的良好組合，良好的機械性能，特別是關於斷裂伸長率，以及對於載具和飛機構造中的許多應用至少足夠的阻燃效果。
發泡體應特別具有高達120℃的持續使用溫度，較佳地係高達150℃。
應該可以藉由各式各樣的方法和多種形式從組成物中實現發泡體。
所解決的其它非明顯式的問題可以從本文的說明書、申請專利範圍或實施例中得出，而不是為此目的而在此明確地敘述。

方法
藉由提供用於製備熱穩定的低可燃性工程的發泡體之新型組成物來解決這些問題。這種用於製備發泡體的組成物，其特徵在於根據本發明其含有60至98重量%的PES和PPSU的混合物，PES和PPSU的比例為1：9至9：1間，較佳地為1：1至8.5：1間，以作為主要成分。
該組成物更包含自0.5至10重量%的發泡劑。它可以進一步包含自0至10重量%的添加劑和自0至20重量%的第三聚合物組分。
該組成物較佳地由90至95重量%的PES和PPSU的混合物，PES和PPSU的比例為自1：1至8：1、自1至9重量%的發泡劑和自1至5重量%的添加劑所組成。
添加劑尤其可包含阻燃劑、塑化劑、顏料，UV穩定劑、成核劑、抗衝改質劑(impact modifiers)、助黏劑、流變改質劑(rheology modifiers)、擴鏈劑、纖維和/或奈米顆粒。
所用的阻燃劑通常是磷化合物，特別是磷酸鹽、膦或亞磷酸鹽。合適的UV穩定劑和/或UV吸收劑是本技術領域的一般知識。HALS化合物、Tiuvins或三唑通常用於此目的。所用的抗衝改質劑通常是包含彈性體和/或軟/柔性相的聚合物珠粒。該些聚合物珠粒通常包含具有外殼的核-(殼-)殼珠，所述外殼本身不超過輕度交聯，並且純聚合物將表現出與PES-PPSU摻合物至少最小的溶混性。原則上可以使用任何已知的顏料。當然，主要量需要測試其對發泡操作的影響，就像所有其它含量高於0.1重量%添加劑的用量一樣。這對於本技術領域具通常知識者來說不是非常麻煩。
合適的塑化劑、流變改質劑及擴鏈劑是從PES、PPSU或其摻合物製備片材、膜或模製品之技術之一般知識，因此可以以最小的成本和不方便地從由根據本發明的組合物製成之泡沫中轉移。
纖維通常是已知的纖維材料，用於添加到聚合物組成物中。在本發明特別合適的實施態樣中，該纖維是PES纖維、PPSU纖維或摻合纖維，後者來自PES和PPSU。
奈米顆粒，例如以管狀、片狀、棒狀、球狀或其它已知形式的形式，通常是無機材料。它們可以在同一時間在最後的發泡體中執行各種功能。這是因為這些顆粒在發泡操作中部分作為成核劑。顆粒可以進一步影響發泡體的機械性能以及(氣體)擴散性質。顆粒進一步對低可燃性做出了額外的貢獻。
除了所述的奈米顆粒之外，亦包含微粒或基本上不混溶的相分離聚合物作為成核劑。在組成物中成核劑的情況下，該聚合物必須與其它成核劑分開觀察，因為後者主要對發泡體的機械性能，組成物的熔體黏度發揮影響，和因此產生對發泡條件的影響。相分離聚合物作為成核劑的額外功效是該組分的額外所需功效，但在這種情況下不是主要功效。因此，這些額外的聚合物在整體計數中顯得更高，與其他添加劑分開。
額外的聚合物可包含例如聚醯胺、聚烯烴，特別是PP、PEEK、聚酯，特別是PET、其它基於硫的聚合物，例如PSU、聚醚醯亞胺或聚甲基丙烯醯亞胺。
發泡劑的選擇是相對自由的，並且對於該技術領域具通常知識者而言，特別是藉由所選擇的發泡方法和發泡溫度來決定。合適的是例如醇類，例如異丙醇或丁醇、酮類，如丙酮或甲基乙基酮、烷烴，如異丁烷、正丁烷、異戊烷、正戊烷、己烷、庚烷或辛烷、烯烴，如戊烯、己烯、庚烯或辛烯、CO2 、N2 、水、醚，例如二乙醚、醛，例如甲醛或丙醛、氫(氯)碳氟化合物、化學發泡劑或其兩種或多種的混合物。
化學發泡劑是相對或完全不揮發的物質，其在發泡條件下經歷化學分解以在分解時形成實際的發泡劑。三級丁醇是一個非常簡單的例子，因為它在發泡條件下形成異丁烯和水。其它實施例是NaHCO3 、檸檬酸、檸檬酸衍生物、偶氮二甲醯胺(ADC)和/或基於其之化合物、甲苯磺醯肼(toluenesulphonylhydrazine, TSH)、氧代雙(苯並磺基氫化物)(oxybis(benzosulphohydroazide), OBSH)或5-苯基四唑(5-phenyltetrazole, 5-PT)。
較佳地用作發泡劑的是CO2 、N2 及其之混合物。
不僅組成物且由本發明組成物製備的發泡體當然亦構成本發明的組成部分。
本發明進一步亦提供了一種本發明組成物的發泡方法。將組成物在150至250℃間的溫度和0.1至2巴間的壓力下進行發泡。較佳地在標準大氣壓力下在180至 230℃的溫度間進行發泡。
本技術領域具通常知識者已知各種發泡聚合組成物的方法，原則上適用於本發明的組成物，特別是在熱塑性發泡體的方法中。然而，有一些特佳的替代品。
在該方法的第一個較佳的方案中，將不含發泡劑的組成物與發泡劑在高壓釜中在20至120℃間的溫度和30至100巴間的壓力下混合，隨後藉由減壓並將溫度升至發泡溫度使其在高壓釜內膨脹。或者，將與發泡劑混合的組成物在高壓釜中冷卻並在冷卻後移出高壓釜(deautoclaved)。然後藉由加熱至發泡溫度，該組成物隨後可膨脹。這也可能例如在進一步模製下或與諸如嵌件或面層的其他元件之組合進行。
在該方法的第二種版本中，含有發泡劑的組成物在擠出機中加熱。
在該方法的第三種版本中，不含發泡劑的組成物在擠出機中加熱並與發泡劑混合，較佳地在擠出機中與CO2 和/或N2 混合。
在第二或第三種版本中將組成物從擠出機中排出的方式隨後產生了進一步的實施態樣。因此，組成物可以藉由寬槽模頭或一些其它成型模頭從擠出機中排出，當其通過模頭到模頭外部時進行膨脹。該版本可與直接隨後的共擠出或層壓結合，使得面層直接施加至由寬槽模具形成的發泡片材或片材上。
在第三或第二版本的第二實施態樣中，組成物在從擠出機中出來時膨脹，並且造粒機將膨脹的擠出物切割成珠粒發泡體。通常，該實施態樣中的造粒機非常接近從模頭出口的點，使得已經分離的珠粒在形成後直接膨脹。
在第二或第三種版本的第三實施態樣中，最後，離開擠出機的組成物可以進入結構發泡體模製設備。在該設備中，膨脹接著直接與模製進行。
第四個替代實施態樣，其特徵在於從擠出機出來的組成物進入水下造粒機，其中存在這樣的溫度和壓力的組合，以防止發泡。裝載有在該程序中獲得的發泡劑的丸粒材料然後可以例如較晚地熱膨脹。
根據本發明的發泡體和/或藉由根據本發明的方法所獲得的發泡體可用於許多目的。該發泡體較佳地用於載具結構，例如公路、鐵路、水路、太空或航空載具的建設。由於它們的低可燃性，本發明的發泡體還可以更佳地安裝在這些載具的內部。其它應用領域包含例如電氣和電子工業、風力發電系統的構造和機械工程。
與純摻合物相比，本發明的發泡體膨脹率較佳地相當於降低1至98%，較佳地50至97%，更佳地70至95%間的密度。發泡體密度較佳地為20至1000 kg/m3 間，較佳地為40至250 kg/m3 間。

Claims (14)

  1. 一種用於製備發泡體的組成物，其特徵在於該組成物包含自60至98重量%的PES和PPSU的混合物，PES和PPSU的比例為1：9至9：1間、0.5至10重量%的發泡劑、自0至10重量%的添加劑和自0至20重量%的第三聚合物組分。
  2. 如申請專利範圍第1項之組成物，其中PES和PPSU以1：1至8.5：1間的比例存在。
  3. 如申請專利範圍第1或2項之組成物，其中該添加劑包含阻燃劑、塑化劑、顏料，UV穩定劑、成核劑、抗衝改質劑(impact modifiers)、助黏劑、流變改質劑(rheology modifiers)、擴鏈劑、纖維和/或奈米顆粒。
  4. 如申請專利範圍第1至3項中一或多項之組成物，其中該發泡劑包含醇、酮、烷烴、烯烴、CO2 、N2 、水、醚、醛、化學發泡劑或其兩種或多種的混合物。
  5. 如申請專利範圍第1至4項中一或多項之組成物，其中該組成物由90至95重量%的PES和PPSU的混合物，PES和PPSU的比例為1：1至8：1間、自1至9重量%的發泡劑和自1至5重量%的添加劑所組成。
  6. 一種由如申請專利範圍第1至5項中一或多項之組成物發泡所獲得的發泡體。
  7. 一種用於將如申請專利範圍第1至5項中一或多項之組成物發泡的方法，其中將該組成物在150至250℃間的溫度和0.1至2巴間的壓力下進行發泡。
  8. 如申請專利範圍第7項之方法，其中該組成物係於標準大氣壓力下在180至230℃的溫度間進行發泡。
  9. 如申請專利範圍第7或8項之方法，其中將不含發泡劑的組成物與發泡劑在高壓釜中在20至120℃的溫度和30至100巴的壓力下混合，隨後該組成物藉由減壓並將溫度升至發泡溫度於高壓釜中膨脹或者在高壓釜外部，接著在高壓釜內冷卻並移出高壓釜(deautoclaving)，藉由加熱至發泡溫度使該組成物膨脹。
  10. 如申請專利範圍第7或8項之方法，其中該組成物在擠出機中加熱。
  11. 如申請專利範圍第7或8項之方法，其中未含發泡劑的組成物在擠出機中加熱並與發泡劑混合。
  12. 如申請專利範圍第10或11項之方法，其中該組成物藉由寬槽模頭或一些其它成型模頭從該擠出機中排出，當其通過該模頭到該模頭外部時進行膨脹。
  13. 如申請專利範圍第10或11項之方法，其中從該擠出機出來的組成物進入水下造粒機，其中存在這樣的溫度和壓力的組合，以防止發泡，及所獲得之裝載發泡劑的丸粒材料係較晚地膨脹。
  14. 如申請專利範圍第10或11項之方法，其中該組成物從該擠出機進入結構發泡體模製設備，在該設備中膨脹及模製。
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