TW201821495A - 基於膨脹熱塑性彈性體之模製發泡體 - Google Patents

基於膨脹熱塑性彈性體之模製發泡體 Download PDF

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TW201821495A
TW201821495A TW106137848A TW106137848A TW201821495A TW 201821495 A TW201821495 A TW 201821495A TW 106137848 A TW106137848 A TW 106137848A TW 106137848 A TW106137848 A TW 106137848A TW 201821495 A TW201821495 A TW 201821495A
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法蘭克 普利索克
古尼 卡瑞沛特雅恩
迪爾克 坎福特
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德商巴斯夫歐洲公司
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Abstract

發泡珠粒，其基於包含至少一種經芳基修飾之矽氧烷的熱塑性彈性體；用於產生發泡珠粒的方法；以及可透過發泡珠粒之熔合獲得的模製發泡體，該熔合係藉由蒸煮或用高頻電磁輻射照射，或藉由黏合性結合，其使用反應性黏合劑、含溶劑的黏合劑、或分散黏合劑。

Description

基於膨脹熱塑性彈性體之模製發泡體
發泡珠粒，其基於包含一種矽氧烷的熱塑性彈性體；用於產生發泡珠粒的方法；以及可透過發泡珠粒之熔合獲得的模製發泡體，該熔合係藉由蒸煮或用高頻電磁輻射照射，或藉由黏合性結合，其使用反應性黏合劑、含溶劑的黏合劑、或分散黏合劑。
作為實例，膨脹熱塑性聚合物係經用於製造各式各樣的發泡固體，實例為：體操墊、護胸、自動車結構中的襯料成分、吸音器和減震器、包裝、及鞋底。在一個較佳方法中，係將由膨脹聚合物所製成的發泡珠粒充入模具，且藉由暴露於熱而使個別發泡珠粒在其表面上小範圍熔融，並因而相互結合以提供模製發泡體。此方法可產生具有底切之簡單或複雜的半成品產品或模。
WO-A 2007/082838揭示了一種用於產生包含發泡劑之膨脹熱塑性聚胺甲酸酯的方法。此方法的第一步驟係擠出熱塑性聚胺甲酸酯以提供顆粒。第二步驟係使用發泡劑以在壓力下、在水性懸浮液中浸漬顆粒，且第三步驟係使顆粒膨脹。該方法的另一具體實例係在擠出機中使熱塑性 聚胺甲酸酯和發泡劑一起熔融，且在沒有任何預防發泡的裝置存在時對熔體進行造粒。
WO 2015/055811描述了一種用於產生膨脹熱塑性聚合物的方法，其包含以下步驟：(a)將以下添加進聚合物加工機的第一段：用於產生熱塑性聚合物的單體及/或寡聚物，以及視情況的其它初始材料；(b)混合該等單體及/或寡聚物，且亦混合經視情況添加的該其它初始材料，並使該單體及/或寡聚物反應，以在聚合物加工機的第一段中提供聚合物熔體；(c)將該聚合物熔體引入該聚合物加工機的第二段並添加發泡劑，且亦視情況添加其它初始材料，以獲得包含該發泡劑的聚合物熔體；以及(d)模製該包含發泡劑的聚合物熔體以提供膨脹熱塑性聚合物。
WO 2013/153190和WO 2014/198779同樣描述了用於產生由熱塑性彈性體所製成之膨脹顆粒的方法，其係透過擠出包含發泡劑的聚合物熔體並進行造粒，以提供膨脹顆粒。熱塑性模製組成物可包含、作為表面活性物質，尤其是有機矽氧烷，諸如二甲基聚矽氧烷。
本發明之一個目標為提供發泡珠粒，其係基於熱塑性彈性體，且其係經加工以提供具高尺寸安定性和具改良機械性質的模製發泡體，特別是在低密度時一併具高抗壓強度和反彈性，以及高撕裂強力。
可藉由如申請專利範圍第1項所主張的發泡珠粒來達成此目標。
所使用的矽氧烷較佳為寡聚有機矽氧烷或聚合有機矽氧烷。矽氧烷較佳具有不跟異氰酸酯反應的有機基團，特別是不反應的芳基團。所提供的特別較佳者為經有機矽烷修飾的聚矽氧烷，其具有經由碳原子進行結合的有機矽烷基團。較佳的聚矽氧烷為具有重複單元-[O-SiR2R3]-的聚二有機矽氧烷，特別是通式為R1 3Si-[O-SiR2R3]-O-SiR1 3者，其中R1、R2及R3可彼此獨立地為氫原子、烷基團、或芳基團。特別較佳的是R1和R2為甲基，且R3為苯乙基。
較佳的是使用以芳基團進行封端之矽氧烷。特別較佳的是使用經芳基修飾之矽氧烷，實例為苯基乙基甲基聚矽氧烷，例如來自Evonik的Tegomer® M-Si 2650。
其它適合的矽氧烷為具有至少一個有機矽氧烷嵌段和一個聚醚嵌段的矽氧烷嵌段聚合物，實例為DE 10 2014 218 635中所描述者。較佳的聚醚嵌段係由EO、PO、或PESOL所組成。所提供的特別較佳者為聚酯矽氧烷或聚醚矽氧烷，例如經三甲基矽氧基封端之二甲基甲基(丙基(氧化丙烷))矽氧烷，實例為DOW CORNING 1248流體。
較佳的矽氧烷使用數量為以熱塑性彈性體計在0.1至5重量%範圍內，特別是在0.1至2重量%範圍內。較佳的是使用單一矽氧烷，特別是經芳基修飾之矽氧烷。然而，亦有可能使用複數種矽氧烷。當使用複數種矽氧烷時，所宣稱數量係以所有矽氧烷的全部數量計。
本發明中所使用的矽氧烷係作為氣室調節劑、氣室穩定劑、 及表面修飾劑。它們提供了平坦、光滑、及經密封的氣室表面，還有從發泡珠粒核心中之較大氣室直徑，到周邊區域中之較小氣室直徑的氣室尺寸分佈梯度。氣室尺寸分佈梯度和緻密表面導致了更強的熔合容易度，以及與其相關的改良機械性能。平坦表面降低了摩擦阻力，並改良了發泡珠粒抵抗磨損的能力。
較佳的是發泡珠粒內側的平均氣室直徑為200-1000微米、較佳為200-600微米；且在周邊區域中之該直徑在0.1至200微米範圍內，較佳為0.1至100微米。用詞「周邊區域(peripheral region)」意指珠粒半徑的外部20%。珠粒中心周圍的內部50%被稱為核心。
適合之熱塑性彈性體的實例為熱塑性聚胺甲酸酯(TPU)、熱塑性聚酯彈性體(例如：聚醚酯和聚酯酯)、熱塑性共聚醯胺(例如聚醚共聚醯胺)、及熱塑性苯乙烯-丁二烯嵌段共聚物。所提供的特別較佳者為基於熱塑性聚胺甲酸酯(TPU)的發泡珠粒。
發泡珠粒的整體密度較佳在30至250kg/m3範圍內。
發泡珠粒可獲自藉由在懸浮液中使用的發泡劑來浸漬含有至少一種矽氧烷的熱塑性彈性體顆粒，或藉由使用用於熔融浸漬熔融熱塑性彈性體之發泡劑；並隨後進行造粒。關於產生基於熱塑性彈性體之發泡珠粒的適合方法，其實例經描述於WO 2005/023920、WO 2007/082838、WO 2013/153190、及WO 2014/198779中。
一種在產生發泡珠粒方面有差異的方法包含：在發泡時使包含矽氧烷的熱塑性彈性體熔融、使發泡劑與其摻合、及對該包含發泡劑的熔體進行造粒。
另一在產生發泡珠粒方面有差異的較佳方法包含以下步驟：(a)將以下添加進聚合物加工機的第一段：用於產生熱塑性彈性體的單體及/或寡聚物、和至少一種矽氧烷、及視情況的其它初始材料；(b)混合該等單體及/或寡聚物和矽氧烷，且亦混合經視情況添加的該其它初始材料，並使該單體及/或寡聚物反應，以在聚合物加工機的第一段中提供聚合物熔體；(c)將該聚合物熔體引入該聚合物加工機的第二段並添加發泡劑，且亦視情況添加其它初始材料，以獲得包含發泡劑的聚合物熔體；以及(d)模製該包含發泡劑的聚合物熔體以提供膨脹熱塑性彈性體。
可特別被使用的聚合物加工機為螺桿活塞機和熔融泵。較佳經用於進行本發明之方法的螺桿活塞機為擠出機。
在本發明的一個具體實例中，係在機器中執行步驟(b)和(c)。在此情況下，第一段是部分螺桿活塞機的第一節，且其中在以下存在時發生單體及/或寡聚物的反應以提供聚合物：矽氧烷和視情況的其它初始材料；又第二段是部分螺桿活塞機的第二節，且其直接接在第一節之後，其中發泡劑係經以計量供給進材料中。
接著在螺桿活塞機的第二段裡，將發泡劑以計量供給進材料中。為了將該試劑均勻分佈在聚合物熔體中，螺桿活塞機的第二段在螺桿上具有例如適合之混合元件。在本發明中亦有可能額外使用靜態混合器。
作為擠出機的替代物，也有可能使用熔融泵。為了獲得發泡劑在聚合物中的均勻分佈，較佳的是在進入造粒系統之前，在熔融泵的下 游有靜態混合器。
為了產生珠粒，聚合物熔體通常係經擠出以提供組成部分(strands)，其接著經切碎以提供發泡珠粒。因為添加了發泡劑，所以從擠出機排出時的壓力下降造成了聚合物熔體的膨脹，並產生發泡產物，從而在進行造粒後提供膨脹發泡珠粒。
為了在步驟(d)中產生發泡珠粒，較佳的是強迫聚合物熔體通過溫控造粒模具進入造粒室、使用切割裝置以將該熔體切碎成個別的膨脹發泡珠粒、及使用液體流以從造粒室排出發泡珠粒。本發明中之溫控造粒模具的溫度較佳為150至280℃。
為了預防造粒室中之聚合物熔體的不受控發泡，並產生經均勻發泡的發泡珠粒，有利的是對造粒室施加高於環境壓力之壓力。更特別較佳的是用液體充滿造粒室，使得直接強迫包含發泡劑的熱塑性聚合物熔體進入液體中。造粒室中所使用的液體較佳為水。
在由包含發泡劑的聚合物熔體產生膨脹發泡珠粒期間，流過造粒室的溫控液體壓力較佳為0.7巴至20巴。較佳地，液體壓力為5至15巴，且特別較佳的是10至15巴的壓力。
在一個較佳具體實例中，發泡劑包含二氧化碳、氮、或二氧化碳和氮的混合物。在本發明中有可能使用任何所欲之氮和二氧化碳的混合物。可替代地或另外地，亦有可能的是發泡劑包含有機發泡劑，例如：烷、鹵化烴、或這些物質的混合物。本發明中之適合的烷實例為乙烷、丙烷、丁烷、及戊烷。單獨使用以下作為發泡劑是特別有利的：CO2、及/或N2、或其組合，其原因在於它們是不可燃的惰性氣體，且因此在生產加工 過程中不會產生爆炸環境。因而不需要昂貴的安全防護措施，並大幅降低了在生產加工期間的潛在危險。同樣有利的是，不需要分開儲存產品以容許揮發性可燃物質的蒸發。
所使用的矽氧烷較佳為寡聚有機矽氧烷或聚合有機矽氧烷。矽氧烷較佳具有不跟異氰酸酯反應的有機基團，特別是不反應的芳基團。所提供的特別較佳者為經有機矽烷修飾的聚矽氧烷，其具有經由碳原子進行結合的有機矽烷基團。較佳的聚矽氧烷為具有重複單元-[O-SiR2R3]-的聚二有機矽氧烷，特別是通式為R1 3Si-[O-SiR2R3]-O-SiR1 3者，其中R1、R2和R3可彼此獨立地為氫原子、烷基團、或芳基團。特別較佳的是R1和R2為甲基，且R3為苯乙基。
較佳的是使用以芳基團進行封端之矽氧烷。特別較佳的是使用經芳基修飾之矽氧烷，實例為苯基乙基甲基聚矽氧烷，例如來自Evonik的Tegomer® M-Si 2650。
其它適合的矽氧烷為具有至少一個有機矽氧烷嵌段和一個聚醚嵌段的矽氧烷嵌段聚合物，實例為DE 10 2014 218 635中所描述者。較佳的聚醚嵌段係由EO、PO、或PESOL所組成(composed of)。所提供的特別較佳者為聚酯矽氧烷或聚醚矽氧烷，例如經三甲基矽氧基封端之二甲基甲基(丙基(氧化丙烷))矽氧烷，實例為DOW CORNING 1248流體。
關於在步驟(a)中所添加、以及在步驟(b)中藉由混合而併入的矽氧烷數量，其較佳以單體和寡聚物計在0.1至5重量%範圍內，特別較佳在0.1至2重量%範圍內。較佳的是使用單一矽氧烷，特別是經芳基修飾之矽氧烷。然而，亦有可能使用複數種矽氧烷。當使用複數種矽氧烷時， 所宣稱數量係以所有矽氧烷的全部數量計。
當將一或多種成核劑作為額外之初始材料添加至包含發泡劑的聚合物熔體時，會獲得進一步的優點。適合的成核劑特別是滑石粉、氟化鈣、苯基膦酸鈉、氧化鋁、碳黑、石墨、顏料、及經細分的聚四氟乙烯，其在各情況下為獨立的，或呈任何所欲之混合物。滑石粉為特別較佳的成核劑。以熱塑性模製組成物或聚合物熔體的全部組成計，成核劑的比例較佳為0至4重量%，特別是0.1至2重量%。可在第一段或第二段裡添加本發明中之成核劑。
實例為可用恰當的發泡劑物理狀態、藉由氣體或液體計量供給單元之手段、經由注入閥將發泡劑添加進聚合物加工機。
如果使用了熱塑性聚胺甲酸酯，則熱塑性聚胺甲酸酯可為所屬技術領域之熟諳此技藝者所習知的任何所欲熱塑性聚胺甲酸酯。熱塑性聚胺甲酸酯及其生產方法已被廣泛地描述，例如在Gerhard W.Becker and Dietrich Braun,Kunststoffhandbuch[Plastics Handbook],volume 7,"Polyurethane"["Polyurethanes"],Carl Hanser Verlag,Munich,Vienna,1993中。
在一個較佳具體實例中，係藉由使異氰酸酯之混合物與以下反應而產生熱塑性聚胺甲酸酯：對異氰酸酯有反應的化合物，其較佳具有0.5kg/mol至10kg/mol的莫耳質量(呈單體或寡聚物形式)；以及視情況的鏈伸長劑，其較佳具有0.05kg/mol至0.5kg/mol的莫耳質量。在另一較佳具體實例中，進一步將以下添加至用於產生熱塑性聚胺甲酸酯的混合物中：至少一種鏈調節劑；一種催化劑；以及視情況的至少一種填料、助劑、 及/或添加劑。
產生熱塑性聚胺甲酸酯總是需要以下混合物：異氰酸酯和對異氰酸酯有反應的化合物。可視情況進一步添加鏈伸長劑、鏈調節劑、催化劑和填料、助劑、及/或添加劑；並可涉及個別化合物或任何可能的變化。
WO 2015/055811描述了由單體及/或寡聚物產生本發明中之發泡珠粒的其它具體實例和適合初始材料。
本發明因而提供了一種用於產生模製發泡體的方法，其係透過上述本發明之發泡珠粒的熱結合，該結合係藉由蒸煮或用高頻電磁輻射照射。
借助於在本發明中所添加的矽氧烷，有可能獲得具有平坦和光滑表面、基於熱塑性彈性體〔特別是基於熱塑性聚胺甲酸酯(TPU)〕的發泡珠粒和模製發泡體。
因為本發明中之模製發泡體具有彈性體性質，所以它們適用於以下應用：運動方面、製鞋方面、及包裝方面。
實施例 比較實施例
在離ZSK32(Coperion)雙螺桿擠出機(直徑D=32mm，長度為56D)的進料端為2D的距離、用以下流速引入下方所列之調配物成分： 且在擠出機中混合該調配物成分並使其反應。螺桿的轉速為150rpm。1-14區的區溫度為170至230℃。
在主擠出機之末端前14D的距離、藉由氣體計量供給單元之手段將0.49g/min的氮氣和2.1g/min的二氧化碳注入熔體，控制反應確保了初始材料的反應已進行至必要程度。在第十區之後使用反向輸送螺桿元件以限制熔體的流動，這是為了分離反應區與氣體計量供給區域。藉由熔融泵、透過水下造粒機的造粒模具來形成包含發泡劑之熔體。孔的直徑為2.5mm。將造粒模具的溫度控制在190℃。造粒室內的轉動葉片會產生顆粒重量為25mg的發泡珠粒。使用造粒液體(壓力為4巴且溫度為30℃)以從造粒室排出珠粒，並將它們輸送至離心乾燥器，使它們在此與水分離並被乾燥。膨脹發泡珠粒的整體密度為130g/l。
本發明實施例1-4
使用與比較實施例之方法類似者，以TPU熔體計，將0.1至2重量%的聚矽氧(Tegomer M-SI 2650,Evonik)用計量供給進第四區(離雙螺桿擠出機之進料端為14D)。所有其它加工參數都跟比較實施例的相同。膨脹顆粒(發泡珠粒)的整體密度同樣為130g/l。表1列出了聚矽氧的比例和所得氣室形態。
在0.75巴下、藉由蒸煮來熔合所得發泡珠粒18秒，以提供厚度為20mm的試樣，並在去除前冷卻100秒。表2列出了試樣的條件和機械性質。圖1至4顯示了比較實施例和本發明實施例2至4的氣室結構。 測量方法： 整體密度係藉由以膨脹珠粒填充2000ml的容器，並使用天平測定重量來進行測定。在本發明中可假定精確度為±5g/l。
試樣(泡沫板)的密度係根據DIN EN ISO 1183-1,A來進行測定。
撕裂強力[N/mm]係藉由基於ASTM D3574 F的方法、在厚度為20mm的測試板上進行測定；並藉由基於DIN ISO 6133的方法進行評估。
發泡板的抗壓強度係在10%、25%、50%、及75%壓縮下，藉由基於DIN EN ISO 3386的方法進行測量。

Claims (11)

  1. 一種發泡珠粒，其基於包含至少一種經芳基修飾之矽氧烷的熱塑性彈性體。
  2. 根據申請專利範圍第1項之發泡珠粒，其包含以該熱塑性彈性體計為0.1至5重量%的矽氧烷。
  3. 根據申請專利範圍第1項或第2項之發泡珠粒，其包含至少一種聚二有機矽氧烷或矽氧烷嵌段共聚物。
  4. 根據申請專利範圍第1項至第3項中任一項之發泡珠粒，其包含苯基乙基甲基聚矽氧烷。
  5. 根據申請專利範圍第1項至第4項中任一項之發泡珠粒，其中該熱塑性彈性體為熱塑性聚胺甲酸酯。
  6. 根據申請專利範圍第1項至第5項中任一項之發泡珠粒，其中該珠粒的整體密度在30至350g/l範圍內。
  7. 一種用於產生根據申請專利範圍第1項至第6項中任一項之發泡珠粒的方法，其包括在發泡時使該含至少一種經芳基修飾之矽氧烷的熱塑性彈性體熔融、使發泡劑與其摻合、及對該包含發泡劑的熔體進行造粒。
  8. 一種用於產生根據申請專利範圍第1項至第6項中任一項之發泡珠粒的方法，其包含以下步驟：(a)將以下添加進聚合物加工機的第一段：用於產生熱塑性彈性體的單體及/或寡聚物、和至少一種經芳基修飾之矽氧烷、及視情況的其它初始材料； (b)混合該等單體及/或寡聚物和矽氧烷，且亦混合經視情況添加的該其它初始材料，並使該單體及/或寡聚物反應，以在聚合物加工機的第一段中提供聚合物熔體；(c)將該聚合物熔體引入該聚合物加工機的第二段並添加發泡劑，且亦視情況添加其它初始材料，以獲得包含發泡劑的聚合物熔體；以及(d)模製該包含發泡劑的聚合物熔體以提供膨脹熱塑性彈性體。
  9. 根據申請專利範圍第7項至第8項之方法，其中該發泡劑包含二氧化碳、氮、或二氧化碳和氮的混合物。
  10. 一種模製發泡體，其可透過根據申請專利範圍第1項至第6項中任一項之發泡珠粒的熔合獲得，該熔合係藉由蒸煮或用高頻電磁輻射照射。
  11. 一種模製發泡體，其可透過根據申請專利範圍第1項至第6項中任一項之發泡珠粒的黏合性結合獲得，該黏合性結合係藉由反應性黏合劑、含溶劑的黏合劑、或分散黏合劑。
TW106137848A 2016-11-04 2017-11-02 基於膨脹熱塑性彈性體之模製發泡體 TW201821495A (zh)

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