WO2001005906A1 - Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids - Google Patents

Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids Download PDF

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Publication number
WO2001005906A1
WO2001005906A1 PCT/EP2000/005661 EP0005661W WO0105906A1 WO 2001005906 A1 WO2001005906 A1 WO 2001005906A1 EP 0005661 W EP0005661 W EP 0005661W WO 0105906 A1 WO0105906 A1 WO 0105906A1
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WO
WIPO (PCT)
Prior art keywords
composition
heat transfer
freezing point
heat
carboxylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/005661
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English (en)
French (fr)
Inventor
Jean-Pierre Maes
Peter Roose
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Texaco Development Corp
Original Assignee
Texaco Development Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU59753/00A priority Critical patent/AU766625B2/en
Priority to DE60012940T priority patent/DE60012940T2/de
Priority to BRPI0012514-8A priority patent/BR0012514B1/pt
Priority to MXPA02000633A priority patent/MXPA02000633A/es
Priority to PL00378971A priority patent/PL193987B1/pl
Priority to SI200030519T priority patent/SI1206504T1/xx
Priority to AT00945781T priority patent/ATE273362T1/de
Priority to JP2001511125A priority patent/JP4854896B2/ja
Priority to PL353341A priority patent/PL192103B1/pl
Priority to CA002379486A priority patent/CA2379486C/en
Application filed by Texaco Development Corp filed Critical Texaco Development Corp
Priority to US10/031,663 priority patent/US6689289B1/en
Priority to EP00945781A priority patent/EP1206504B1/en
Publication of WO2001005906A1 publication Critical patent/WO2001005906A1/en
Priority to BG06285A priority patent/BG106285A/bg
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • 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
    • C09K5/08—Materials not undergoing a change of physical state when used

Definitions

  • the present invention relates to aqueous heat transfer fluids particularly antifreeze coolants and general cooling fluids that provide both frost protection and corrosion protection by use of synergistic combinations of carboxylic acids.
  • the heat transfer fluids of this invention are non-toxic, environmentally friendly and provide improved heat -transfer properties, compared to traditional glycol based coolants and heat-transfer fluids. Improved corrosion protection is obtained compared to formate and acetate based heat transfer fluids using conventional corrosion inhibitors.
  • the heat transfer fluids of the present invention can be used in any heat-exchange application including industrial heat-exchangers, refrigeration- and cooling systems, cooling towers, open and closed heat exchangers and for cooling internal combustion engines . The fluids protect the equipment from frost and corrosion damage.
  • Heat transfer fluids whether used for heat-transfer in industrial or automotive applications have been, almost without exception, water-based.
  • the efficiency of a heat transfer fluid to transport heat away from heat producing surfaces can be expressed in terms of the specific heat and thermal conductivity of the fluid.
  • Specific heat of a substance is the ratio of its thermal capacity to that of water.
  • the thermal capacity is the quantity of heat necessary to produce unit change of temperature in unit mass.
  • Thermal conductivity of a substance is the time rate of transfer of heat by conduction through a mass of unit thickness, across a unit area for a unit difference of temperature.
  • Viscosity of the heat transfer fluid is also a factor in evaluating the overall heat exchange efficiency - a better fluidity will contribute to an effective heat transport.
  • water has the highest specific heat, the highest thermal conductivity and lowest viscosity. Whilst water is a most effective heat transfer fluid, it does not provide the required freezing and corrosion protection.
  • Heat transfer fluids and engine coolants are known that contain high concentrations of inorganic salts to depress the freezing point.
  • Calcium chloride is an example of the salts used to that purpose.
  • inorganic salts used for frost protection it is extremely corrosive and corrosion cannot be adequately prevented by inhibitors.
  • Another disadvantage of such coolants is that at very low temperatures, the solubility of inorganic salts is reduced.
  • Petroleum products such as kerosene have also been used in heat -exchange and cooling systems as a total replacement for water, but their adverse effect on rubber hoses, poor heat- transfer, and flammability has made their use impractical.
  • Organic hydroxy compounds were found more reliable and ethylene glycol came into widespread use.
  • Other heat transfer fluid bases included glycerol, the lower boiling point alcohols such as methanol, and propylene glycol. Of these only propylene glycol is still under active consideration because of its low toxicity compared to ethylene glycol.
  • water/glycol mixtures are used today because they are chemically stable and compatible with the elastomers and plastics used in heat- exchange systems.
  • ethylene glycol is preferred as a heat transfer fluid base because of its high boiling point and flash point compared to methyl alcohol, its lower viscosity (better fluidity) and low cost compared to propylene glycol .
  • Propylene glycol is used in applications where a lower toxicity is desirable. The heat-exchange capacity of water/freezing point depressant solutions is reduced with increasing freezing point depressant content .
  • Pure water remains a better heat transfer fluid compared to any mixture of ethylene- or propylene glycol.
  • a compromise between the required freezing protection and heat exchange efficiency has to be made.
  • Aqueous glycol solutions have higher viscosities at higher glycol concentrations. A better fluidity is thus obtained in solutions containing less freezing point depressant.
  • Alkali salts of low molecular organic acids such as alkali metal acetate and alkali metal formate can also provide frost protection when dissolved in water.
  • acetate and formate solutions have improved heat- transfer properties and lower viscosities, for a same level of frost protection. They are also more environmentally friendly than glycols.
  • Formate and acetate based fluids have found applications as heat-exchange fluid and airport runway deicing fluids. US Patent 5,104,562 describes a coolant composition containing a potassium formate and potassium acetate.
  • Corrosion in heat-exchange- and engine cooling systems will have two main effects: deterioration of the metal component either by uniform wastage or localised attack (pitting, crevice corrosion) , and the production of insoluble corrosion products that will tend to block heat-exchangers, thermostat valves, filters and other components and to impede heat transfer by deposition on heat exchange surfaces. Regardless of the composition of the freezing point depressant, corrosion inhibitors are needed to reduce and control corrosion of the metals in contact with the fluid.
  • One aspect of the invention is that specific aqueous solutions of organic carboxylates show very low freezing points at eutectic compositions i.e. compositions mixed in such proportions that the freezing-point is a minimum, the constituents freezing simultaneously. This is very important, as the total organic salt content can be significantly reduced compared with conventional monocarbon carboxylates (formate or acetate) systems offering the same frost protection.
  • the advantage is not only in improved economics but also, in better heat-transfer due to a higher specific heat and improved fluidity resulting from the higher water content at the same frost protection.
  • solutions of low carbon (C ⁇ C,) carboxylic acid salts, in combination with higher carbon (C 3 -C 3 ) carboxylic acid salts provide synergistic frost protection.
  • Very effective eutectica have been found for the combination of the alkali salts of a C : carboxylic acid (methanoic- or formic acid) and a C 3 carboxylic acid (propanoic- or propionic acid) .
  • Another aspect of the present invention is that improved synergistic frost protection and corrosion protection is found by adding one or a plurality of C 6 -C 12 carboxylic acids. It has been found that higher carbon carboxylates (C 12 -C ⁇ 6 ) also increase the corrosion protection, but their solubility in the salt solutions is very limited. Optionally the addition of hydrocarbyl triazoles or thiazoles can further improve the corrosion protection.
  • the pure solution of potassium formate (40:0) in water has a freezing point of -36°C.
  • the same concentration of sodium propanoate (40:0) in water has a freezing point of -32°C.
  • a freezing point below -48°C is found at a ratio 20:20, which is remarkably lower than the expected mid-point of -34 °C calculated using the addition rule.
  • the laws of molecular freezing point depression are apparently no longer valid for this type of solution.
  • the combination of the added organic salts seem to interfere with the solidification of water to ice crystals in a way that it inhibits the possibility to obtain a regular crystal structure in the water molecules.
  • C 6 -C 12 carboxylates as corrosion inhibitors has been investigated in aqueous solutions of low carbon (Ci-C j ) and higher carbon (C 3 -C 5 ) carboxylic acid salts used as freezing point depressants.
  • low carbon (Ci-C j ) and higher carbon (C 3 -C 5 ) carboxylic acid salts used as freezing point depressants Different combinations of conventional inhibitors such as borax, benzoates, molybdates and nitrites are currently used with hydrocarbyl triazole for corrosion protection in acetate and formate salt solutions. Some of these inhibitors are toxic and harmful to the environment . Others are not very stable in organic salts solutions and may precipitate out of solution under conditions of high temperatures or severe frost.
  • Tables 3 and 4 show the results of corrosion tests.
  • Comparative Example A (Traditional Formate-Based Formulation)
  • aqueous formulation comprising of 320 g potassium hydroxide, 275 ml formic acid (98%) , 13 g 2- ethylhexanoic acid, 1 g sebacic acid, 0.8 g tolyltriazole and 4 g sodium hydroxide, adjusted to pH 9.
  • an aqueous antifreeze formulation comprising of 115 g potassium hydroxide, 110 ml formic acid (98%), 200 g sodium propanoate, 16.2 g 2 -ethylhexanoic acid, 1.26 g sebacic acid, 1.0 g tolyltriazole and 4 g sodium hydroxide, adjusted to pH 9.
  • Comparative Example B (Traditional Acetate-Based Formulation)
  • An aqueous antifreeze formulation comprising of 400 g potassium hydroxide, 60 ml formic acid (98%), 360 ml acetic acid (99.5%), 800 ml water, 5 g sodium benzoate and 1 g benzotriazole .
  • aqueous antifreeze formulation comprising 400 g potassium formate, 16.2 g 2-ethylhexanoic acid, 1.26 g sebacic acid, 1.0 g tolyltriazole and 4 g sodium hydroxide, adjusted to pH 8.8.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Treatment Of Sludge (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Detergent Compositions (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
PCT/EP2000/005661 1999-07-16 2000-06-20 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids Ceased WO2001005906A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
PL353341A PL192103B1 (pl) 1999-07-16 2000-06-20 Ciekła kompozycja do przenoszenia ciepła i jej zastosowanie
BRPI0012514-8A BR0012514B1 (pt) 1999-07-16 2000-06-20 composição de fluido de transferência térmica e uso de uma composição compreendendo uma mistura de sais de ácido carboxìlico.
MXPA02000633A MXPA02000633A (es) 1999-07-16 2000-06-20 Combinaciones sinergisticas de carboxilatos para utilizarse como depresores del punto de congelamiento e inhibidores de corrosion en fluidos de termotransferencia.
PL00378971A PL193987B1 (pl) 1999-07-16 2000-06-20 Zastosowanie wodnej kompozycji do przenoszenia ciepła
SI200030519T SI1206504T1 (en) 1999-07-16 2000-06-20 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids
AT00945781T ATE273362T1 (de) 1999-07-16 2000-06-20 Synergistische kombinationen von carboxylaten zur verwendung als gefrierpunkterniedriger und korrosionsinhibitoren in wärmeübertragungsflüssigkeiten
JP2001511125A JP4854896B2 (ja) 1999-07-16 2000-06-20 伝熱液中の凝固点降下剤および腐食防止剤として用いるためのカルボン酸塩の相乗的組合せ
AU59753/00A AU766625B2 (en) 1999-07-16 2000-06-20 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids
DE60012940T DE60012940T2 (de) 1999-07-16 2000-06-20 Synergistische kombinationen von carboxylaten zur verwendung als gefrierpunkterniedriger und korrosionsinhibitoren in wärmeübertragungsflüssigkeiten
CA002379486A CA2379486C (en) 1999-07-16 2000-06-20 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids
US10/031,663 US6689289B1 (en) 1999-07-16 2000-06-20 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids
EP00945781A EP1206504B1 (en) 1999-07-16 2000-06-20 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids
BG06285A BG106285A (bg) 1999-07-16 2002-01-08 Синергични комбинации от карбоксилати с приложение за понижаване на точката на замръзване и като инхибитори на корозия в топлопренасящи течности

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99305665.4 1999-07-16
EP99305665A EP1087004A1 (en) 1999-07-16 1999-07-16 Synergistic combinations of carboxylates for use as freezing point depressants and corrosion inhibitors in heat transfer fluids

Publications (1)

Publication Number Publication Date
WO2001005906A1 true WO2001005906A1 (en) 2001-01-25

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US (1) US6689289B1 (enExample)
EP (3) EP1087004A1 (enExample)
JP (1) JP4854896B2 (enExample)
KR (1) KR100674347B1 (enExample)
CN (1) CN1213125C (enExample)
AT (2) ATE479733T1 (enExample)
AU (1) AU766625B2 (enExample)
BG (1) BG106285A (enExample)
BR (2) BR0012514B1 (enExample)
CA (2) CA2379486C (enExample)
CZ (2) CZ298867B6 (enExample)
DE (2) DE60012940T2 (enExample)
ES (2) ES2352542T3 (enExample)
MX (1) MXPA02000633A (enExample)
PL (2) PL193987B1 (enExample)
PT (1) PT1206504E (enExample)
RU (1) RU2240338C2 (enExample)
SI (1) SI1206504T1 (enExample)
TR (2) TR200200078T2 (enExample)
WO (1) WO2001005906A1 (enExample)
ZA (1) ZA200200261B (enExample)

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WO2004015023A1 (de) * 2002-08-02 2004-02-19 Basf Aktiengesellschaft Glykolfreie wässrige gefrierschutzmittel enthaltend dicarbonsäuresalze
CZ299952B6 (cs) * 2001-05-10 2009-01-07 Basf Aktiengesellschaft Mrazuvzdorný koncentrát obsahující barvivo C.I. Reactive Violet 5
EP2864437B1 (en) 2012-06-22 2023-03-01 Esseco Uk Limited De-icer and/or anti-icer compositions and methods

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KR101331986B1 (ko) * 2006-12-20 2013-11-25 주식회사 지코스 유기산염 고농도 농축액 조성물, 이의 제조방법 및 이를함유하는 내연 기관용 냉각수
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US20090001313A1 (en) * 2007-06-28 2009-01-01 Chevron U.S.A. Inc. Antifreeze Concentrate and Coolant Compositions and Preparation Thereof
US7790054B2 (en) 2007-06-28 2010-09-07 Chevron U.S.A. Inc. Antifreeze concentrate and coolant compositions and preparation thereof
JP2009040803A (ja) * 2007-08-06 2009-02-26 National Institute Of Advanced Industrial & Technology 伝熱媒体
CA2634382A1 (en) 2008-06-06 2009-12-06 Dnp Canada Inc. Compositions made from fermentation broth and methods of use
US20100270494A1 (en) * 2009-04-22 2010-10-28 Chevron U.S.A. Inc. Hot test fluid containing vapor phase inhibition
CN102634323A (zh) * 2012-04-16 2012-08-15 贾振勇 一种采暖防冻剂
JP6256757B2 (ja) * 2014-01-15 2018-01-10 公立大学法人 富山県立大学 凍結防止剤とその利用方法
JP6154371B2 (ja) * 2014-12-26 2017-06-28 トヨタ自動車株式会社 冷却液組成物及びこれを用いた内燃機関の運転方法
CN107250318B (zh) * 2015-03-04 2023-10-27 布拉斯通产品公司 超浓缩添加剂溶液组合物
CN106857803A (zh) * 2017-01-20 2017-06-20 东莞市领升等离子抛光设备有限公司 一种低冰点速冻保鲜液
JP2020128839A (ja) * 2019-02-08 2020-08-27 株式会社デンソー 熱輸送システム
MX2022001739A (es) * 2019-08-22 2022-03-11 Arteco Nv Fluido de transferencia de calor basado en glicol que comprende acido carboxilico organico o una sal del mismo, metodos para sus preparaciones y usos del mismo.
CN113349219B (zh) * 2021-05-25 2022-09-23 中国船舶重工集团公司第七一八研究所 一种抗冻消毒剂及其制备方法

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CZ299952B6 (cs) * 2001-05-10 2009-01-07 Basf Aktiengesellschaft Mrazuvzdorný koncentrát obsahující barvivo C.I. Reactive Violet 5
WO2004015023A1 (de) * 2002-08-02 2004-02-19 Basf Aktiengesellschaft Glykolfreie wässrige gefrierschutzmittel enthaltend dicarbonsäuresalze
CN100338168C (zh) * 2002-08-02 2007-09-19 巴斯福股份公司 含有二羧酸盐且不含二醇的含水防冻剂
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EP2428542A2 (de) 2002-08-02 2012-03-14 Basf Se Glykolfreie wässrige Gefrierschutzmittel enthaltend Dicarbonsäuresalze
US8202444B2 (en) 2002-08-02 2012-06-19 Basf Aktiengesellschaft Glycol-free aqueous anti-freeze agent containing dicarboxylic salts
EP2428542A3 (de) * 2002-08-02 2014-01-22 Basf Se Glykolfreie wässrige Gefrierschutzmittel enthaltend Dicarbonsäuresalze
EP2864437B1 (en) 2012-06-22 2023-03-01 Esseco Uk Limited De-icer and/or anti-icer compositions and methods

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PL192103B1 (pl) 2006-08-31
RU2240338C2 (ru) 2004-11-20
ATE479733T1 (de) 2010-09-15
CA2379486A1 (en) 2001-01-25
US6689289B1 (en) 2004-02-10
CA2599138A1 (en) 2001-01-25
EP1449903A3 (en) 2008-03-19
ES2352542T3 (es) 2011-02-21
PL193987B1 (pl) 2007-04-30
BG106285A (bg) 2002-09-30
TR200201931T2 (tr) 2002-10-21
CZ2002177A3 (cs) 2002-05-15
DE60012940D1 (de) 2004-09-16
AU766625B2 (en) 2003-10-23
ES2228567T3 (es) 2005-04-16
CA2379486C (en) 2007-11-27
PL353341A1 (en) 2003-11-17
DE60012940T2 (de) 2005-08-18
CZ298580B6 (cs) 2007-11-14
CN1213125C (zh) 2005-08-03
DE60044914D1 (de) 2010-10-14
SI1206504T1 (en) 2005-02-28
TR200200078T2 (tr) 2002-06-21
EP1449903B1 (en) 2010-09-01
EP1206504A1 (en) 2002-05-22
JP2003505532A (ja) 2003-02-12
ATE273362T1 (de) 2004-08-15
CN1360622A (zh) 2002-07-24
ZA200200261B (en) 2002-09-25
BR0012514B1 (pt) 2011-03-22
EP1449903A2 (en) 2004-08-25
BR0012514A (pt) 2002-05-28
KR100674347B1 (ko) 2007-01-24
JP4854896B2 (ja) 2012-01-18
MXPA02000633A (es) 2003-07-21
CZ298867B6 (cs) 2008-02-27
PT1206504E (pt) 2005-01-31
BR0017508B1 (pt) 2012-12-25
AU5975300A (en) 2001-02-05
KR20020015714A (ko) 2002-02-28
CA2599138C (en) 2010-07-13
EP1087004A1 (en) 2001-03-28
EP1206504B1 (en) 2004-08-11

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