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TWI868190B - 含有聚矽氧烷己內酯多元醇之熱塑性聚胺酯及提高物品之耐熱性的方法 - Google Patents

含有聚矽氧烷己內酯多元醇之熱塑性聚胺酯及提高物品之耐熱性的方法 Download PDF

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TWI868190B
TWI868190B TW109126481A TW109126481A TWI868190B TW I868190 B TWI868190 B TW I868190B TW 109126481 A TW109126481 A TW 109126481A TW 109126481 A TW109126481 A TW 109126481A TW I868190 B TWI868190 B TW I868190B
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thermoplastic polyurethane
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diisocyanate
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翠尼達德皮德拉 克里曼特
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美商盧伯利索先進材料有限公司
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Abstract

耐熱性熱塑性聚胺酯組合物係藉由包含多元醇組分之反應製得，該多元醇組分包括聚矽氧烷與ε-己內酯之反應產物。

Description

含有聚矽氧烷己內酯多元醇之熱塑性聚胺酯及提高物品之耐熱性的方法
熱塑性聚胺酯材料在各種應用中的效用在許多新興行業中為吾人所瞭解。然而，熱塑性聚胺酯材料通常可見的一個缺點為暴露於高溫時效能損失。
因此，需要在高溫應用中保持良好物理特性的熱塑性聚胺酯組合物。
本發明為一種包括多元醇組分與聚異氰酸酯組分之反應產物的熱塑性聚胺酯組合物，其中該多元醇組分包括聚矽氧烷與ε-己內酯之反應產物，其中聚矽氧烷與ε-己內酯以1：12至1：25，例如1：12至1：15之莫耳比反應。
在一個實施例中，多元醇組分包括
Figure 109126481-A0305-12-0001-1
其中n與m可相同或不同，n或m可為0至15，其限制條件為n+m為至少12，例如12-15；y可為25至33；R1與R2可相同或不同且為直鏈或分支鏈C1至C10基團。使此多元醇組分與二異氰酸酯及視情況選用之增鏈劑反應以形成熱塑性聚胺酯組合物。
熱塑性聚胺酯組合物通常由多元醇組分、二異氰酸酯組分及視情況選用之增鏈劑組分的反應產物形成。如本文所描述，數目平均分子量係藉由分析末端官能基確定。多元醇組分
在本發明中，用於製備本發明之熱塑性聚胺酯組合物之多元醇組分包括ε-己內酯與聚矽氧烷多元醇引發之反應產物。
ε-己內酯或簡稱為己內酯為具有七員環的內酯(環酯)。ε-己內酯係本領域中眾所周知的單體。
適合的聚矽氧烷多元醇包含經α-ω-羥基或胺或羧酸或硫醇或環氧基封端之聚矽氧烷。實例包含用羥基或胺或羧酸或硫醇或環氧基封端之聚(二甲基矽氧烷)。在一些實施例中，聚矽氧烷多元醇為經羥基封端之聚矽氧烷。在一些實施例中，聚矽氧烷多元醇之數目平均分子量在300至5,000或400至3,000範圍內。
聚矽氧烷多元醇可藉由聚矽氧烷氫化物與脂族多元醇或聚氧化烯醇之間的脫氫反應獲得以將醇羥基引入聚矽氧烷主鏈上。
在一些實施例中，聚矽氧烷可由一或多種具有下式之化合物表示： 其中：各R1 及R2 獨立地為氫、1至4個碳原子烷基、苯甲基或苯基；各E為OH或NHR3 ，其中R3 為氫、1至6個碳原子烷基或5至8個碳原子環烷基；a及b各自獨立地為2至8的整數；c為3至50的整數。在含胺基聚矽氧烷中，E基團中之至少一者為NHR3 。在含羥基聚矽氧烷中，E基團中之至少一者為OH。在一些實施例中，R1 及R2 均為甲基。
可用於本發明中之聚矽氧烷材料之實例包含二羥基聚二甲基矽氧烷、經α,ω-羥丙基封端之聚(二甲基矽氧烷)及經α,ω-胺基丙基封端之聚(二甲基矽氧烷)，其均為市售材料。其他實例包含聚(二甲基矽氧烷)材料與聚(環氧烷)之共聚物。
在一個實施例中，本發明之多元醇組分包括聚二甲基矽氧烷與ε-己內酯之反應產物，其中聚二甲基矽氧烷與ε-己內酯以1:12至1:25或1:12至15之莫耳比反應。
在一個實施例中，多元醇組分適用於本發明，該多元醇組分為 其中n與m可相同或不同，n或m可為0至15，其限制條件為n+m為至少12，例如12-15，進一步例如12、13、14或15；y可為25至33，例如25、26、27、28、29、30、31、32或33；R1 與R2 可相同或不同且為直鏈或分支鏈C1 至C10 基團，例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、苯基、環己基、甲氧基乙基或3,3'-氧基二丙基。在一個實施例中，R1 及R2 為CH2 -CH2 -CH2 。
在一個實施例中，本發明之多元醇組分基本上由以下組成或由以下組成： 其中n或m可為0至15，其限制條件為n+m為至少12，例如12至25，或甚至12至15，進一步例如12、13、14或15，且y為25至33，例如25、26、27、28、29、30、31、32或33；R1與R2可相同或不同且為直鏈或分支鏈C1至C10基團，例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、苯基、環己基、甲氧基乙基或3,3'-氧基二丙基。在一個實施例中，R1及R2為CH2-CH2-CH2。
多元醇組分可具有約2000至4000，例如約3000至4000，進一步例如約3500的數目平均分子量。聚異氰酸酯組分
適用於製備本發明之熱塑性聚胺酯組合物之聚異氰酸酯包含一或多種二異氰酸酯，通常選自芳族聚異氰酸酯或脂族聚異氰酸酯或其組合。適用的聚異氰酸酯之實例包含芳族二異氰酸酯，諸如4,4´-亞甲基雙(苯基異氰酸酯)(MDI)、間二甲苯二異氰酸酯(XDI)、3,3'-二甲氧基-4,4'-伸聯苯基二異氰酸酯、伸苯基-1,4-二異氰酸酯(PDI)、伸苯基-1,3-二異氰酸酯、萘-1,5-二異氰酸酯、3,3'-二甲基-4,4'-伸聯苯基二異氰酸酯(TODI)、1,5-萘二異氰酸酯(NDI)及二異氰酸甲苯酯(TDI)；以及脂族二異氰酸酯，諸如異佛酮二異氰酸酯(IPDI)、二異氰酸1,4-環己酯(CHDI)、癸烷-1,10-二異氰酸酯、離胺酸二異氰酸酯(LDI)、1,4-丁烷二異氰酸酯(BDI)、六亞甲基二異氰酸酯(HDI)、1,4-雙(異氰酸酯基甲基)環己烷(1,4-H6XDI)及二環己基甲烷-4,4´-二異氰酸酯(H12MDI)。可使用兩種或更多種聚異氰酸酯之混合物。
在一個實施例中，聚異氰酸酯組分基本上由4,4´-亞甲基雙(苯基異氰酸酯)組成或由其組成。在另一實施例中，聚異氰酸酯基本上由六亞甲基二異氰酸酯組成或由其組成。增鏈劑組分
本文所描述之熱塑性聚胺酯組合物視情況包含增鏈劑組分。增鏈劑包含二醇、二胺及其組合。
適合的增鏈劑包含相對較小的聚羥基化合物，例如具有2至20個、或2至12個、或2至10個碳原子的低碳數脂族或短鏈二醇。適合的實例包含乙二醇、二乙二醇、三乙二醇、四乙二醇、丙二醇、二丙二醇、1,4-丁二醇(BDO)、1,6-己二醇(HDO)、1,3-丁二醇、1,5-戊二醇、新戊二醇、1,4-環己烷二甲醇(CHDM)、2,2-雙[4-(2-羥乙氧基)苯基]丙烷(HEPP)、庚二醇、壬二醇、十二烷二醇、3-甲基-1,5-戊二醇及羥乙基間苯二酚(HER)、戊螺環乙二醇(PSG)、氫醌雙(2-羥乙基)醚氫醌(HQEE)、二丙二醇(DPG)、2-甲基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇(BEPD)及其類似物，以及其混合物。在本發明之一個實施例中，增鏈劑基本上由1,4-丁二醇組成或由其組成。在另一實施例中，增鏈劑組分基本上由氫醌雙(2-羥乙基)醚氫醌組成或由其組成。在另一實施例中，增鏈劑組分基本上由戊螺環乙二醇組成或由其組成。如本文所用，「戊螺環乙二醇」或PSG係指諸如美國專利第2,945,008號中所描述之多元醇，例如由下式表示之3,9-雙(1,1-二甲基-2-羥乙基)-2,4,8,10-四氧雜螺[5.5]十一烷：。
為了製備根據本發明之熱塑性聚胺酯組合物，組分(多元醇、二異氰酸酯及視情況選用之增鏈劑)可一起反應以形成本發明之熱塑性聚胺酯組合物。使組分反應之任何已知方法可用於製備本發明之熱塑性聚胺酯組合物。在一個實施例中，該方法為所謂的「一次性」方法，其中將所有三種組分添加至擠出機反應器中且反應。
本發明之熱塑性聚胺酯組合物亦可利用預聚物方法製備。在預聚物途徑中，使多元醇中間物與通常當量過量之一或多種二異氰酸酯反應以形成其中具有游離或未反應之二異氰酸酯之預聚合物溶液。隨後，如上文所指出，以通常等於異氰酸酯端基以及任何游離或未反應之二異氰酸酯化合物之當量添加增鏈劑。通常，預聚物途徑可在包含擠出機之任何習知裝置中進行。在此類實施例中，多元醇中間物在擠出機之第一部分中與當量過量之二異氰酸酯反應以形成預聚物溶液，且增鏈劑隨後在下游部分處添加且與預聚物溶液反應。
在一個實施例中，在單螺桿或雙螺桿擠出機上混合成分，在其進料端與其模具端之間具有多個加熱區及多個進料口。可在進料口中之一或多者處添加成分，且可粒化離開擠出機之模具端之所得熱塑性聚胺酯組合物。
本發明之熱塑性聚胺酯組合物之製備可藉由任何已知習知程序及方法或以後開發之程序及方法來進行。本領域熟習此項技術者將理解其特定組分之量、各種反應物比率、處理溫度、其催化劑之量、諸如各種類型之擠出機的聚合設備及其類似者。
在聚合反應期間可存在一或多種聚合催化劑。通常，可利用任何習知催化劑使二異氰酸酯與多元醇中間物或增鏈劑反應。特定言之促進二異氰酸酯之NCO基團與多元醇之羥基及增鏈劑之間的反應的適合的催化劑之實例為自先前技術已知的習知三級胺，例如三乙胺、二甲基環己胺、N-甲基嗎啉、N,N′-二甲基哌嗪、2-(二甲胺基乙氧基)乙醇、二氮雜二環[2.2.2]辛烷及其類似者，且亦特定言之有機金屬化合物，諸如鈦酯；鐵化合物，例如乙醯基丙酮酸鐵；錫化合物例如二乙酸亞錫、二辛酸亞錫、二月桂酸亞錫或脂族羧酸之二烷基錫鹽，例如二乙酸二丁基錫、二月桂酸二丁基錫或其類似者；丙酸苯汞；辛酸鉛；乙醯基丙酮酸鐵；乙醯基丙酮酸鎂或鉍化合物，諸如辛酸鉍、月桂酸鉍及其類似者。
本發明之熱塑性聚胺酯組合物可具有95A或更小之肖氏A硬度(Shore A hardness)，例如35A至95A，進一步例如50A至95A。
其他視情況選用之組分可在聚合反應期間存在，及/或併入至上文所描述之熱塑性聚胺酯組合物中以改良處理及其他特性。此等添加劑包含(但不限於)抗氧化劑，諸如酚類、有機亞磷酸酯、膦及亞膦酸二酯、受阻胺、有機胺、有機硫化合物、內酯及羥胺化合物；殺生物劑；殺真菌劑；抗微生物劑；增容劑；電耗散劑或抗靜電添加劑；填充劑及增強劑，諸如二氧化鈦、氧化鋁、黏土及碳黑；阻燃劑，諸如磷酸鹽、鹵化材料及烷基苯磺酸鹽的金屬鹽；抗衝擊改質劑，諸如甲基丙烯酸脂-丁二烯-苯乙烯(「MBS」)及甲基丙烯酸甲酯丙烯酸丁酯(「MBA」)；脫模劑，諸如蠟、脂肪及油；顏料及著色劑；塑化劑；聚合物；流變改質劑，諸如單胺、聚醯胺蠟、聚矽氧及聚矽氧烷；助滑添加劑，諸如石蠟、烴類聚烯烴及/或氟化聚烯烴；及UV穩定劑，其可具有受阻胺光穩定劑(HALS)及/或UV光吸收劑(UVA)類型。其他添加劑可用於增強熱塑性聚胺酯組合物或摻合產物之效能。上文所描述之所有添加劑可以此等物質之習用有效量使用。
此等額外添加劑可併入至熱塑性聚胺酯組合物之組分中或併入至用於製備熱塑性聚胺酯組合物之反應混合物中或在製備熱塑性聚胺酯組合物之後併入。在另一方法中，所有材料均可與熱塑性聚胺酯組合物混合且隨後熔融，或其可直接併入至熱塑性聚胺酯組合物之熔融物中。
本發明之熱塑性聚胺酯組合物或其任何摻合物亦可用於使用諸如擠出或模製之已知技術製備各種製品。擠出或模製方法為本領域中一般技術者所熟知，且包含(但不限於)澆鑄模製、冷成型對模模製、壓縮模製、發泡模製、射出模製、氣體輔助射出模製、型面共擠出、型面擠出、旋轉模製、薄片擠出、凝塑模製、噴塗技術、熱成型、轉移模製、真空成型、濕式疊層或接觸模製、吹塑、擠出吹塑、射出吹塑及射出拉伸吹塑或其組合。
本發明之熱塑性聚胺酯組合物可用於製備用於期望耐熱性之熱塑性聚胺酯之應用的製品。熱塑性聚胺酯組合物可用於汽車、電子設備、便攜式電子設備、電子配件、電氣、通信、電氣設備及醫學應用之零件或組件中。舉例而言，其可用於生產電纜絕緣、汽車零件、電子設備及電氣設備之組件。
其他應用可包含(但不限於)：保護蓋；液體管線組件及空氣管道；建築密封件；瓶封閉件；傢俱組件；用於手持式裝置之耐磨及感覺柔軟的手柄；封裝組件，諸如密封件、瓶子、罐、杯子；醫學及衛生裝置；炊具零件及配件；體育及休閒用品，諸如球拍、腳踏車零件；鞋類鞋底、玩具及一般橡膠零件；醫學裝置；體育用品；穿戴式裝置(錶帶、健身追蹤器、眼鏡鼻托)；以及一般橡膠零件。
藉由以下實例進一步說明本發明。在實例中，PCL-BDO(2000)係指由0.84莫耳ε-己內酯與0.052莫耳1,4-丁二醇引發之反應製得之多元醇組分。PCL-PDMS(3500)係指由0.35莫耳ε-己內酯與0.029莫耳直鏈聚二甲基矽氧烷丙基羥基共聚物引發之反應製得之多元醇組分，BDO係指1,4-丁二醇，HQEE係指氫醌雙(2-羥乙基)醚，MDI係指4,4´-亞甲基雙(苯基異氰酸酯)，HDI係指六亞甲基二異氰酸酯。莫耳計算係基於製備100 g聚己內酯多元醇。
藉由使表1中所指出之組分反應形成一系列比較熱塑性聚胺酯組合物。表 1
C1 C2 C3
聚矽氧橡膠
多元醇(MW) PCL-BDO (2000) PCL-BDO (2000)
二異氰酸酯 MDI HDI
硬鏈段(%) 30 33
增鏈劑 BDO BDO
硬度(肖氏A) 60 85 85
壓縮永久變形 (100℃，22小時) (ASTM 395B) 不可能 量測，樣本不係最佳尺寸 63 78
TMA1 (起始℃) 135℃ 140℃ 122℃
微波測試 (900w-30秒)2 (視覺評估) 極佳：形狀或大小無變化 差：樣本完全變形或熔融 差：樣本完全 變形或熔融
1 熱機械分析：在Mettler TMA/SDTA 2+單元上，在-25℃至250℃之溫度範圍內記錄熱分析圖。在10℃/分鐘之加熱速率下進行分析。將板用作測試穿透類型中之樣本。所施加之力為0.02 N。
藉由使表2中所指出之組分反應來形成一系列本發明之熱塑性聚胺酯組合物。表 2.
實例1 實例2 實例3 實例4 實例5 實例6
多元醇(MW) PCL-PDMS (3500) PCL-PDMS (3500) PCL-PDMS (3500) PCL-PDMS (3500) PCL-PDMS (3500) PCL-PDMS (3500)
二異氰酸酯 MDI MDI MDI HDI HDI HDI
硬 鏈段(%) 10 30 40 33 10 17
增 鏈劑 BDO BDO HQEE BDO BDO BDO
硬度 (肖氏A) 50 88 95 90 50 70
壓縮永久變形 (100℃，22小時) (ASTM 395B) 62 48 37 47 60 57
TMA1 (起始℃) 225℃ 未測試 235℃ 210℃ 202℃ 206℃
微波測試 (900w- 30秒)2 (視覺 評估) 一般：形狀變形較小，大小變化小 良好：形狀保持不變，大小幾乎沒有變化 良好：形狀保持不變，大小幾乎沒有變化 良好：形狀保持不變，大小幾乎沒有變化 一般：形狀變形較小，大小變化小   良好：形狀保持不變，大小幾乎沒有變化
如上表所示，本發明之熱塑性聚胺酯組合物提供了優於單獨的聚矽氧橡膠材料及其他基於聚己內酯的熱塑性聚胺酯的優良結果，特別在耐熱性方面。
無。
無。

Claims (10)

  1. 一種熱塑性聚胺酯組合物，其包括以下各者之反應產物：(a)多元醇組分，其包括
    Figure 109126481-A0305-13-0001-2
     其中n及m個別地為0至15，其限制條件為n+m為12至15，y為25至33，且R1與R2為相同或不同，且係選自直鏈或分支鏈C1至C10基團；以及(b)二異氰酸酯。
  2. 如請求項1之熱塑性聚胺酯組合物，其中R1與R2為相同或不同，且係選自甲基、乙基、正丙基、異丙基、正丁基、異丁基、苯基、環己基、甲氧基乙基或3,3'-氧基二丙基(3,3’-oxidipropyl)。
  3. 如請求項1之熱塑性聚胺酯組合物，其進一步包括增鏈劑組分。
  4. 如請求項2之熱塑性聚胺酯組合物，其中該增鏈劑係由1,4-丁二醇所組成。
  5. 如請求項2之熱塑性聚胺酯組合物，其中該增鏈劑係由氫醌雙(2-羥乙基)醚所組成。
  6. 如請求項1之熱塑性聚胺酯組合物，其中該二異氰酸酯係由4,4'-亞甲基雙(苯基異氰酸酯)所組成。
  7. 如請求項1之熱塑性聚胺酯組合物，其中該二異氰酸酯係由六亞甲基二異氰酸酯所組成。
  8. 一種由如請求項1至7中任一項之熱塑性聚胺酯組合物所製得之物品。
  9. 一種提高物品之耐熱性的方法，其包括以下步驟：(i)使(a)多元醇組分，該多元醇組分包括
    Figure 109126481-A0305-13-0002-3
     其中n及m個別地為0至15，其限制條件為n+m為12至15，y為25至33，且R1與R2為相同或不同且係選自直鏈或分支鏈C1至C10基團；與(b)二異氰酸酯進行反應；(ii)藉由擠出或模製以形成物品。
  10. 如請求項9之方法，其中R1與R2為相同或不同，且係選自甲基、乙基、正丙基、異丙基、正丁基、異丁基、苯基、環己基、甲氧基乙基或3,3'-氧基二丙基。
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