TWI803450B - 類共沸物組成物 - Google Patents

類共沸物組成物 Download PDF

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TWI803450B
TWI803450B TW105141039A TW105141039A TWI803450B TW I803450 B TWI803450 B TW I803450B TW 105141039 A TW105141039 A TW 105141039A TW 105141039 A TW105141039 A TW 105141039A TW I803450 B TWI803450 B TW I803450B
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菊地秀明
松本剛徳
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Abstract

本發明旨在藉由提供一種新的類共沸物組成物，其可用於廣泛範圍之工業用途，而解決前述問題。

提供一種類共沸物組成物，其包括93.0至99.0質量% Z-1,1,1,4,4,4-六氟-2-丁烯以及0.1至7質量%異丙醇。

Description

類共沸物組成物
本發明係關於一種由Z-1,1,1,4,4,4-六氟-2-丁烯與異丙醇所組成之類共沸物組成物。
到目前為止，許多工業內，鹵化烴諸如氯氟碳化物(CFC)、氫氯氟碳化物(HCFC)、和氫氟碳化物(HFC)係已用在廣泛範圍的應用中，包括氣膠推噴劑、冷媒、溶劑、清潔劑、用於發泡劑(發泡體膨脹劑)之熱塑性及熱固性發泡體、熱傳遞介質、氣體介電質、滅火劑和抑火劑、動力循環工作流體、聚合介質、粒子除去流體、載體流體、拋光研磨劑、及置換乾燥劑。
同時，CFC與HCFC已知係臭氧傷害物質，而HFC雖然不會傷害臭氧層，但其卻是衝擊全球暖化的溫室氣體。因此，現在正在尋求具有較低環境衝擊，換句話說，臭氧消耗潛力係零以及就全球暖化而言具有極低潛力之替代性組成物。
共沸物，其在於蒸發使用或收集時之期間不會分餾，換句話說，其具有固定沸點特性，且當經沸騰或經蒸發時不會分餾，係已知有效作為這種類之替代性組成物(參見，例如，專利文件1、2、及3)。然而，如專利文件1所指出，理論上不可能預期共沸物 是否將會形成，且因此，仍持續考慮關於將各式物質組合在一起以尋求具有優異特性之新共沸物。
先前技術相關文件
專利文件1：專利標記H6-501949
專利文件2：專利標記2013-514444
專利文件3：專利標記2012-528922
本發明旨在藉由提供一種新的類共沸物組成物，其可用於廣泛範圍之工業用途，而解決前述問題。
本發明之發明人已發現Z-1,1,1,4,4,4-六氟-2-丁烯(Z-HFO-1336mzzm)，其具有係零的臭氧消耗潛力，以及係低於10的全球暖化潛力，形成異丙醇(IPA)以及一共沸物，其中體積電阻率係進一步藉由一小量IPA顯著降低，藉此達成本發明。
換句話說，本發明具有下述特性。
1.一種類共沸物組成物，其包括93.0至99.9質量% Z-1,1,1,4,4,4-六氟-2-丁烯以及0.1至7質量%異丙醇。
2.一種固體表面清潔劑，其包括1中之該類共沸物組成物。
3.2中之清潔劑，其中該固體表面係一半導體表面。
4.一種冷卻劑，其包括1中之類共沸物組成物。
5.一種發泡劑，其包括1中之類共沸物組成物。
本發明允許提供一種類共沸物組成物，其具有係零之臭氧消耗潛力，以及極低之全球暖化潛力。
本發明中之組成物具有低體積電阻率，其允許因為靜電之微觀粒子附著或再附著受到控制、確保低黏度和表面張力、以及高密度，於是其具有高滲透力，且係特別適合用於作為清潔劑，尤其是用於固體表面的清潔劑(表面加工劑)使用，例如用於從半導體表面除去微觀粒子。
再者，Z-HFO-1336mzzm變成添加有一微觀量IPA之一共沸物，IPA便宜且無害，且其進一步顯著降低體積電阻率，結果是該共沸物不會變得易燃，且額外地，因為僅需要一微觀量之IPA，而可以限制被大氣中水汽汙染，該水汽係與IPA極度相容。
圖1：描繪Z-HFO-1336mzzm與IPA之混合物的沸騰曲線。
圖2：描繪Z-HFO-1336mzzm與IPA之混合物的體積電阻率。
下面係本發明之詳細說明。
本發明係一種類共沸物組成物，其實質上形成自Z-1,1,1,4,4,4-六氟-2-丁烯(Z-HFO-1336mzzm)與異丙醇(IPA)。本發明之組成物內之組分皆係已知化學物質。例如，Z-HFO-1336mzzm可使用揭示於美國已公開之專利申請案第2008-0269532A1號之詳細說明中的方法製造。
如為相關技術領域所認知者，共沸物組成物係二或更多種不同物質的混合物，共沸物組成物在給定壓力條件下呈液體形式，且在一特定溫度實質上沸騰；其中，該溫度係高於或低於個別組分之沸騰溫度，且於沸騰期間提供一蒸汽組成物，其實質上相同於整體液體組成物(例如，參見M.F.Doherty與M.F.Malone之Conceptual Design of Distillation Systems,McGraw-Hill(New York),2001,pp.185-186,351-359))。
在此時點，接近共沸物混合物液體組成物之在一範圍內的液體組成物，若以各種方式改變，並經測量以判定在固定壓力之蒸汽-液體平衡關係，則已知共沸物之沸點將被最大化或最小化。
據此，共沸物組成物之實質屬性是，其作為一液體組成物在給定壓力條件下之沸點係固定的，以及於沸騰期間，組成物之上方蒸汽之組成係實質上沸騰期間該液體之整體之組成(換句話說，該液體組成物之組分根本不會分餾)。也為相關技術領域中已知的是，若共沸物組成物在一不同壓力沸騰，沸點與共沸物組成物之各組分的質量%兩者都可能改變。據此，共沸物組成物可從組分之間的具體關係之角度、或從組分之組成範圍之角度、或從取決於在 特定之壓力時固定之沸點的組成物中各組分之精確質量%之角度來定義。
為了滿足本發明之目標，本發明中之類共沸物組成物係視為表現得像一共沸物組成物(換句話說，其具有固定之沸點屬性以及當沸騰或蒸發時不分餾之傾向)。因此，於沸騰或蒸發期間，即使是蒸汽-液體組成改變了，該等改變係經最小化或係一可被忽略之程度。這與非類共沸物組成物相反，非類共沸物組成物之蒸汽-液體組成於沸騰或蒸發期間經歷顯著改變。
再者，本發明中之類共沸物組成物展示不具有實質溫度差異的液相線與汽相線。換句話說，在給定壓力之液體溫度與氣體溫度間之值的差異係小的。於本發明中，相信展示出與液相溫度(基於最小共沸物點)差異最大值係2℃之組成物係類共沸物。
再者，若一系統之相對揮發度接近1.0，該系統於本領域中已知被定義為形成共沸物組成物或類共沸物組成物。相對揮發度係組分1的揮發度與組分2的揮發度之比率。一組分之揮發度係藉由找出一組份於蒸汽中之莫耳分率與於液體中者之比而計算。
本發明中之類共沸物，含有Z-HFO-1336mzzm與IPA，於大氣壓力下之沸點係較佳於範圍33.5℃±2℃、或較佳±1℃內，以及更較佳於該範圍±0.5℃，具有Z-HFO-1336mzz：IPA=99.9至93質量%：0.1至7質量%，或較佳，Z-HFO-1336mzz：IPA=99.9至95質量%：0.1至5質量%，或更較佳，99.9至97質量%：0.1 至3質量%，或甚至更較佳，99.9至98質量%：0.1至2質量%，或最較佳，99.9至99質量%：0.1至1質量%之組成。
有需要時，本發明中之類共沸物組成物可包括一或多種硝基烷、環氧化物、呋喃、苯并三唑、酚、胺、或磷酸酯(phosphate)作為穩定劑，且關於類共沸物組成物之組成體積係0.01至5wt%，較佳0.05至0.5wt%。
額外地，視需要，本發明中之類共沸物組成物可含有其他組分諸如醇(IPA以外者)、酮、醚、酯、烴、胺、二醇醚或矽氧烷，限制條件是其不對本發明之屬性有害。
本發明中之類共沸物組成物具有係零之臭氧消耗潛力(ODP)，以及大概低於100，較佳低於50，以及更較佳低於10的全球暖化潛力(GWP)。此處，如應用至本發明，ODP及GWP係定義在臭氧消耗科學評估(Scientific Assessment of Ozone Depletion,2002)中，其係一份由世界氣象組織發表的報告。
本發明中之類共沸物組成物可用在其中已習知地使用鹵化烴之廣泛範圍的用途中，諸如氣膠推噴劑、冷卻劑、溶劑、清潔劑、粒子除去流體、用於發泡劑(發泡體膨脹劑)之熱塑性及熱固性發泡體、熱傳遞介質、氣體介電質、滅火劑和抑火劑、動力循環工作流體、聚合介質、載體流體、拋光研磨劑、及置換乾燥劑。
這些中，本發明中之類共沸物組成物係特別適合用於作為清潔劑(微觀粒子除去流體)，用於清洗被有機或無機物質汙染之固體表面，諸如半導體表面、電子基材表面、電子電路、CMOS (互補金屬氧化物半導體)、MEMS(微機電系統)、硬碟表面以及其他微結構，以及尤其，用於清洗被微觀粒子汙染之半導體表面。
再者，本發明中之類共沸物組成物也適合用於作為冷卻劑，用於冷凍用途。尤其，因為其具有於範圍30至40℃之一沸點，且展示共沸物特性，其也特別適於用於使用涉及冷凝本發明中之類共沸物組成物，以及將其在需要冷卻之物質的附近蒸發之一冷卻程序，而作為冷卻劑(沸騰冷卻)。
額外地，當製造熱塑性或熱固性發泡體時，本發明中之類共沸物組成物係特別適合用於作為發泡劑(發泡體膨脹劑)。
下面係一參考實施例之本發明的實施方式。
實施例
一包括Z-HFO-1336mzzm與IPA(Wako，等級1)之混合物係使用下面方法測量，以建立其之沸點、體積電阻率、黏度、表面張力、密度以及閃點。
沸點(平衡回返沸點)
沸點(平衡回返沸點)的測量係根據JIS K 2233，使用5℃冷卻水溫度，並在加熱板與燒瓶之間無東西之情況下實施加熱。
結果於圖1中給出。在IPA 0.5質量%附近展示了一最小化沸點，因此確認Z-HFO-1336mzzm與IPA展示一共沸物組成物。
體積電阻率
體積電阻率係使用由ADC Co.,Ltd製造之非電阻測量裝置Digital Electronmeter 5415測量。使用1ml體積之一單元，且外加一50V電壓，於1分鐘後測量數值。量測期間之環境溫度係於23至25℃之間，濕度在28至35%之間。
結果於圖2給出。一小量IPA之添加顯著地降低Z-HFO-1336mzzm之體積電阻率。
黏度、表面張力、密度
混合物之黏度、表面張力及密度係使用下面式子計算。
˙表面張力：Macleod-Sugden相關性方程式。
σ1/4=[P](ρL-ρV)/MW
σ：表面張力
P：等張比容係數(Parachor coefficient)
ρL：液體比重
ρL：蒸汽比重
MW：分子量
Z-HFO-1336mzzm之表面張力係13.5mN/m(設定在USA NIST「REFPROP」計算值，25℃)。
˙黏度：McAllister方法
1nηm=Σxif(ηi)
η：黏度
x：莫耳分率
f(η)：黏度對數
Z-HFO-1336mzzm黏度係0.39mPa*s(設定在USA NIST「REFPROP」計算值，25℃)，IPA黏度係2.08mPa*s(使用Solvent Pocketbook,Soc.Of Synthetic Organic Chemistry，25℃(20℃及30℃之間的中點))。
˙密度：Amagat定律(Amagat’s law)
Vm=ΣxjVj
V：密度
x：莫耳分率
Z-HFO-1336mzzm之密度係1.36g/ml(設定在USA NIST「REFPROP」計算值，25℃)，且IPA密度係0.79g/ml(使用25℃，流體之熱特性(Thermal properties of fluids,Japan Soc.Of Mechanical Engineers))。
閃點
閃點之測量係根據JIS K 2265-1980，使用Tag閉式與Cleveland開式閃點測試(the Tag closed and Cleveland open flashpoint test)進行。
包括99質量% Z-HFO-1336mzzm與1質量% IPA之類共沸物組成物之GWP、沸點、體積電阻率、黏度、表面張力、密度及閃點係顯示於表1中。
Figure 105141039-A0202-12-0010-1
除了顯著降低表面張力，納入1% IPA還顯著降低體積電阻率，使得該物質極度適合用於作為清潔劑。

Claims (5)

  1. 一種類共沸物組成物，其包含93.0至99.9質量%Z-1,1,1,4,4,4-六氟-2-丁烯以及0.1至7質量%異丙醇。
  2. 一種固體表面清潔劑，其包含如請求項1之該類共沸物組成物。
  3. 如請求項2之清潔劑，其中該固體表面係一半導體表面。
  4. 一種冷卻劑，其包含如請求項1之類共沸物組成物。
  5. 一種發泡劑，其包含如請求項1之類共沸物組成物。
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