CN100580049C - 用于保护镁及其合金的基于聚二醇和酰胺的防冻浓缩物和冷却剂组合物 - Google Patents
用于保护镁及其合金的基于聚二醇和酰胺的防冻浓缩物和冷却剂组合物 Download PDFInfo
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- CN100580049C CN100580049C CN200480011102A CN200480011102A CN100580049C CN 100580049 C CN100580049 C CN 100580049C CN 200480011102 A CN200480011102 A CN 200480011102A CN 200480011102 A CN200480011102 A CN 200480011102A CN 100580049 C CN100580049 C CN 100580049C
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- 239000012153 distilled water Substances 0.000 description 1
- RCFKEIREOSXLET-UHFFFAOYSA-N disulfamide Chemical compound CC1=CC(Cl)=C(S(N)(=O)=O)C=C1S(N)(=O)=O RCFKEIREOSXLET-UHFFFAOYSA-N 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 1
- RMSHYQAVCSUECE-UHFFFAOYSA-N hexane-1-sulfonamide Chemical compound CCCCCCS(N)(=O)=O RMSHYQAVCSUECE-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- MJTGQALMWUUPQM-UHFFFAOYSA-N m-Chlorobenzamide Chemical compound NC(=O)C1=CC=CC(Cl)=C1 MJTGQALMWUUPQM-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- PSEXPFNBJCCKPF-UHFFFAOYSA-N magnesium;methanesulfonic acid Chemical compound [Mg].CS(O)(=O)=O PSEXPFNBJCCKPF-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- MVILWLLYYQVYNH-UHFFFAOYSA-N pyridine-2-carboxamide Chemical compound NC(=O)C1=CC=CC=N1.NC(=O)C1=CC=CC=N1 MVILWLLYYQVYNH-UHFFFAOYSA-N 0.000 description 1
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009747 swallowing Effects 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 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
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/164—Sulfur-containing compounds containing a -SO2-N group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种基于亚烷基二醇、甘油和/或1,3-丙二醇的防冻浓缩物。所述防冻浓缩物包含a)基于该浓缩物的总量为0.05-10重量%,优选0.5-5重量%的一种或几种聚乙二醇和/或聚丙二醇,和b)基于该浓缩物的总量为0.01-10重量%,优选0.05-10重量%的一种或几种羧酰胺和/或磺酰胺。通过用水稀释本发明浓缩物可以得到即用型含水冷却剂组合物,其含有30-70重量%,尤其是40-60重量%的该浓缩物。所述冷却剂组合物的特征在于对镁和镁合金的有效腐蚀。
Description
本发明涉及基于聚二醇和羧酰胺和/或磺酰胺的防冻浓缩物和可以由该浓缩物得到的即用型含水冷却剂组合物。本发明还涉及这些防冻浓缩物在制备尤其适于含镁和/或铝内燃机的含水冷却剂组合物中的用途。
用于例如汽车中内燃机的冷却循环的防冻浓缩物通常含有亚烷基二醇,尤其是乙二醇或丙二醇作为主要组分。为了用于冷却系统中,用水稀释它们且除了防冻外,还应确保除热良好。然而,亚烷基二醇/水混合物在内燃机的操作温度下极具腐蚀性。因此必须充分保护冷却系统中存在的各种金属及其合金以防各种类型的腐蚀,例如点腐蚀、裂隙腐蚀、侵蚀或气蚀。
根据现有技术,在该类冷却系统中将大量化学物质用作各种不同金属如钢、铸铁、铜、黄铜、铝及其合金以及焊接金属如锡焊料的缓蚀剂。当它们用于冷却当前主要由汽车工业使用且包含灰铸铁或铸铝合金的发动机时,所得散热器防冻剂满足防腐的预期。
在汽车构造中,目前正试图通过降低汽车重量来降低燃料消耗。例如,正尝试通过部分或完全由镁或镁合金制造发动机而降低其重量。
然而,试验表明由于镁的化学活性高,当前市售的散热器防冻剂仅对该金属及其合金提供非常有限的防腐。
目前仅有几篇专利公开提供了对这些问题的解决方案。
早在1931年,DRP 569 771(1)描述了一种用于由镁合金组成的内燃机部件的冷却液,该冷却液在存在或不存在水下包含含有少量碱金属氟化物的多元醇。
在同一年,DRP 579 185(2)描述了将碱金属硫化物用于相同目的。
然而,现在不再希望使用氟化物或硫化物,因为这些类型的物质在毒理上不可接受。
WO 95/07323(3)描述了基于丙二醇,含有钼酸盐、硝酸盐和唑类衍生物如甲苯并三唑(tolutriazole)的无水散热器防冻剂,其用于各种金属,包括镁及其合金的防腐。然而,无水散热器防冻剂因其导热性差而不适于实践。
EP 229 440 B1(4)描述了还据说对镁具有防腐性能的冷却剂浓缩物,其包含脂族单羧酸盐、脂族二羧酸盐和烃-三唑以及需要的话额外还有碱金属硼酸盐、硅酸盐、苯甲酸盐、硝酸盐、亚硝酸盐或钼酸盐和/或烃-咔唑。对镁没有描述具体的腐蚀试验结果。
EP 251 480 B1(5)描述了包含烷基苯甲酸盐、脂族单羧酸盐和三唑以及需要的话其他组分的冷却剂浓缩物,据说该浓缩物不仅在当前常用于发动机构造的金属情况下而且在镁情况下导致改进的防腐。这里对镁并没有提到具体的腐蚀试验结果。
作为与(5)相比的改进,WO 00/22189(6)描述了含有羧酸盐与氟化物和/或氟代羧酸的组合的冷却液。然而,这里的缺点是尤其使用毒理上不可接受的氢氟酸。
WO 99/19418(7)描述了一种用于镁组分的基于多元醇的冷却液,其由支化脂族羧酸盐以及链烷醇胺磷酸酯和甲苯并三唑/苯并三唑的组合形成,其中需要的话可以加入其他添加剂如脂族或芳族单-和/或二羧酸盐、巯基苯并噻唑或羧甲基纤维素。然而,腐蚀试验结果并不充分,特别是在较大量水存在下。
WO 02/08354(8)描述了防冻浓缩物和包含它们的冷却剂组合物,其用于保护镁及镁合金且含有0.05-10重量%羧酰胺和/或磺酰胺。描述了基于水含量为30%的乙二醇的实例,其给出非常良好的腐蚀试验结果。
本发明的目的是提供不再具有现有技术的缺点的对应防冻配方。待制备的防冻剂尤其具有良好的导热性、无毒且确保镁和镁合金以及铝和铝合金的良好防腐。
我们发现该目的由基于亚烷基二醇、甘油和/或1,3-丙二醇的防冻浓缩物实现,所述浓缩物包含如下组分:
a)基于该浓缩物的总量为0.05-10重量%,优选0.5-5重量%的一种或多种聚乙二醇和/或聚丙二醇,和
b)基于该浓缩物的总量为0.01-10重量%,优选0.05-10重量%的一种或多种羧酰胺和/或磺酰胺。
惊人的是,已经发现通过向根据(8)的混合物中添加少量聚乙二醇得到用于镁和镁合金的有效冷却剂配方。
在优选的实施方案中,组分a)选自二甘醇、三甘醇、四甘醇、五甘醇、六甘醇、二丙二醇、三丙二醇、四丙二醇、五丙二醇、六丙二醇及其混合物,优选三甘醇、四甘醇、三丙二醇、四丙二醇及其混合物,尤其是三丙二醇。
在本发明上下文中,术语丙二醇应理解为1,2-丙二醇。
组分b)优选选自各自具有2-16个,优选3-12个碳原子的线性和支化脂族、环脂族、芳族和杂芳族羧酸和/或磺酸的酰胺。
组分b)的酰胺和磺酰胺,需要的话可以在酰氨基的氮原子上烷基取代,例如被C1-C4烷基取代。该分子的芳族或杂芳族骨架当然还可以带有烷基。在该分子中可以存在一个或多个,优选1或2个酰氨基。酰胺可以带有额外的官能团,优选C1-C4烷氧基、氨基、氯、氟、羟基和/或乙酰基,该类官能团尤其是存在的芳族或杂芳族环上的取代基。
该类羧酰胺和磺酰胺的典型实例如下给出。
·芳族羧酰胺:
苯甲酰胺
2-甲基苯甲酰胺
3-甲基苯甲酰胺
4-甲基苯甲酰胺
2,4-二甲基苯甲酰胺
4-叔丁基苯甲酰胺
3-甲氧基苯甲酰胺
4-甲氧基苯甲酰胺
2-氨基苯甲酰胺(邻氨基苯甲酰胺)
3-氨基苯甲酰胺
4-氨基苯甲酰胺
3-氨基-4-甲基苯甲酰胺
2-氯苯甲酰胺
3-氯苯甲酰胺
4-氯苯甲酰胺
2-氟苯甲酰胺
3-氟苯甲酰胺
4-氟苯甲酰胺
2,6-二氟苯甲酰胺
4-羟基苯甲酰胺
邻苯二甲酰胺
对苯二甲酰胺
·杂芳族羧酰胺:
烟酰胺(吡啶-3-甲酰胺)
吡啶酰胺(吡啶-2-甲酰胺)
·脂族羧酰胺:
琥珀酰胺
己二酰二胺
丙酰胺
己酰胺
·具有作为环的一部分的酰氨基的环脂族羧酰胺:
2-吡咯烷酮
N-甲基-2-吡咯烷酮
2-哌啶酮
ε-己内酰胺
·脂族磺酰胺:
甲磺酰胺
己烷-1-磺酰胺
·芳族磺酰胺:
苯磺酰胺
邻甲苯磺酰胺
间甲苯磺酰胺
对甲苯磺酰胺
4-叔丁基苯磺酰胺
4-氟苯磺酰胺
4-羟基苯磺酰胺
2-氨基苯磺酰胺
3-氨基苯磺酰胺
4-氨基苯磺酰胺
4-乙酰基苯磺酰胺
在进一步优选的实施方案中,本发明的防冻浓缩物额外含有一种或多种下列非离子化合物:
c)基于该浓缩物的总量为0-10重量%,优选0.05-5重量%的一种或多种具有2-15个碳原子的脂族、环脂族或芳族胺,其可以额外含有醚氧原子或羟基,和/或
d)基于该浓缩物的总量为0-10重量%,优选0.05-5重量%的一种或多种具有4-10个碳原子的单核或双核不饱和或部分不饱和杂环,其可以苯并稠合且可以带有额外的官能团,和/或
e)基于该浓缩物的总量为0-10重量%,优选0.05-5重量%的一种或多种四(C1-C8烷氧基)硅烷(原硅酸四C1-C8烷基酯)。
具有2-15个,优选4-8个碳原子且可以额外含有醚氧原子或羟基的脂族、环脂族或芳族胺c)的实例包括乙胺、丙胺、异丙胺、正丁胺、异丁胺、仲丁胺、叔丁胺、正戊胺、正己胺、正庚胺、正辛胺、异壬胺、二正丙胺、二异丙胺、二正丁胺、六亚甲基四胺(乌洛托品)、单-、二-和三乙醇胺、哌啶、吗啉、苯胺和苄基胺。c)组的脂族和环脂族胺的有机基团优选是饱和的。
杂环d)的实例包括具有1、2或3个氮原子或具有1个氮原子和1个硫原子的单核5或6元体系,其可以是苯并稠合的。还可以使用包含通常具有2、3或4个氮原子的5和/或6元环的双核体系。d)组的杂环可以额外带有官能团,优选C1-C4烷氧基、氨基和/或巯基。杂环骨架当然还可以带有烷基。
杂环d)的实例包括苯并三唑、甲苯并三唑、氢化甲苯并三唑、1H-1,2,4-三唑、苯并咪唑、苯并噻唑、巯基苯并噻唑、腺嘌呤、嘌呤、6-甲氧基嘌呤、吲哚、异吲哚、二氢异吲哚、吡啶、嘧啶、3,4-二氨基吡啶、2-氨基嘧啶和2-巯基嘧啶。
四(C1-C8烷氧基)硅烷e)的实例包括四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷和四正丁氧基硅烷。
本发明的防冻浓缩物还可以含有一种或多种下列化合物:
f)基于该浓缩物的总量为0-10重量%,优选0.05-5重量%的一种或多种各自具有3-16个碳原子的脂族或芳族单羧酸,其呈碱金属盐、铵盐或取代铵盐的形式,和/或
g)基于该浓缩物的总量为0-10重量%,优选0.05-5重量%的一种或多种各自具有4-20个碳原子的脂族或芳族二羧酸,其呈碱金属盐、铵盐或取代铵盐的形式,和/或
h)基于该浓缩物的总量各自为0-1重量%的一种或多种碱金属硼酸盐、碱金属磷酸盐、碱金属硅酸盐、碱金属亚硝酸盐、碱金属或碱土金属硝酸盐、钼酸盐或碱金属或碱土金属氟化物,和/或
i)基于该浓缩物的总量为0-1重量%的一种或多种硬水稳定剂,其基于聚丙烯酸、聚马来酸、丙烯酸/马来酸共聚物、聚乙烯基吡咯烷酮、聚乙烯基咪唑、乙烯基吡咯烷酮/乙烯基咪唑共聚物和/或不饱和羧酸和烯烃的共聚物。
f)、g)和h)组的化合物是额外的缓蚀剂。
f)组的线性、支化或环状脂族单羧酸的实例包括丙酸、戊酸、己酸、环己基乙酸、辛酸、2-乙基己酸、壬酸、异壬酸、癸酸、十一烷酸和十二烷酸。
f)组的芳族单羧酸的实例尤其包括苯甲酸以及还有C1-C8烷基苯甲酸,例如邻-、间-和对甲基苯甲酸或对叔丁基苯甲酸,C1-C4烷氧基苯甲酸,例如邻-、间-和对甲氧基苯甲酸,含羟基的芳族单羧酸,例如邻-、间-或对羟基苯甲酸,邻-、间和对(羟基甲基)苯甲酸,以及卤代苯甲酸,例如邻-、间-或对氟苯甲酸。
g)组的二羧酸的实例包括丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、二环戊二烯二甲酸、邻苯二甲酸和对苯二甲酸。
所有提到的羧酸以其碱金属盐,尤其是钠或钾盐存在,或以铵盐或取代铵盐(胺盐)存在,例如与氨、三烷基胺或三链烷醇胺的盐。
在h)下所述的额外缓蚀剂的实例包括四硼酸钠(硼砂)、磷酸氢二钠、磷酸三钠、硅酸钠、亚硝酸钠、硝酸钠、硝酸镁、氟化钠、氟化钾、氟化镁和钼酸钠。
当存在碱金属硅酸盐时,上述抑制剂有利地通过常规有机硅膦酸盐或有机硅磺酸盐以常规量稳定。
除了所述抑制剂组分如镁与有机酸的可溶性盐,例如苯磺酸镁、甲磺酸镁、乙酸镁或丙酸镁外,还可以以常规量将DE-A 196 05 509中所述的氢化咔唑或季铵化咪唑用作其他抑制剂。
本发明防冻浓缩物的pH通常为4-11,优选4-10,尤其是4.5-8.5。需要的话,所需pH还可以通过向配制剂中加入碱金属氢氧化物、氨或胺而产生,其中固体氢氧化钠或氢氧化钾以及氢氧化钠或氢氧化钾水溶液特别适合该目的。待使用的羧酸有利地以对应的碱金属盐直接加入,以自动位于所需pH范围内;然而,还可以将羧酸作为游离酸加入并随后用碱金属氢氧化物、氨或胺中和并调节至所需pH范围。
本发明防冻浓缩物的主组分是至少一种亚烷基二醇、甘油、1,3-丙二醇或其混合物。该组分或这些组分优选以≥75重量%,尤其≥85重量%的量存在。亚烷基二醇优选是乙二醇和/或丙二醇。
在优选的实施方案中,该主组分基于乙二醇、丙二醇或其混合物。乙二醇和/或丙二醇以至少95重量%的量存在,此外可以存在甘油或1,3-丙二醇。该主组分尤其是乙二醇、丙二醇或其混合物。
本发明的防冻浓缩物还可以含有常规的少量消泡剂(通常为0.003-0.008重量%)、染料以及在吞咽情况下出于卫生目的和安全目的的苦味物质(例如denatonium苯甲酸盐型物质)作为其他常规助剂。
本发明还涉及具有低凝固点的即用型含水冷却剂组合物,尤其用于汽车领域的散热器保护,其包含70-30重量%,优选60-40重量%水和30-70重量%,尤其是40-60重量%本发明的防冻剂浓缩物。即用型冷却剂组合物通过用水稀释本发明的防冻剂浓缩物而得到。
本发明的防冻剂浓缩物的特征尤其在于在镁和镁合金情况下与现有技术的组合物相比具有更为有效的缓蚀作用。
因此,本发明的另一目的是使用本发明的含水冷却剂组合物在内燃机中防止镁和镁合金的腐蚀。对经由冷却循环与冷却剂组合物接触的那些部件实现该保护。
下列实施例说明本发明但不限制本发明。
实施例
由本发明防冻浓缩物制备冷却剂组合物实施例1并由根据WO02/08354的浓缩物制备对比例,各组合物的水含量为50%且所述组成示于表1中。防冻浓缩物例如可以通过将各组分溶于乙二醇中而容易地得到。含水冷却剂组合物可以通过用水简单稀释而由其得到。
这些含水冷却剂组合物的测试在没有进一步稀释下在静态热表面试验(ASTM D 4340-98)中使用合金AZ91HP的镁试样或合金GalSi6Cu4的铸铝试样直接进行。代替浓硝酸,使用对该金属更合适的铬酸对试验后的镁试样进行清洁。
结果示于表2中。它们表明在镁的情况下,使用本发明冷却剂组合物获得比根据作为现有技术的WO 02/08354的对比例显著更好的防腐。
同时,在铝的情况下也获得良好的防腐。这里,在本发明实施例1中在铸铝的情况下轻微的重量增加表明形成了稳定的保护层。
表1:测试的冷却剂组合物
组分[重量%] | 实施例1 | 根据WO 02/08354的对比例 |
对甲苯磺酰胺、三乙醇胺和1H-1,2,4-三唑的混合物 | 2.5 | 2.5 |
三丙二醇 | 3 | --- |
蒸馏水 | 50 | 50 |
单乙二醇 | 余量 | 余量 |
表2:根据ASTM D 4340-98的静态热腐蚀试验
腐蚀速率[mg/cm<sup>2</sup>/周] | 实施例1 | 根据WO 02/08354的对比例 |
Mg AZ91HPGalSi6Cu4 | -3.43+0.25 | -13.40--- |
Claims (11)
1.一种基于乙二醇、1,2-丙二醇或其混合物,甘油和/或1,3-丙二醇的防冻浓缩物,其包含如下组分:
a)基于该浓缩物的总量为0.05-10重量%的一种或多种聚乙二醇和/或聚丙二醇,选自三甘醇、四甘醇、五甘醇、六甘醇、三丙二醇、四丙二醇、五丙二醇、六丙二醇及其混合物,
b)基于该浓缩物的总量为0.01-10重量%的一种或多种羧酰胺和/或磺酰胺,其中磺酰胺的酰氨基团未被取代或被烷基取代,
c)基于该浓缩物的总量为0.05-10重量%的一种或多种具有2-15个碳原子的脂族、环脂族或芳族胺,其额外含有或不含有醚氧原子或羟基,和
d)基于该浓缩物的总量为0.05-10重量%的一种或多种选自苯并三唑、氢化甲苯并三唑、1H-1,2,4-三唑、苯并咪唑、苯并噻唑、嘌呤、吲哚、异吲哚、二氢异吲哚、吡啶和嘧啶的杂环化合物,其中所述杂环未被取代或被C1-C4烷氧基、氨基、巯基和/或烷基取代。
2.如权利要求1所要求的浓缩物,其中组分a)选自三甘醇、四甘醇、三丙二醇、四丙二醇及其混合物。
3.如权利要求1所要求的浓缩物,其中组分b)选自各自具有2-16个碳原子的线性和支化脂族、环脂族、芳族和杂芳族羧酸和/或磺酸的酰胺。
4.如权利要求3所要求的浓缩物,其中组分b)选自芳族羧酰胺、杂芳族羧酰胺、脂族羧酰胺、具有作为环的一部分的酰氨基的环脂族羧酰胺、脂族磺酰胺和芳族磺酰胺。
5.如权利要求1或2所要求的浓缩物,其额外包含下列化合物:
e)基于该浓缩物的总量为0-10重量%的一种或多种四(C1-C8烷氧基)硅烷(原硅酸四C1-C8烷基酯)。
6.如权利要求1或2所要求的浓缩物,其额外包含一种或多种下列化合物:
f)基于该浓缩物的总量为0-10重量%的一种或多种各自具有3-16个碳原子的脂族或芳族单羧酸,其呈碱金属盐、铵盐或取代铵盐的形式,和/或
g)基于该浓缩物的总量为0-10重量%的一种或多种各自具有4-20个碳原子的脂族或芳族二羧酸,其呈碱金属盐、铵盐或取代铵盐的形式,和/或
h)基于该浓缩物的总量各自为0-1重量%的一种或多种碱金属硼酸盐、碱金属磷酸盐、碱金属硅酸盐、碱金属亚硝酸盐、碱金属或碱土金属硝酸盐、钼酸盐或碱金属或碱土金属氟化物,和/或
i)基于该浓缩物的总量为0-1重量%的一种或多种硬水稳定剂,其基于聚丙烯酸、聚马来酸、丙烯酸/马来酸共聚物、聚乙烯基吡咯烷酮、聚乙烯基咪唑、乙烯基吡咯烷酮/乙烯基咪唑共聚物和/或不饱和羧酸和烯烃的共聚物。
7.如权利要求1或2所要求的浓缩物,其额外含有镁和有机酸的可溶性盐、氢化咔唑和/或季铵化咪唑。
8.如权利要求1或2所要求的浓缩物,其中乙二醇、1,2-丙二醇、甘油、1,3-丙二醇或其混合物以≥75重量%的量存在。
9.如权利要求1或2所要求的浓缩物,其pH为4-11。
10.一种含水冷却剂组合物,包含水和30-70重量%如权利要求1或2所要求的浓缩物。
11.根据权利要求10的含水冷却剂组合物在内燃机中防止镁和镁合金腐蚀中的用途。
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DE10313280.5 | 2003-03-25 | ||
DE10313280A DE10313280A1 (de) | 2003-03-25 | 2003-03-25 | Gefrierschutzmittelkonzentrate und Kühlmittelzusammensetzungen auf Basis von Polyglykolen und Amiden zum Schutz von Magnesium und dessen Legierungen |
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CN100580049C true CN100580049C (zh) | 2010-01-13 |
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US (1) | US7588695B2 (zh) |
EP (1) | EP1618167B1 (zh) |
CN (1) | CN100580049C (zh) |
AT (1) | ATE407988T1 (zh) |
AU (1) | AU2004224163B2 (zh) |
BR (1) | BRPI0408712A (zh) |
CA (1) | CA2520246C (zh) |
DE (2) | DE10313280A1 (zh) |
ES (1) | ES2311149T3 (zh) |
MX (1) | MXPA05010060A (zh) |
NO (1) | NO20054795L (zh) |
PL (1) | PL1618167T3 (zh) |
PT (1) | PT1618167E (zh) |
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2003
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2004
- 2004-03-24 EP EP04722834A patent/EP1618167B1/de not_active Expired - Lifetime
- 2004-03-24 US US10/550,740 patent/US7588695B2/en not_active Expired - Fee Related
- 2004-03-24 CN CN200480011102A patent/CN100580049C/zh not_active Expired - Fee Related
- 2004-03-24 BR BRPI0408712-7A patent/BRPI0408712A/pt not_active Application Discontinuation
- 2004-03-24 PL PL04722834T patent/PL1618167T3/pl unknown
- 2004-03-24 ES ES04722834T patent/ES2311149T3/es not_active Expired - Lifetime
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- 2004-03-24 AT AT04722834T patent/ATE407988T1/de active
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AU2004224163B2 (en) | 2009-12-17 |
AU2004224163A1 (en) | 2004-10-07 |
ZA200507692B (en) | 2007-03-28 |
ES2311149T3 (es) | 2009-02-01 |
WO2004085566A1 (de) | 2004-10-07 |
DE502004008029D1 (de) | 2008-10-23 |
BRPI0408712A (pt) | 2006-03-07 |
NO20054795L (no) | 2005-10-24 |
EP1618167B1 (de) | 2008-09-10 |
ATE407988T1 (de) | 2008-09-15 |
CA2520246C (en) | 2013-02-12 |
US20070034825A1 (en) | 2007-02-15 |
CN1780894A (zh) | 2006-05-31 |
US7588695B2 (en) | 2009-09-15 |
MXPA05010060A (es) | 2005-11-23 |
PT1618167E (pt) | 2008-10-01 |
PL1618167T3 (pl) | 2009-03-31 |
CA2520246A1 (en) | 2004-10-07 |
DE10313280A1 (de) | 2004-10-07 |
EP1618167A1 (de) | 2006-01-25 |
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