TW201418437A - 熱傳送流體及其使用之腐蝕抑制劑調配物 - Google Patents
熱傳送流體及其使用之腐蝕抑制劑調配物 Download PDFInfo
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- TW201418437A TW201418437A TW102132247A TW102132247A TW201418437A TW 201418437 A TW201418437 A TW 201418437A TW 102132247 A TW102132247 A TW 102132247A TW 102132247 A TW102132247 A TW 102132247A TW 201418437 A TW201418437 A TW 201418437A
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- heat transfer
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
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- 239000011236 particulate material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 235000019828 potassium polyphosphate Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- 235000003702 sterols Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OKUCEQDKBKYEJY-UHFFFAOYSA-N tert-butyl 3-(methylamino)pyrrolidine-1-carboxylate Chemical compound CNC1CCN(C(=O)OC(C)(C)C)C1 OKUCEQDKBKYEJY-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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Abstract
本文揭示一種熱傳送流體濃縮物，其包含：大於或等於90重量%之凝固點降低劑；16至80 ppm之鎂離子；唑化合物；無機磷酸鹽；羧酸鹽；及基於丙烯酸酯之聚合物，其中該熱傳送流體濃縮物之pH值為7-9.5，且基於丙烯酸酯之聚合物與鎂離子之重量比為1至25。該熱傳送流體濃縮物可用於製造熱傳送流體。
Description
現代車輛引擎通常需要熱傳送流體(液體冷卻劑)來為其冷卻系統提供持久的常年保護。熱傳送流體之主要要求為其可提供有效熱傳送以控制並維持引擎溫度以便實現有效燃料經濟性及潤滑，並且防止由於凍結、沸騰溢出或過熱所致之引擎故障。熱傳送流體之另一關鍵要求為其可在廣泛的溫度及操作條件範圍內為所有冷卻系統金屬提供腐蝕保護。對引擎體、氣缸頭、水泵、熱交換器及由鋁或鋁合金製成之其他組件的鋁腐蝕保護尤其重要。除金屬保護外，腐蝕保護有助於熱傳送流體實現其將過量熱量自引擎傳送至散熱器以便消散的主要功能。
持續需要具有良好熱傳送及腐蝕保護之熱傳送流體。
此需要至少部分可由包含以下各物之熱傳送流體濃縮物來滿足：大於或等於85重量%之凝固點降低劑；16至80ppm之鎂離子；唑化合物；無機磷酸鹽；羧酸鹽；及基於丙烯酸酯之聚合物，其中該熱傳送流體濃縮物之pH值為7至9.5，且基於丙烯酸酯之聚合物與鎂離子之重量比為1至25。
可將熱傳送流體濃縮物稀釋以形成熱傳送流體冷卻劑，其包含：小於90重量%之凝固點降低劑；水；8至60ppm之鎂離子；唑化
合物；無機磷酸鹽；羧酸；大於0.5ppm之鈣離子；及基於丙烯酸酯之聚合物，其中該熱傳送流體之pH值為7-9.5，且基於丙烯酸酯之聚合物與鎂離子之重量比為1至25。
本文中亦描述熱傳送系統，其包含如本文中所描述之熱傳送流體濃縮物或熱傳送冷卻劑及熱傳送裝置。
本文中揭示熱傳送流體濃縮物及熱傳送流體組合物，該等熱傳送流體組合物顯示組合物之組分之間的協同效應。在包含乙二醇、水、羧酸鹽、無機磷酸鹽及唑化合物之熱傳送流體中，觀測到鎂離子與基於丙烯酸酯之聚合物之間的協同效應，如腐蝕測試及儲存測試中所示。當熱傳送流體濃縮物中基於丙烯酸酯之聚合物與鎂離子(均以ppm或wt%表示)之比率為1至25時觀測到最佳效能。在熱傳送流體之情況下，結果顯示添加1-15ppm鈣離子可確保儲存穩定性及良好腐蝕效能。鈣離子對鎂離子在含磷酸鹽之熱傳送流體中之溶解度的作用尤其令人驚訝。各種鈣磷酸鹽在pH值介於7與9.5之間的水溶液中的高度不溶性質會導致熟習此項技術者預測不良溶解度係由於溶液熱力學因素所致。
熱傳送流體濃縮物及熱傳送流體可能不含矽酸鹽、硼酸鹽及胺。以熱傳送流體濃縮物或熱傳送流體之總重量計，硝酸鹽含量以重量計可能小於50ppm。
凝固點降低劑可為醇或醇混合物。例示性醇包括一元醇或多元醇及其混合物。醇可選自由以下組成之群：甲醇、乙醇、丙醇、丁醇、糠醛、糠醇、四氫糠醇、乙氧基化糠醇、乙二醇、丙二醇、1,3-丙二醇、甘油、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、二
丙二醇、丁二醇、甘油-1,2-二甲醚、甘油-1,3-二甲醚、甘油單乙醚、山梨糖醇、1,2,6-己三醇、三羥甲基丙烷、烷氧基烷醇(諸如甲氧基乙醇)及上述兩者或兩者以上之組合。
在熱傳送流體濃縮物中，以熱傳送流體濃縮物之總重量計，凝固點降低劑之存在量大於或等於85重量%(wt%)且小於或等於99wt%。在此範圍內，凝固點濃縮物之量可大於或等於86wt%、大於或等於87wt%、大於或等於88wt%、大於或等於89wt%、大於或等於90wt%、大於或等於91wt%、大於或等於92wt%、大於或等於93wt%、大於或等於94wt%、大於或等於95wt%、大於或等於96wt%、大於或等於97wt%或大於或等於98wt%。
羧酸鹽具有6至20個碳原子。術語「羧酸鹽」包括羧酸、其鹽及羧酸與羧酸鹽之組合。羧酸鹽可包含單一或多個羧基且可為直鏈或分支鏈。明確預期可使用羧酸鹽之組合且其由術語「羧酸鹽」或「羧酸」涵蓋。例示性脂族羧酸鹽包括2-乙基己酸、己酸、庚酸、辛酸、新癸酸、癸酸、壬酸、異庚酸、十二酸、癸二酸、己二酸、庚二酸、辛二酸、壬二酸、十二烷二酸及上述兩者或兩者以上之組合。例示性芳族羧酸鹽包括苯甲酸、甲苯甲酸或甲基苯甲酸、第三丁基苯甲酸、烷氧基苯甲酸(例如甲氧基苯甲酸(或鄰茴香酸、對茴香酸、間茴香酸))、水楊酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯乙酸、扁桃酸、1,2,4-苯三甲酸及上述兩者或兩者以上之組合。
在熱傳送流體濃縮物中，以熱傳送流體濃縮物之總重量計，羧酸鹽之存在量為1wt%至10wt%。在此範圍內，該量可大於或等於1.5wt%或更特定言之，大於或等於2wt%。亦在此範圍內，該量可小於或等於7wt%或更特定言之，大於或等於5wt%。
無機磷酸鹽可為磷酸、正磷酸鈉、正磷酸鉀、焦磷酸鈉、焦磷酸鉀、聚磷酸鈉、聚磷酸鉀、六偏磷酸鈉、六偏磷酸鉀或前述無機磷
酸鹽中之兩者或兩者以上之組合。
在熱傳送流體濃縮物中，以熱傳送流體濃縮物之總重量計，無機磷酸鹽之存在量可為0.10wt%至0.60wt%。在此範圍內，該量可大於或等於0.11wt%或更特定言之，大於或等於0.12wt%。亦在此範圍內，該量可小於或等於0.45wt%或更特定言之，大於或等於0.40wt%。
熱傳送流體添加劑組合物包含唑。例示性唑包括苯并三唑、甲苯基三唑、甲基苯并三唑(例如4-甲基苯并三唑及5-甲基苯并三唑)、丁基苯并三唑及其他烷基苯并三唑(例如烷基含有2至20個碳原子)、巰基苯并噻唑、噻唑及其他經取代之噻唑、咪唑、苯并咪唑及其他經取代之咪唑、吲唑及經取代之吲唑、四唑、四氫甲苯基三唑及經取代之四唑。亦可使用前述唑中之兩者或兩者以上之組合，且唑之組合包括於術語「唑」中。
在熱傳送流體濃縮物中，以熱傳送流體濃縮物之總重量計，唑化合物之存在量可為0.01wt%至3wt%。在此範圍內，唑化合物之存在量可大於或等於0.05wt%或更特定言之，大於或等於0.1wt%。亦在此範圍內，唑化合物之存在量可小於或等於2wt%或更特定言之，大於或等於1wt%。
鎂離子來源於可在室溫下溶解於含水溶液中時產生鎂離子的鎂化合物。鎂化合物可為無機鎂化合物，諸如硝酸鎂、硫酸鎂、鉬酸鎂、鎢酸鎂、釩酸鎂、過氯酸鎂、氫氧化鎂或其組合。鎂化合物可溶於熱傳送流體中。如本文中所用，可溶定義為溶解以使得肉眼不可見顆粒物質。鎂化合物亦可為鎂離子與含有一或多個羧酸基之有機酸之間形成的鎂鹽，諸如聚丙烯酸鎂、聚順丁烯二酸鎂、乳酸鎂、檸檬酸鎂、酒石酸鎂、葡糖酸鎂、葡糖庚酸鎂、羥乙酸鎂、葡糖二酸鎂、丁二酸鎂、羥基丁二酸鎂、己二酸鎂、草酸鎂、丙二酸鎂、胺基苯磺酸
鎂、甲酸鎂、乙酸鎂、丙酸鎂、脂族三羧酸或脂族四羧酸之鎂鹽及前述鎂化合物之組合。
在熱傳送流體濃縮物中，鎂化合物係以使得熱傳送流體之鎂離子濃度以熱傳送流體濃縮物之重量計為16至80百萬分率(ppm)之量存在。在此範圍內，鎂離子濃度可大於或等於20ppm或更特定言之，大於或等於22ppm。亦在此範圍內，鎂離子濃度可小於或等於75ppm或更特定言之，小於或等於70ppm。
熱傳送流體濃縮物包含基於丙烯酸酯之聚合物。基於丙烯酸酯之聚合物為水溶性聚合物(平均分子量為200至200,000道爾頓)。例示性丙烯酸酯聚合物包括聚丙烯酸酯、基於丙烯酸酯之聚合物、共聚物、三元共聚物及四元共聚物，諸如丙烯酸酯/丙烯醯胺共聚物、聚甲基丙烯酸酯、聚順丁烯二酸或順丁烯二酸酐聚合物、基於順丁烯二酸之聚合物、其共聚物及三元共聚物、經改質之基於丙烯醯胺之聚合物，包括聚丙烯醯胺、基於丙烯醯胺之共聚物及三元共聚物。通常，適用的水溶性聚合物包括具有以下單體單元之均聚物、共聚物、三元共聚物及互聚物：(1)至少一個含有C3至C16單烯系不飽和單羧酸或二羧酸或其鹽之單體單元；或(2)至少一個含有C3至C16單烯系不飽和單羧酸或二羧酸衍生物(諸如醯胺、腈、羧酸酯、酸鹵化物(例如氯化物)及酸酐)之單體單元及其組合。在一些實施例中，基於丙烯酸酯之聚合物包含膦基聚丙烯酸酯。
在熱傳送流體濃縮物(及由該濃縮物製造之熱傳送流體)中，基於丙烯酸酯之聚合物之量係基於鎂離子之量來選擇。基於丙烯酸酯之聚合物與鎂離子之比率係大於1且小於25。在此範圍內，該比率可大於或等於2，或更特定言之，大於或等於3。亦在此範圍內，該比率可小於或等於20，或更特定言之，小於或等於15。丙烯酸根離子之比率係使用溶解於該濃縮物中之基於丙烯酸酯之聚合物的量(重量)來確定。
熱傳送流體濃縮物可進一步包含鈣離子。鈣離子係來源於可在室溫下溶解於含水溶液中時產生鈣離子的鈣化合物。鈣化合物可為無機鈣化合物，諸如硝酸鈣、氯化鈣、過氯酸鈣、鉬酸鈣、鎢酸鈣、釩酸鈣、氫氧化鈣或其組合。鈣化合物可溶於熱傳送流體中。如本文中所用，可溶係定義為溶解以使得肉眼不可見顆粒物質。鈣化合物亦可為在鈣離子與含有一或多個羧酸基之有機酸之間形成的鈣鹽，諸如聚丙烯酸鈣、聚順丁烯二酸鈣、乳酸鈣、檸檬酸鈣、酒石酸鈣、葡糖酸鈣、葡糖庚酸鈣、羥乙酸鈣、葡糖二酸鈣、丁二酸鈣、羥基丁二酸鈣、己二酸鈣、草酸鈣、丙二酸鈣、胺基苯磺酸鈣、甲酸鈣、乙酸鈣、丙酸鈣、脂族三羧酸或脂族四羧酸之鈣鹽及前述鈣化合物之組合。
鈣化合物係以使得熱傳送流體濃縮物之鈣離子濃度以熱傳送流體之總重量計大於0.5百萬分率之量存在。在此範圍內，鈣離子之量可小於20ppm。在此範圍內，鈣離子之量可小於或等於10ppm。
熱傳送流體可進一步包含鋰離子。鋰離子來源於可在室溫下溶解於含水溶液中時產生鋰離子的鋰化合物。鋰化合物可為無機鋰化合物，諸如氫氧化鋰、磷酸鋰、硼酸鋰、硝酸鋰、過氯酸鋰、硫酸鋰、鉬酸鋰、釩酸鋰、鎢酸鋰、碳酸鋰或其組合。鋰化合物可溶於熱傳送流體中。如本文中所用，可溶定義為溶解以使得肉眼不可見顆粒物質。鋰化合物亦可為鋰離子與含有一或多個羧酸基之有機酸之間形成的鋰鹽，諸如乙酸鋰、苯甲酸鋰、聚丙烯酸鋰、聚順丁烯二酸鋰、乳酸鋰、檸檬酸鋰、酒石酸鋰、葡糖酸鋰、葡糖庚酸鋰、羥乙酸鋰、葡糖二酸鋰、丁二酸鋰、羥基丁二酸鋰、己二酸鋰、草酸鋰、丙二酸鋰、胺基苯磺酸鋰、甲酸鋰、丙酸鋰、脂族單羧酸、二羧酸或三羧酸或芳族單羧酸、二羧酸或三羧酸之鋰鹽及前述鋰化合物之組合。
鋰化合物可以使得熱傳送流體濃縮物之鋰離子濃度以熱傳送流
體之重量計為50至2000百萬分率(ppm)之量存在。在此範圍內，鋰離子濃度可小於或等於1500ppm或更特定言之，小於或等於1000ppm。亦在此範圍內，鋰離子濃度可大於或等於60ppm或更特定言之，大於或等於65ppm。
在室溫下，熱傳送流體濃縮物之pH值為7至9.5。在此範圍內，該pH值可大於或等於7.5或大於或等於7.8。亦在此範圍內，該pH值可小於或等於9.0或小於或等於8.8。
熱傳送流體濃縮物可進一步包含膦醯基羧酸酯。膦醯基羧酸酯為具有以下通式之膦酸化化合物：H[CHRCHR]n-PO3M2，其中各單元中至少一個R基團為COOM、CH2OH、磺醯基或膦醯基且另一R基團(其可與第一個R基團相同或不同)為氫或COOM、羥基、膦醯基、磺醯基、硫酸基、C1-7烷基、C1-7烯基或羧酸酯基、膦醯基、磺醯基、硫酸基及/或經羥基取代之C1-7烷基或C1-7烯基，n為1或大於1之整數，且各M為氫或鹼金屬離子，諸如鈉離子、鉀離子及其類似物。此外，至少一個COOM基團將存在於R基團之一中。膦醯基羧酸酯較佳為順丁烯二酸之膦酸化寡聚物或膦酸化寡聚物之混合物，其具有式H[CH(COOM)CH(COOM)]n-PO3M2，其中n為1或大於1之整數，且M為陽離子性物質(例如鹼金屬陽離子)，以使得該化合物可溶於水。例示性膦醯基羧酸酯包括膦醯基丁二酸、1-膦醯基-1,2,3,4-四羧基丁烷及1-膦醯基-1,2,3,4,5,6-六羧基己烷。膦醯基羧酸酯可為具有前述化學式(具有不同的「n」值)之化合物的混合物。「n」之平均值可為1至2，或更特定言之，1.3至1.5。膦醯基羧酸酯之合成方法為已知的且描述於美國專利第5,606,105號中。膦醯基羧酸酯獨立且不同於上述羧酸酯。上述羧酸酯由碳、氫及氧組成且不含非氧雜原子。
在熱傳送流體濃縮物中，以熱傳送流體濃縮物之總重量計，膦醯基羧酸酯之存在量可為10至500ppm。在此範圍內，膦醯基羧酸酯之存在量可大於或等於20ppm或大於或等於40ppm。亦在此範圍內，膦醯基羧酸酯之存在量可小於或等於400ppm或小於或等於300ppm。
熱傳送流體濃縮物可進一步包含膦基羧酸酯。膦基羧酸酯為具有以下通式之化合物：H[CHR1CHR1]n-P(O2M)-[CHR2CHR2]mH，其中各單元中至少一個R1基團為COOM、CH2OH、磺醯基或膦醯基且另一R1基團(其可與第一個R1基團相同或不同)為氫或COOM、羥基、膦醯基、磺醯基、硫酸基、C1-7烷基、C1-7烯基或羧酸酯基、膦醯基、磺醯基、硫酸基及/或經羥基取代之C1-7烷基或C1-7烯基，n為等於或大於1之整數，且各M為氫或鹼金屬離子，諸如鈉離子、鉀離子及其類似物。類似地，各單元中至少一個R2基團為COOM、CH2OH、磺醯基或膦醯基且另一R2基團(其可與第一個R2基團相同或不同)為氫或COOM、羥基、膦醯基、磺醯基、硫酸基、C1-7烷基、C1-7烯基或羧酸酯基、膦醯基、磺醯基、硫酸基及/或經羥基取代之C1-7烷基或C1-7烯基，m為等於或大於0之整數。此外，至少一個COOM基團將存在於R1及R2基團之一中。例示性膦基羧酸酯包括如美國專利第6,572,789號及第5,018,577號中所描述之一元膦酸基丁二酸及水溶性鹽、一元膦酸基雙(丁二酸)及水溶性鹽以及一元膦酸基丁二酸寡聚物及鹽。膦醯基羧酸酯可為具有前述化學式(具有不同的「n」及「m」值)之化合物的混合物。膦基羧酸酯獨立且不同於上述羧酸酯。
在熱傳送流體濃縮物中，以熱傳送流體濃縮物之總重量計，膦基羧酸酯之存在量可為10至500ppm。在此範圍內，膦基羧酸酯之存在量可大於或等於20ppm或大於或等於40ppm。亦在此範圍內，膦基羧酸酯之存在量可小於或等於400ppm或小於或等於300ppm。
熱傳送流體濃縮物(且因此熱傳送流體)可視情況包含消泡劑或去泡劑、分散劑、防垢劑、界面活性劑、著色劑及其他冷卻劑添加劑中之一或多者。
例示性消泡劑包括基於聚二甲基矽氧烷乳液之消泡劑。其包括得自Performance Chemicals,LLC(Boscawen,NH)之PC-5450NF；得自CNC International(Woonsocket,RI)之CNC消泡劑XD-55 NF及XD-56。適用於本發明之其他消泡劑包括環氧乙烷(EO)與環氧丙烷(PO)之共聚物，諸如得自BASF之Pluronic L-61。
通常，視情況選用之消泡劑可包含聚矽氧，例如SAG 10或可得自OSI Specialties、Dow Corning或其他供應商之類似產品；環氧乙烷-環氧丙烷(EO-PO)嵌段共聚物及環氧丙烷-環氧乙烷-環氧丙烷(PO-EP-PO)嵌段共聚物(例如Pluronic L61、Pluronic L81或其他Pluronic及Pluronic C產品)；聚(環氧乙烷)或聚(環氧丙烷)，例如PPG 2000(亦即平均分子量為2000之聚環氧丙烷)；疏水性非晶二氧化矽；基於聚二有機矽氧烷之產品(例如含有聚二甲基矽氧烷(PDMS)之產品及其類似物)；脂肪酸或脂肪酸酯(例如硬脂酸及其類似物)；脂肪醇、烷氧基化醇及聚二醇；聚醚多元醇乙酸酯、聚醚乙氧基化山梨糖醇六油酸酯及聚(環氧乙烷-環氧丙烷)單烯丙基醚乙酸酯；蠟、石腦油、煤油及芳族油；及包含前述消泡劑中之一或多者之組合。
例示性界面活性劑包括脂肪酸酯，諸如脫水山梨糖醇脂肪酸酯、聚烷二醇、聚烷二醇酯、環氧乙烷(EO)與環氧丙烷(PO)之共聚物、脫水山梨糖醇脂肪酸酯之聚環氧烷衍生物及其混合物。非離子性界面活性劑之平均分子量可為55至300,000或更特定言之，110至10,000。合適脫水山梨糖醇脂肪酸酯包括脫水山梨糖醇單月桂酸酯(例如以商標名Span® 20、Arlacel® 20、S-MAZ® 20M1出售)、脫水山梨糖醇單棕櫚酸酯(例如Span® 40或Arlacel® 40)、脫水山梨糖醇單
硬脂酸酯(例如Span® 60、Arlacel® 60或S-MAZ® 60K)、脫水山梨糖醇單油酸酯(例如Span® 80或Arlacel® 80)、脫水山梨糖醇單倍半油酸酯(例如Span® 83或Arlacel® 83)、脫水山梨糖醇三油酸酯(例如Span® 85或Arlacel® 85)、脫水山梨糖醇三硬脂酸酯(例如S-MAZ® 65K)、脫水山梨糖醇單樹脂酸酯(例如S-MAZ® 90)。合適聚烷二醇包括聚乙二醇、聚丙二醇及其混合物。適用的聚乙二醇之實例包括得自Dow Chemical Company之CARBOWAXTM聚乙二醇及甲氧基聚乙二醇(例如CARBOWAX PEG 200、300、400、600、900、1000、1450、3350、4000及8000等)或得自BASF Corp.之PLURACOL®聚乙二醇(例如Pluracol® E 200、300、400、600、1000、2000、3350、4000、6000及8000等)。合適聚烷二醇酯包括各種脂肪酸之單酯及二酯，諸如得自BASF之MAPEG®聚乙二醇酯(例如MAPEG® 200ML或PEG 200單月桂酸酯、MAPEG® 400 DO或PEG 400二油酸脂、MAPEG® 400 MO或PEG 400單油酸酯，及MAPEG® 600 DO或PEG 600二油酸脂等)。合適的環氧乙烷(EO)與環氧丙烷(PO)之共聚物包括得自BASF之各種Pluronic及Pluronic R嵌段共聚物界面活性劑、得自DOW Chemical之DOWFAX非離子性界面活性劑、UCONTM流體及SYNALOX潤滑劑。合適的脫水山梨糖醇脂肪酸酯之聚環氧烷衍生物包括聚環氧乙烷20脫水山梨糖醇單月桂酸酯(例如以商標TWEEN 20或T-MAZ 20出售之產品)、聚環氧乙烷4脫水山梨糖醇單月桂酸酯(例如TWEEN 21)、聚環氧乙烷20脫水山梨糖醇單棕櫚酸酯(例如TWEEN 40)、聚環氧乙烷20脫水山梨糖醇單硬脂酸酯(例如TWEEN 60或T-MAZ 60K)、聚環氧乙烷20脫水山梨糖醇單油酸酯(例如TWEEN 80或T-MAZ 80)、聚環氧乙烷20三硬酯酸酯(例如TWEEN 65或T-MAZ 65K)、聚環氧乙烷5脫水山梨糖醇單油酸酯(例如TWEEN 81或T-MAZ 81)、聚環氧乙烷20脫水山梨糖醇三油酸酯(例如TWEEN 85或T-MAZ 85K)及其類似物。
可稀釋(通常用水)熱傳送流體濃縮物以形成熱傳送流體。舉例而言，可將熱傳送流體濃縮物稀釋至10體積%至75體積%以形成熱傳送流體。在一些實施例中，稀釋用水為如ASTM D3306-10之章節4.5中所描述之去離子水。
在熱傳送流體中，以熱傳送流體之總重量計，凝固點降低劑之存在量為1wt%至小於90wt%。在此範圍內，以熱傳送流體之總重量計，凝固點降低劑之量可大於或等於30wt%、大於或等於40wt%、大於或等於50wt%、大於或等於55wt%、大於或等於60wt%、大於或等於70wt%、大於或等於75wt%、大於或等於80wt%、大於或等於85wt%、大於或等於86wt%、大於或等於87wt%、大於或等於88wt%或大於或等於89wt%，但小於90wt%。此外，在此範圍內，以熱傳送流體之總重量計，凝固點降低劑之量可小於或等於30wt%、小於或等於40wt%、小於或等於50wt%、小於或等於55wt%、小於或等於60wt%、小於或等於70wt%、小於或等於75wt%、小於或等於80wt%、小於或等於85wt%、小於或等於86wt%、小於或等於87wt%、小於或等於88wt%或小於或等於89wt%，但大於1wt%。
在熱傳送流體中，以熱傳送流體之總重量計，羧酸鹽之存在量為0.5wt%至8wt%。在此範圍內，該量可大於或等於0.6wt%，或更特定言之，大於或等於0.7wt%。亦在此範圍內，該量可小於或等於7wt%，或更特定言之，小於或等於6wt%。
在熱傳送流體中，以熱傳送流體之總重量計，無機磷酸鹽之存在量可為0.05wt%至0.4重量%。在此範圍內，該量可大於或等於0.07wt%或更特定言之，大於或等於0.08wt%。亦在此範圍內，該量可小於或等於0.35wt%或更特定言之，小於或等於0.30wt%。
在熱傳送流體中，以熱傳送流體之總重量計，唑化合物之存在量可為0.005wt%至2wt%。在此範圍內，唑化合物之存在量可大於或
等於0.007wt%或更特定言之，大於或等於0.01wt%。亦在此範圍內，唑化合物之存在量可小於或等於1.5wt%或更特定言之，小於或等於1wt%。
在熱傳送流體中，鎂化合物係以使得熱傳送流體之鎂離子濃度以熱傳送流體之重量計為2至60百萬分率(ppm)之量存在。在此範圍內，鎂離子濃度可大於或等於4ppm或更特定言之，大於或等於6ppm。亦在此範圍內，鎂離子濃度可小於或等於65ppm或更特定言之，小於或等於60ppm。
鈣化合物可以使得熱傳送流體之鈣離子濃度以熱傳送流體之總重量計大於0.5百萬分率之量存在。在此範圍內，鈣離子之量可小於60ppm。亦在此範圍內，鈣離子之量可小於或等於40ppm。
鋰化合物可以使得熱傳送流體之鋰離子濃度以熱傳送流體之重量計為20至1800百萬分率(ppm)之量存在。在此範圍內，鋰離子濃度可小於或等於1200ppm或更特定言之，小於或等於900ppm。亦在此範圍內，鋰離子濃度可大於或等於30ppm或更特定言之，大於或等於65ppm。
在室溫下，熱傳送流體之pH值為7至9.5。在此範圍內，該pH值可大於或等於7.5或大於或等於7.8。亦在此範圍內，該pH值可小於或等於9.0或小於或等於8.8。
防止腐蝕之方法包含使本文中所描述之熱傳送流體與熱傳送系統接觸。熱傳送系統可包含藉由控制氛圍硬焊製造的組件。熱傳送系統可包含鋁。
亦預期在一些應用(諸如重型引擎)中，可能需要併入一或多種額外腐蝕抑制劑，諸如亞硝酸酯、鉬酸酯及其鹽。
藉由以下非限制性實例進一步說明熱傳送流體。
使用表1中所示之材料製造實例。
表2中所示之濃縮物組合物係藉由混合所列出之成分與小於0.03重量%染料來製造。用去離子水將濃縮物稀釋至25體積%且添加100ppm氯化物。在263±3℉下使用砂鑄鋁319對經稀釋之溶液進行改進型GM9066P測試。結果示於以下表2中。
除非上下文另外明確指出，否則單數形式「一(a)」、「一(an)」及「該」包括複數參考物。敍述相同特徵或組分之所有範圍之端點均可獨立地組合且包括所述端點在內。所有參考文獻均以引用的方式併入本文中。本文中之術語「第一」、「第二」及其類似術語不表示任何次序、數量或重要性，而是用於區分一個要素與另一要素。本文中所描述之各種實施例及範圍均可組合至使描述不矛盾之程度。
儘管已出於說明目的闡述典型實施例，但前述描述不應被視為對本文範疇之限制。因此，熟習此項技術者可在不偏離本文之精神及範疇的情況下作出各種修改、調整及替代。
Claims (12)
- 一種熱傳送流體濃縮物，其包含：大於90重量%之凝固點降低劑；16至80ppm之鎂離子；唑化合物；無機磷酸鹽；羧酸鹽；及基於丙烯酸酯之聚合物，其中該熱傳送流體之pH值為7至9.5，且基於丙烯酸酯之聚合物與鎂離子之重量比為1至25。
- 如請求項1之熱傳送流體濃縮物，其進一步包含鈣離子。
- 如請求項1之熱傳送流體濃縮物，其進一步包含50至2000ppm鋰離子。
- 如請求項1之熱傳送流體濃縮物，其進一步包含鈣離子及50至2000ppm鋰離子。
- 如請求項1之熱傳送流體濃縮物，其中該基於丙烯酸酯之聚合物包含膦基聚丙烯酸酯。
- 如請求項1之熱傳送流體濃縮物，其進一步包含一或多種選自由亞硝酸酯、鉬酸酯及其鹽組成之群的其他腐蝕抑制劑。
- 一種熱傳送流體，其包含：小於90重量%之凝固點降低劑；水；2至60ppm之鎂離子；唑化合物；無機磷酸鹽；羧酸鹽； 大於0.5ppm之鈣離子；及基於丙烯酸酯之聚合物，其中該熱傳送流體之pH值為7至9.5，且基於丙烯酸酯之聚合物與鎂離子之重量比為1至25。
- 如請求項7之熱傳送流體，其中該熱傳送流體包含小於60ppm鈣離子。
- 如請求項7之熱傳送流體，其中該熱傳送流體包含小於40ppm鈣離子。
- 如請求項7之熱傳送流體，其進一步包含20至1800ppm鋰離子。
- 如請求項7之熱傳送流體，其中該基於丙烯酸酯之聚合物包含膦基聚丙烯酸酯。
- 如請求項7之熱傳送流體，其進一步包含一或多種選自由亞硝酸酯、鉬酸酯及其鹽組成之群的其他腐蝕抑制劑。
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