CN101128558B - 具有防腐功能的含甘油的防冻浓缩物 - Google Patents
具有防腐功能的含甘油的防冻浓缩物 Download PDFInfo
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- CN101128558B CN101128558B CN2006800063343A CN200680006334A CN101128558B CN 101128558 B CN101128558 B CN 101128558B CN 2006800063343 A CN2006800063343 A CN 2006800063343A CN 200680006334 A CN200680006334 A CN 200680006334A CN 101128558 B CN101128558 B CN 101128558B
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- Prior art keywords
- weight
- enriched material
- acid
- antifreeze
- alkali metal
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 28
- 230000002528 anti-freeze Effects 0.000 title claims description 27
- 238000005260 corrosion Methods 0.000 title abstract description 18
- 230000007797 corrosion Effects 0.000 title abstract description 17
- 239000012141 concentrate Substances 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 52
- -1 alkali metal salt Chemical class 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 239000002826 coolant Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 229940124530 sulfonamide Drugs 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 7
- 230000002421 anti-septic effect Effects 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 2
- DBBAUITUQRZERI-UHFFFAOYSA-N 2-ethenyl-1h-imidazole;1-ethenylpyrrolidin-2-one Chemical compound C=CC1=NC=CN1.C=CN1CCCC1=O DBBAUITUQRZERI-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 2
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 239000008233 hard water Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001444 polymaleic acid Polymers 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 66
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 4
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 230000003340 mental effect Effects 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- QXSAKPUBHTZHKW-UHFFFAOYSA-N 4-hydroxybenzamide Chemical compound NC(=O)C1=CC=C(O)C=C1 QXSAKPUBHTZHKW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UHBGYFCCKRAEHA-UHFFFAOYSA-N P-toluamide Chemical compound CC1=CC=C(C(N)=O)C=C1 UHBGYFCCKRAEHA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
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- 230000008014 freezing Effects 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 235000005152 nicotinamide Nutrition 0.000 description 2
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- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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- 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
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Abstract
本发明涉及防冻/防腐浓缩物，其含有基于浓缩物的总量为10-50％重量的甘油，由超浓缩物制备所述浓缩物的方法，含有这些浓缩物的含水冷却剂组合物，以及它们的用途，例如它们在内燃机中的用途。
Description
本发明涉及防冻/防腐浓缩物，由超浓缩物制备所述浓缩物的方法，包含这些浓缩物的含水冷却剂组合物及它们的用途。
用于例如汽车中内燃机的冷却回路的冷却剂组合物通常含有亚烷基二醇，主要是乙二醇和/或丙二醇，作为防冻组分。
除了其它组分以外，还尤其存在缓蚀剂。
尤其在现代内燃机中，获得热应力对使用的材料提出了很高的要求。任意类型和任意程度的腐蚀都构成一种潜在的危险因素，即可能导致内燃机的运行时间缩短且可靠性下降。此外，在现代发动机中正日益增加对大量不同材料的使用，例如，铸铁、铜、黄铜、软焊条、钢、及镁和铝的合金。这些大量的金属材料额外地产生潜在腐蚀问题，特别是在不同金属彼此接触的接触点。尤其是在这些接触点，可能相对容易发生大量的不同类型的腐蚀，例如小孔腐蚀、裂隙腐蚀、侵蚀或空化腐蚀。
同样，冷却剂组合物也必须与冷却回路中的非金属组分相容，例如与用于软管连接件或者密封件的弹性体和塑料相容，且必须不得改变它们。
而且，冷却剂组合物在现代内燃机的传热方面起着关键作用。
对于已经含有所述即用型冷却剂组合物的冷却剂容器，防冻/防腐浓缩物甚至会变得更重要。仅需要将水加入到这些浓缩物中，以获得即用型冷却剂组合物。
因而，防冻/防腐浓缩物同样含有首先用于防冻(即，用于降低混合物的凝固点)的组分和其次用于防腐的缓蚀剂。基于浓缩物的总量，防腐组分在浓缩物中的比例通常不超过10％重量。浓缩物在现填充型的散热器保护剂中的比例通常为10-60％重量。浓缩物可以已经含有少量水。
尤其出于运输原因，要额外可以获得具有减少量防冻组分(即，通常是乙二醇)的超浓缩物，以提供非常紧凑的容器。在此情形下，浓缩物中除去的防冻组分量通常应使得其它组分刚好以溶解形式保留在浓缩物中。
因此，可由超浓缩物通过将一定量的防冻组分与如果合适的话，一些水混入其中而得到防冻/防腐浓缩物。超浓缩物在浓缩物中的比例通常为3-60％重量。
如上所述，亚烷基二醇、主要是乙二醇和/或丙二醇通常成为防冻组分的主要成分。
用作防冻组分的缓蚀剂是本领域公知的。含有羧酸、钼酸和***的防冻剂公开在DE-A 19547449、EP-B 552988或US-A 4,561,990中。
EP-B 229440描述了一种防腐组分，其由脂族单羧酸、烃基二羧酸和烃基-***组成。
作为防腐组分的具体酸公开在EP-B 479470中。季铵化咪唑描述在DE-A 19605509中。
除了常用的乙二醇和丙二醇以外，EP-A 816467还公开了高级二元醇和二醇醚作为防冻组分。甘油也是通常已知的作为防冻组分的可能组分。
例如，DE-A 3413416、US-A 2004/0104375和WO-A 02/090462提到除了常规的二元醇如乙二醇以外，甘油也是一种可能的凝固点降低组分。
WO-A 02/072728涉及通过添加少量甘油使乙二醇基防冻浓缩物的毒性降低。
利用目前已知的混合物和浓缩物实现的防腐和可实现的凝固点通常是良好的。然而，由于新型内燃机的性能日益增加，因此不断地需要改进的防冻/防腐浓缩物。
本发明的目的是提供所述防冻/防腐浓缩物，其不再具有现有技术的缺点或者具有至少减少的缺点。这些混合物应当具有平衡比例的防腐、传热和防起霜性能。
本发明的目的通过含有基于浓缩物的总量为10-50％重量的甘油的防冻/防腐浓缩物而实现。
已经发现，在浓缩物中使用一定范围量的甘油能够实现防冻/防腐浓缩物的改进性能。
基于浓缩物的总量，甘油量优选为15-35％重量，特别优选20-30％重量。
在该浓缩物中，选自一元醇、二元醇、不是甘油的三元醇、多羟基醇，这些醇的醚或其混合物的醇可额外地作为防冻组分存在。
额外的醇可以是乙二醇、丙二醇、二甘醇、二丙二醇、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、二醇的单醚，如乙二醇、丙二醇、二甘醇和二丙二醇的甲基、乙基、丙基和丁基醚。优选乙二醇和丙二醇。特别优选乙二醇。
在本发明的上下文中，术语“丙二醇”是指1，2-丙二醇。
基于浓缩物的总量，防冻组分(甘油和额外的一种或多种醇)的量优选为至少75％重量，更优选至少85％重量，特别优选至少90％重量。
基于浓缩物的总量，防腐组分的量优选为1-70％重量，更优选2-35％重量，特别优选3-8％重量。
在优选实施方案中，根据本发明的防冻/防腐浓缩物额外含有至少一种基于浓缩物的总量各自为如下所示量的下述组分：
(a)至多5％重量的一种或多种呈其碱金属盐、铵盐或取代铵盐形式的各自具有3-16个碳原子的脂族、环脂族或芳族单羧酸；
(b)至多5％重量的一种或多种呈其碱金属盐、铵盐或取代铵盐形式的各自具有3-21个碳原子的脂族或芳族二或三羧酸；
(c)至多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、碱金属钼酸盐或者碱金属或碱土金属氟化物；
(d)至多5％重量的一种或多种具有2-15个碳原子并且可以额外含有醚氧原子或羟基的脂族、环脂族或芳族胺；
(e)至多5％重量的一种或多种具有4-10个碳原子并且可以为苯并稠合的和/或带有额外官能团的单环或双环不饱和或部分不饱和杂环；
(f)至多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)；
(g)至多10％重量的一种或多种羧酰胺或磺酰胺；
(h)至多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/或不饱和羧酸与烯烃的共聚物。
a)-g)组的化合物是常用的缓蚀剂。
(a)组有用的线性或支化链脂族或环脂族单羧酸是例如丙酸、戊酸、己酸、环己基乙酸、辛酸、2-乙基己酸、壬酸、异壬酸、癸酸、十一烷酸或十二烷酸。(a)组合适的芳族单羧酸尤其是苯甲酸；其它有用的还包括例如C1-C8烷基苯甲酸，如邻-、间-、对-甲基苯甲酸或对叔丁基苯甲酸，以及含羟基的芳族单羧酸，如邻-、间-、对-羟基苯甲酸，邻-、间-、对-(羟甲基)苯甲酸或卤代苯甲酸如邻-、间-、对-氟苯甲酸。
(b)组二或三羧酸的典型实例是丙二酸、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、二聚环戊二烯二甲酸、邻苯二甲酸、对苯二甲酸和三嗪三亚氨基羧酸如6，6’，6”-(1，3，5-三嗪-2，4，6-三基三亚氢基)三己酸。
(a)组和(b)组中的所有这些羧酸以其碱金属盐，特别是钠盐或钾盐的形式存在，或者以铵盐或取代的铵盐(胺盐)形式存在，例如与氨、三烷基胺或三烷醇胺的盐。
(c)组提到的缓蚀剂的典型实例是四硼酸钠(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。
当使用碱金属硅酸盐时，它们可以适当地通过常规的有机硅膦酸盐或者有机硅磺酸盐以常规量稳定。
(d)组具有2-15个、优选4-8个碳原子且可额外含有醚氧原子、特别是1-3个醚氧原子或羟基、特别是1-3个羟基的可能的脂族、环脂族或芳族胺例如是乙胺、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、单-、二-和三乙醇胺、哌啶、吗啉、苯胺或苄基胺。(d)组脂族和环脂族胺通常是饱和的。
(e)组的杂环例如是具有1、2或3个氮原子或具有1个氮原子和1个硫原子且可以是苯并稠合的单五元环或六元环体系。还可以使用由通常具有2、3或4个氮原子的五和/或六元环构成的双环体系。
(e)组的杂环可额外带有官能团，优选C1-C4烷氧基、氨基和/或巯基。基本的杂环骨架当然还可以带有烷基，特别是C1-C4烷基。
(e)组杂环的典型实例是苯并***、甲苯并***、氢化甲苯并***、1H-1，2，4-***、苯并咪唑、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。
对于(f)组的四(C1-C8烷氧基)硅烷，有用的实例是四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷或四正丁氧基硅烷。
(g)组的酰胺可任选在酰胺基的氮原子上被烷基取代，例如被C1-C4烷基取代。该分子的基本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、优选一个或两个酰胺基。酰胺可带有额外的官能团，优选C1-C4烷氧基、氨基、氯、氟、羟基和/或乙酰基；所述官能团特别是以所存在的芳族或杂芳族环上的取代基而存在。
(g)组中所述的羧酰胺和磺酰胺的典型实例列于DE-A 10036031中。
(g)组中所述的羧酰胺和磺酰胺的典型实例尤其如下所示。
·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；
·具有的酰胺结构部分作为环的组分部分的环脂族羧酰胺：
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。
除了(a)-(g)组这些防腐组分以外，还可以将例如DE-A 19605509中描述的可溶性的有机酸镁盐例如苯磺酸镁、乙磺酸镁、乙酸镁或丙酸镁，氢化咔唑或季铵化咪唑以常规量用作额外的抑制剂。
在上面所列的本发明防冻/防腐浓缩物的额外组分中，还优选使用(a)组和/或(b)组的羧酸和/或(e)组的杂环。
在特别优选的实施方案中，本发明防冻/防腐浓缩物在每种情形下额外含有至多5％重量、尤其0.5-3％重量的两种来自(a)组和/或(b)组的不同羧酸以及0.05-5％重量、尤其0.1-0.5％重量的一种或多种(e)组的杂环。
这些不同的羧酸例如可以是脂族单羧酸和脂族二羧酸的混合物、芳族单羧酸和脂族二羧酸的混合物、脂族单羧酸和芳族单羧酸的混合物、两种脂族单羧酸的混合物或两种脂族二羧酸的混合物。这里优选额外使用的合适杂环尤其是苯并***和甲苯并***。
本发明防冻浓缩物的pH值一般是4-11，优选4-10，尤其是4.5-8.5。如果需要的话，所需pH还可以通过向配制剂中加入碱金属氢氧化物、氨或胺而调节；固体氢氧化钠或氢氧化钾和氢氧化钠或氢氧化钾的水溶液特别适于此目的。
优选额外使用的羧酸直接以相应的碱金属盐适当地加入，以自动落在所需pH范围内。然而，羧酸也可以游离酸的形式加入，随后用碱金属氢氧化物、氨或胺中和，并可以建立所需pH值范围。
作为其它的常规助剂，本发明防冻/防腐浓缩物还可以含有常规少量的消泡剂(通常是0.003-0.008％重量)，以及出于万一被吞食的卫生和安全原因，还可以含有苦味物质(例如苯酸苄胺酰铵类)和染料。
本发明防冻/防腐浓缩物可通过将各个组分简单混合而制备。
本发明防冻/防腐浓缩物也可以例如由市购超浓缩物而制备。
因此，本发明进一步提供一种制备防冻/防腐浓缩物的方法，其包括如下步骤：
将含有缓蚀剂的防冻超浓缩物与甘油组分混合，所述甘油组分含有的甘油量使得在所得混合物中基于该混合物总量含有10-50％重量的甘油。
在该方法中，超浓缩物与甘油组分的重量比例优选为5∶1-1∶50，更优选为1∶1-1∶20。
基于甘油组分的总量，甘油量优选至少15％重量，更优选至少20％重量。其它组分可以是防冻组分的常规组分，优选乙二醇和水。
本发明还提供含水的冷却剂组合物，其具有降低的凝固点，尤其用于汽车领域的内燃机的散热器保护，其含有水和10-90％重量、尤其是20-60％重量的本发明防冻/防腐浓缩物。
本发明进一步提供本发明冷却剂组合物在其中要确保水的霜冻保护(一般范围为0℃至-40℃，优选为-20℃至-35℃)和同时确保含水容器的金属壳的防腐的***中的用途。本文中，内燃机的冷却回路、尤其是汽车如客车和卡车中的内燃机冷却回路特别令人感兴趣。本发明冷却剂组合物也可以用于固定的发动机、中央加热***的热水回路、电阻加热的散热器、太阳能动力回路以及冷却剂冷却的循环***中。
实施例
下述实施例描述的散热器保护剂HK1、HK2和HK3是商业上典型的具有综合的已测试和已证实性能集合的超浓缩物。以本发明比例加入甘油进一步改进了这一性能集合。
实施例1含/不含甘油的HK1的结冰点确定
HK1是32.6份的乙二醇、26.9份的氢氧化钾水溶液(50％重量)、33份的乙基己酸、2.2份的二水合钼酸钠、2.4份的甲苯并***、2.8份水和助剂(＜0.2份)的混合物。
上表所示对比表明，甘油在含有乙二醇的共混物中作为防冻组分能够实现合乎规格的防冻保护。
实施例2含/不含甘油的HK1的传热腐蚀测试
该测试根据ASTM D 4340用如实施例1的组合物中含/不含甘油的HK1以25％体积的浓度(水类型：ASTM D 4340)进行。
| 铸铝测试金属 | 重量变化，mg/cm2 | 金属外观 |
| 含甘油的HK1 | -0.05 | 灰色锈蚀低沉积 |
| 不含甘油的HK1 | +0.30 | 浅色锈蚀 |
| 规范：英国标准BS 6580 | ＜1 | 无信息 |
上表所示对比表明，含甘油的混合物产生更好的腐蚀结果，因为铝样品的重量变化更低。
实施例3热腐蚀循环装置中的动态腐蚀实验
热腐蚀循环装置设计成类似于根据FVV[German ResearchFoundation for Combustion Engines]book R 4431986的已知装置。当选择对FVV装置及程序的改变时，从下述列表的综述中清楚可见。对于本发明的目的，选择更严苛的操作模式HK 96h。
| 说明 | HK 96h | FVV book R 4431986 |
| 测试液体的温度：加热室入口，℃加热室出口，℃ | 95105 | 80- |
| 升高的压力，巴 | 1.5 | 1.5 |
| 流速，L/h | 210 | 260 |
| 运行时间，h | 96 | 30 |
| 测试液体的体积，L | 1 | 2.3 |
| 加热输出，W | 2300 | 1500 |
| 理论的加热表面应力，W/cm2 | 75 | 50 |
| 材料样品 | GALSi6Cu4(约重65g) | GG-26GAlSi10Mgwa |
| 测试液体的浓度，％体积 | 30 | 20/40 |
| 水的类型 | ASTM D 1384 | 10°GH |
将如ASTM D1384中制备的金属包装拧在一起。假如需要的话，将测试液体引入到容器中，从而将该容器通过循环的热测试液体冲洗。金属包装由下述的金属和合金组成，观察到其顺序是ASTM D 1384的顺序，以及将另外的金属拧在铝上。金属包装由如下合金组成：
铜F-Cu、软焊条LPbSn30(Sb)、黄铜Ms-63、钢II、灰铸铁GG-26、G-AlSi6Cu4、AlMn、Al99.5、G-AlSi12。
用常规方式(即如在ASTM D 1384或FVV R4431986)处理金属。如无另外的指示，浸蚀后记录重量变化。
实施例4含/不含甘油的HK2的动态腐蚀实验
该实验按实施例3所述进行。
HK2是87.8份的乙二醇、5.4份的氢氧化钠水溶液(50％重量)、1.3份的己二酸、5.0份的癸二酸、0.4份的甲苯并***和助剂(＜0.2份)的混合物。
| 含甘油的HK2 | 不含甘油的HK2 | |
| 混合物(180g) | 100g的HK238g的乙二醇42g的甘油 | 100g的HK280g的乙二醇 |
| 铝样品的重量变化(圆形样品)HK 96hKV23922 | 13mg | 36mg |
上表所示对比表明，含甘油的混合物产生更好的腐蚀结果，因为在持续96h的实验后，铝样品的重量变化更低。
实施例5含/不含甘油的HK3的动态腐蚀实验
该实验按实施例3所述进行。
HK3是81.5份的乙二醇、5.9份的氢氧化钠水溶液(50％重量)、5.4份的乙基己酸、3.1份的癸二酸、0.03份的稳定化硅酸盐、2.7份的硼砂、0.3份的甲苯并***、0.7份的硝酸钠和助剂(＜0.4份)的混合物。
| 含甘油的HK3 | 不含甘油的HK3 | |
| 混合物(270g) | 100g的HK3107g的乙二醇63g的甘油 | 100g的HK3170g的乙二醇 |
| 铝样品的温度变化(圆形样品)HK 96hKV23931 | 1℃ | 5℃ |
上表所示对比表明，含甘油的混合物产生更好的腐蚀结果，因为在持续96h的实验后，铝样品的温度升高更低。
Claims (6)
1.一种防冻/防腐浓缩物，其含有如下组分：
-甘油，其中甘油量基于浓缩物的总量为15-35％重量；
-作为防冻组分的选自一元醇、二元醇、不是甘油的三元醇、多羟基醇，这些醇的醚或其混合物的醇，其中醇和甘油的总量基于浓缩物的总量至少为75％重量；
-防腐组分，其中防腐组分量基于浓缩物的总量为1-70％重量，
其中该防冻/防腐浓缩物中的所有组分的含量之和为100％重量。
2.根据权利要求1所述的浓缩物，其额外含有至少一种基于浓缩物的总量各自为如下所示量的下述组分：
(a)至多5％重量的一种或多种呈其碱金属盐、铵盐或取代铵盐形式的各自具有3-16个碳原子的脂族、环脂族或芳族单羧酸；
(b)至多5％重量的一种或多种呈其碱金属盐、铵盐或取代铵盐形式的各自具有3-21个碳原子的脂族或芳族二或三羧酸；
(c)至多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、碱金属钼酸盐或者碱金属或碱土金属氟化物；
(d)至多5％重量的一种或多种具有2-15个碳原子并且可以额外含有醚氧原子或羟基的脂族、环脂族或芳族胺；
(e)至多5％重量的一种或多种具有4-10个碳原子并且可以为苯并稠合的和/或带有额外官能团的单环或双环不饱和或部分不饱和杂环；
(f)至多5％重量的一种或多种四(C1-C8烷氧基)硅烷；
(g)至多10％重量的一种或多种羧酰胺或磺酰胺；
(h)至多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/或不饱和羧酸与烯烃的共聚物。
3.根据权利要求1或2所述的浓缩物，其中浓缩物的pH值为4-11。
4.一种制备防冻/防腐浓缩物的方法，其包括如下步骤：
将含有缓蚀剂的防冻超浓缩物与甘油组分混合，所述甘油组分含有的甘油量使得在所得混合物中基于该混合物的总量含有15-35％重量的甘油，以及其中所得混合物得到根据权利要求1-3中任一项所述的防冻/防腐浓缩物。
5.一种含水的冷却剂组合物，其含有10-90％重量的根据权利要求1-3任一项所述的浓缩物。
6.根据权利要求5的冷却剂组合物在其中要确保水的霜冻保护和同时确保含水容器的金属壳的防腐的***中的用途。
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| EP05004305.8 | 2005-02-28 | ||
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| EP05004450.2 | 2005-03-01 | ||
| EP05004450 | 2005-03-01 | ||
| PCT/EP2006/060213 WO2006092376A1 (de) | 2005-02-28 | 2006-02-23 | Glyzerinhaltige gefrierschutzmittelkonzentrate mit korrisionsschutz |
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| Publication number | Publication date |
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| KR101437690B1 (ko) | 2014-09-03 |
| US20110163260A1 (en) | 2011-07-07 |
| EP1859002B1 (de) | 2011-04-27 |
| WO2006092376A1 (de) | 2006-09-08 |
| AR053686A1 (es) | 2007-05-16 |
| DK1859002T3 (da) | 2011-07-25 |
| EP1859002A1 (de) | 2007-11-28 |
| DE502006009393D1 (de) | 2011-06-09 |
| US8454854B2 (en) | 2013-06-04 |
| ATE507276T1 (de) | 2011-05-15 |
| PL1859002T3 (pl) | 2011-09-30 |
| SI1859002T1 (sl) | 2011-08-31 |
| PT1859002E (pt) | 2011-06-07 |
| CN101128558A (zh) | 2008-02-20 |
| US7927505B2 (en) | 2011-04-19 |
| KR20070116052A (ko) | 2007-12-06 |
| BRPI0608737A2 (pt) | 2010-12-07 |
| US20080149883A1 (en) | 2008-06-26 |
| MY145834A (en) | 2012-04-30 |
| US20130105407A1 (en) | 2013-05-02 |
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