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US20060180793A1 - Thermal liquids providing glass corrosion protection especially for solar systems - Google Patents

Thermal liquids providing glass corrosion protection especially for solar systems Download PDF

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Publication number
US20060180793A1
US20060180793A1 US10/542,776 US54277605A US2006180793A1 US 20060180793 A1 US20060180793 A1 US 20060180793A1 US 54277605 A US54277605 A US 54277605A US 2006180793 A1 US2006180793 A1 US 2006180793A1
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US
United States
Prior art keywords
concentrate
weight
heat transfer
hydrocarbon
transfer liquid
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.)
Abandoned
Application number
US10/542,776
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English (en)
Inventor
Bernd Wenderoth
Claudius Kormann
Horst Zollner
Ladislaus Meszaros
Frank Hillerns
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BASF SE
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Individual
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Filing date
Publication date
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Assigned to BASF AKTIENGESELLSCHAFT reassignment BASF AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HILLERNS, FRANK, KORMANN, CLAUDIUS, MESZAROS, LADISLAUS, WENDEROTH, BERND, ZOLLNER, HORST
Publication of US20060180793A1 publication Critical patent/US20060180793A1/en
Abandoned 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
    • 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
    • C09K5/10—Liquid materials

Definitions

  • the present invention relates in particular to borate-free concentrates based on glycols with glass corrosion protection for heat transfer liquids, in particular for solar plants, comprising amines and, if required, stabilized silicates and hydrocarbon-thiazoles and hydrocarbon-triazoles; further corrosion inhibitors and other components may also be present.
  • the present invention furthermore relates to ready-to-use aqueous heat transfer liquids which are based on said concentrates, and their use in solar plants.
  • Concentrates for heat transfer liquids in particular for solar plants, generally contain alkylene glycols, especially 1,2-propylene glycol or ethylene glycol, as the main component.
  • alkylene glycols especially 1,2-propylene glycol or ethylene glycol
  • they are diluted with water and, in addition to preventing freezing, should ensure good heat transfer.
  • Alkylene glycol/water mixtures are, however, very corrosive at the high temperatures occurring in intense sunlight and in particular those occurring when the plant is not operating; the various metals, for example copper, brass, steel, cast iron (gray cast iron), lead, tin, chromium, zinc, aluminum, magnesium and alloys thereof and solder metals, for example tin solder (soft solder), which in principle can occur in the heat transfer circulation of solar plants therefore have to be adequately protected from various types of corrosion, for example pitting, crevice corrosion, erosion or cavitation.
  • a large number of individual chemical substances is known from the prior art for use as corrosion inhibitors for metals in such systems.
  • EP 0 971 013 A1 describes aqueous heat transfer media for solar plants, which contain tri- and/or tetraethylene glycol, 1,2-propylene glycol and/or ethylene glycol, comprising a content of borates, silicates, mono- or dicarboxylic acids, sodium benzoate, benzotriazoles, tolutriazoles, nitrites or nitrates as corrosion inhibitors.
  • EP 0 109 377 A2 claims a solar collector which contains a heat transfer liquid comprising monoethylene glycol or glycerol, water, formic acid and a quaternary ammonium salt.
  • EP 0 092 687 B1 describes an aqueous corrosion-inhibiting heat transfer composition which is also suitable for solar systems and contains an alcohol, for example ethylene glycol or propylene glycol, and an organosiloxane/silicate copolymer and, in the absence of nitrite, contains at least one nitrate salt.
  • known corrosion inhibitors for metals such as molybdate, borate, phosphate, benzoate, hydroxybenzoate, nitrite, tolutriazole, mercaptobenzothiazole and benzotriazole may be present.
  • the liquids to be provided should no longer have the disadvantages of glass corrosion of the prior art.
  • heat transfer liquid concentrates with glass corrosion protection in particular for solar plants, comprising, in addition to at least one glycol,
  • novel concentrates for heat transfer liquids can be used in conventional solar plants, but in particular in newer systems comprising special glass, in which the heat transfer liquid no longer flows through metal tubes inside evacuated glass tubes but directly through the glass tubes, with the result that particular protection of the internal glass surfaces from opacity due to corrosion is required.
  • R 1 to R 3 are selected from hydrogen, alkyl radicals with 2 to 9 carbon atoms and alkyl radicals with 1 to 9 carbon atoms which have one or more hydroxyl substituents.
  • R 1 to R 3 are selected from hydrogen and alkyl groups with 3 or 4 carbon atoms and alkyl radicals with 3 or 4 carbon atoms which have one or more hydroxyl substituents.
  • Examples of preferred amines are ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, isononylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, triethylamine, diisopropylamine, butyldiethanolamine and mono-, di- and triethanolamine.
  • alkyl-substituted amines in which at least one alkyl radical carries at least one hydroxyl substituent are particularly preferred.
  • Diisopropanolamine or butyldiethanolamine is particularly preferably used for component a).
  • the component b) contains at least one alkali metal silicate, particularly suitable silicates being those described in EP-A 0 189 527.
  • suitable silicates being those described in EP-A 0 189 527.
  • suitable silicates are alkali metal orthosilicates, alkali metal metasilicates, alkali metal tetrasilicates and alkali metal silicates.
  • the sodium salts are preferred. In particular, sodium metasilicate is used.
  • the alkali metal silicate is furthermore preferably stabilized by conventional organosilicophosphonates, for example according to EP-A 0 189 527 or DE-OS 29 12 430, or conventional organosilicosulfonates, for example according to EP-A 0 061 694, in conventional amounts. Silicates stabilized by organosilicophosphonates are particularly preferred.
  • the organosilicophosphonates disclosed in EP-A 0 189 527 and DE-OS 29 12 430 and the organosilicosulfonates disclosed in EP-A 0 061 694 are an important component of the present invention and are hereby incorporated by reference in the present Application.
  • the component c) is a mixture of at least two hydrocarbon-thiazoles, a mixture of at least one hydrocarbon-triazole and one hydrocarbon-thiazole or a mixture of at least two different hydrocarbon-triazoles.
  • preferred hydrocarbon-thiazoles are benzothiazole and 2-mercaptobenzothiazole.
  • a mixture of at least two different hydrocarbon-triazoles is preferably used. These are selected in particular from benzotriazole, tolutriazole and 1H-1,2,4-triazole.
  • the component d) contains sodium molybdate, in particular sodium molybdate dihydrate.
  • the component d) contains at least one hard water stabilizer based on polyacrylic acid, polymaleic acid, acrylic acid/maleic acid copolymers, polyvinylpyrrolidone, polyvinylimidazole, vinylpyrrolidone/vinylimidazole copolymers and copolymers of unsaturated carboxylic acids and olefins.
  • soluble magnesium salts of organic acids preferably magnesium benzenesulfonate, magnesium methanesulfonate, magnesium acetate or magnesium propionate, and furthermore hydrocarbazoles and/or quaternized imidazoles, as described in DE-A 196 05 509, in conventional amounts may also be used as further inhibitors.
  • the pH of the novel heat transfer concentrates is usually from 6 to 11, preferably from 7 to 10, in particular from 7.5 to 10.
  • the desired pH is established, as a rule, by adding alkali metal hydroxide to the formulation.
  • Solid sodium hydroxide or potassium hydroxide and aqueous sodium hydroxide solution and potassium hydroxide solution are particularly suitable for establishing the pH.
  • novel concentrates contain no borate.
  • borate may be present in the heat transfer liquids or concentrates, but then the advantages according to the invention are not achieved in most cases.
  • greater glass corrosion is generally to be found, which can assume substantial levels depending on the composition of the liquid.
  • the borate usually used is borax (sodium tetraborate).
  • the novel heat transfer liquid concentrates preferably furthermore contain a freezing point depressant which is selected from alkylene glycols and derivatives thereof.
  • the freezing point depressant is preferably present in the novel concentrates in an amount of at least 75, more preferably at least 85, % by weight.
  • lower alkylene glycols and derivatives thereof for example ethylene glycol and 1,2-propylene glycol
  • higher glycols and glycol ethers are also suitable, for example diethylene glycol, dipropylene glycol, tri- and tetraethylene glycol, polyethylene glycol, monoethers of glycols, for example the methyl, ethyl, propyl and butyl ethers of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • 1,3-Propanediol and glycerol are furthermore suitable.
  • a single solvent or a mixture of two or more solvents may be used.
  • Ethylene glycol and/or 1,2-propylene glycol are preferably used, in particular 1,2-propylene glycol.
  • the freezing point depressant is based on 1,2-propylene glycol or mixtures thereof with other polyalcohols, at least 85, preferably 90, % by weight of 1,2-propylene glycol being present in the mixture.
  • novel heat transfer concentrates may also contain, in conventional small amounts, antifoams, preferably in amounts of from 0.003 to 0.008% by weight, dyes and bitter substances for reasons of hygiene and safety in the event of swallowing, for example of the denatonium benzoate type, as further conventional assistants.
  • the present invention also relates to ready-to-use aqueous heat transfer liquids having a depressed freezing point and the use thereof in solar plants, which comprise water and from 10 to 90, in particular from 20 to 60, % by weight of the novel heat transfer concentrates.
  • novel heat transfer concentrates are distinguished not only by effective corrosion inhibition of the metals or alloys listed at the outset and good high-temperature stability but in particular additionally provide very good protection from glass corrosion in applications in modern solar plants in which the heat transfer liquid is in direct contact with the glass of the solar plant, for example the glass tubes.
  • Comparative Comparative Concentrate 1 concentrate A concentrate B % by weight % by weight % by weight 1,2-Propylene glycol 94 94 94 Polyacrylic acid ⁇ 0.5 ⁇ 0.5 ⁇ 0.5 (Sokalan ® CP 10 S) Potassium hydroxide ⁇ 0.3 ⁇ 0.3 ⁇ 0.3 solution (50% strength) Tolutriazole ⁇ 0.2 ⁇ 0.2 ⁇ 0.2 Benzotriazole ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 Sodium molybdate ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 dihydrate Hydroxyalkylamine ⁇ 5 ⁇ 5 ⁇ 5 Antifoam 40 ppm 40 ppm 40 ppm (Pluriol ® PE 10100) Borax (sodium — — 0.20 tetraborate ⁇ 10H 2 O) Sodium metasilicate 0.20 — — (stabilized with silicophosphonate) Water Remainder
  • 1,2-Propylene glycol was initially taken, and polyacrylic acid, potassium hydroxide solution, tolutriazole, benzotriazole, sodium molybdate dihydrate, the hydroxyalkylamine and antifoam were added in succession while stirring at room temperature. After complete dissolution of all starting materials, the sodium metasilicate diluted beforehand in the ratio 1:9 with water and stabilized with silicophosphonate was added and stirring was carried out until a clear, homogeneous liquid was present.
  • novel concentrate 1 thus obtained and the analogously prepared comparative concentrates A and B were diluted in the ratio 45:55 with water and tested as in example 1 according to the invention and as comparative examples A and B in the tests described below.
  • borosilicate glass ampoules (dimensions in mm: 14.75 ⁇ 0.55) are used. Each container is washed twice with distilled water and once with doubly distilled water. After drying for about 1 hour at 150° C., the ampoules are cooled to room temperature, cleaned on the outside with ethanol and weighed. The ampoules are then filled with 5.5 ml of test solution, closed with an aluminum foil and left for 24 hours at 135° C. in an autoclave (type 112 from KSG Sterilisatoren GmbH, 82140 Olching, temperature regulation of the thermocouple directly in a test specimen in each case).
  • autoclave type 112 from KSG Sterilisatoren GmbH, 82140 Olching, temperature regulation of the thermocouple directly in a test specimen in each case).
  • the containers are removed from the autoclave while taking the usual precautions and are cooled to room temperature in the course of one hour.
  • the ampoules are emptied, washed about five times with distilled water, dried again for about one hour at 150° C., cooled and weighed.
  • Example 1 The test results with example 1 according to the invention and comparative examples A and B are shown in table 1.
  • Example 1 Comp. example A
  • Example B Weight change Weight change Weight change Glass ampoule [mg] [mg] [mg] 1 +0.1 ⁇ 0.1 ⁇ 0.1 2 +0.1 ⁇ 0.2 ⁇ 0.3 3 +0.1 ⁇ 0.2 ⁇ 0.3 4 +0.2 ⁇ 0.2 ⁇ 0.3 5 +0.2 ⁇ 0.1 ⁇ 0.3 6 +0.2 ⁇ 0.3 ⁇ 0.4 7 +0.1 ⁇ 0.2 ⁇ 0.3 8 +0.1 0 ⁇ 0.4 9 +0.1 ⁇ 0.4 ⁇ 0.3 10 +0.2 ⁇ 0.1 ⁇ 0.3 11 +0.1 ⁇ 0.2 ⁇ 0.4 12 +0.1 ⁇ 0.3 ⁇ 0.2 13 +0.2 ⁇ 0.4 0 14 +0.1 ⁇ 0.2 ⁇ 0.3 15 +0.2 ⁇ 0.2 ⁇ 0.2 ⁇ weight change +0.1 ⁇ 0.2 ⁇ 0.3 pH before 9.7 8.4 9.7 pH after 9.7 8.5 9.6
  • Table 2 shows the test results TABLE 2 Glassware corrosion test according to ASTM D 1384-97
  • Example 1 Comp. example A Comp. example B Weight change Weight change Weight change Test specimen [mg/cm ⁇ 2 ] [mg/cm 2 ] [mg/cm 2 ] Copper ⁇ 1.1 ⁇ 0.7 ⁇ 1.4 Soft solder ⁇ 0.6 ⁇ 0.9 ⁇ 67.2 Brass ⁇ 0.8 ⁇ 1.0 ⁇ 2.2 Steel +0.1 ⁇ 0.3 ⁇ 0.1 Gray cast iron +0.6 ⁇ 0.9 ⁇ 0.6 Cast aluminum +0.9 ⁇ 1.5 ⁇ 1.9 pH before 9.7 8.4 9.7 pH after 9.6 8.6 9.2

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
US10/542,776 2003-01-21 2004-01-21 Thermal liquids providing glass corrosion protection especially for solar systems Abandoned US20060180793A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10302093A DE10302093A1 (de) 2003-01-21 2003-01-21 Wärmeträgerflüssigkeiten mit Glaskorrosionsschutz insbesondere für Solaranlagen
DE10302093.4 2003-01-21
PCT/EP2004/000447 WO2004065516A1 (de) 2003-01-21 2004-01-21 Wärmeträgerflüssigkeiten mit glaskorrosionsschutz insbesondere für solaranlagen

Publications (1)

Publication Number Publication Date
US20060180793A1 true US20060180793A1 (en) 2006-08-17

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US10/542,776 Abandoned US20060180793A1 (en) 2003-01-21 2004-01-21 Thermal liquids providing glass corrosion protection especially for solar systems

Country Status (13)

Country Link
US (1) US20060180793A1 (pt)
EP (1) EP1594937B1 (pt)
CN (1) CN100372907C (pt)
AT (1) ATE550402T1 (pt)
AU (1) AU2004205757A1 (pt)
BR (1) BRPI0406870A (pt)
CA (1) CA2514103A1 (pt)
DE (1) DE10302093A1 (pt)
MX (1) MXPA05007703A (pt)
NO (1) NO20053744L (pt)
PL (1) PL378018A1 (pt)
WO (1) WO2004065516A1 (pt)
ZA (1) ZA200505811B (pt)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060090592A1 (en) * 2004-11-04 2006-05-04 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Liquid, its use for the preparation of powder mixtures on the basis of iron or stainless steel as well as a method for the preparation of powder mixtures on the basis of iron or stainless steel
US20060091579A1 (en) * 2004-11-04 2006-05-04 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Liquid and its use for the preparation of hard metals
US20070200088A1 (en) * 2006-02-10 2007-08-30 Ann Wehner Heat transfer compositions comprising renewably-based biodegradable 1,3-propanediol
WO2022034534A1 (en) * 2020-08-13 2022-02-17 Toyota Jidosha Kabushiki Kaisha Coolant composition and concentrated coolant composition
EP4117085A1 (en) * 2021-07-07 2023-01-11 Basf Se Novel coolant with low electrical conductivity

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331977C (zh) * 2004-11-26 2007-08-15 吉林正基科技开发有限责任公司 聚苯胺防锈不冻液
CN101831279B (zh) * 2010-05-24 2013-06-19 深圳市平驰实业有限公司 高聚物复合的防冻液
CN104562040B (zh) * 2013-10-24 2017-05-17 中国石油化工股份有限公司 一种氮杂环改性聚硅氧烷缓蚀剂组合物及其制备方法
US20230227706A1 (en) * 2020-08-26 2023-07-20 Basf Se Novel coolants with improved storage stability

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US4117682A (en) * 1976-11-01 1978-10-03 Smith Otto J M Solar collector system
US4452758A (en) * 1981-07-08 1984-06-05 Basf Wyandotte Corporation Compositions and process for inhibiting corrosion of aluminum
US4683081A (en) * 1986-06-27 1987-07-28 Ferro Corporation Aqueous corrosion inhibitor compositions of a half-amide and a dicarboxylic acid amine salt
US5064552A (en) * 1988-09-24 1991-11-12 Basf Aktiengesellschaft Nitrite- and phosphate-free antifreeze based on glycol
US5387360A (en) * 1992-10-07 1995-02-07 Ethylene Chemical Co., Ltd. Engine antifreeze coolant composition
US6045719A (en) * 1996-02-15 2000-04-04 Basf Aktiengesellschaft Use of quaternized imidazoles as corrosion inhibitors for non-ferrous metals, and coolant compositions and antifreeze concentrates comprising them
US6093341A (en) * 1998-07-08 2000-07-25 Clariant Gmbh Heat transfer medium based on alkylene glycols for solar units

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NL283904A (pt) * 1961-10-04
DE2938868C2 (de) * 1979-09-26 1982-12-02 Deutsche Bp Ag, 2000 Hamburg Gefrierschutzmittel für Kühlflüssigkeiten
CN1076956A (zh) * 1993-04-13 1993-10-06 赵颖 汽车水箱五防液
DE19525090A1 (de) * 1995-07-10 1997-01-16 Basf Ag Verfahren und Mittel zur Verhinderung der Abscheidung von Feststoffen in Solarabsorbern
CN1058945C (zh) * 1997-09-02 2000-11-29 齐齐哈尔铁路机务工贸总公司信德化工厂 内燃机车防沸、防冻冷却液及其制造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117682A (en) * 1976-11-01 1978-10-03 Smith Otto J M Solar collector system
US4452758A (en) * 1981-07-08 1984-06-05 Basf Wyandotte Corporation Compositions and process for inhibiting corrosion of aluminum
US4683081A (en) * 1986-06-27 1987-07-28 Ferro Corporation Aqueous corrosion inhibitor compositions of a half-amide and a dicarboxylic acid amine salt
US5064552A (en) * 1988-09-24 1991-11-12 Basf Aktiengesellschaft Nitrite- and phosphate-free antifreeze based on glycol
US5387360A (en) * 1992-10-07 1995-02-07 Ethylene Chemical Co., Ltd. Engine antifreeze coolant composition
US6045719A (en) * 1996-02-15 2000-04-04 Basf Aktiengesellschaft Use of quaternized imidazoles as corrosion inhibitors for non-ferrous metals, and coolant compositions and antifreeze concentrates comprising them
US6093341A (en) * 1998-07-08 2000-07-25 Clariant Gmbh Heat transfer medium based on alkylene glycols for solar units

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060090592A1 (en) * 2004-11-04 2006-05-04 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Liquid, its use for the preparation of powder mixtures on the basis of iron or stainless steel as well as a method for the preparation of powder mixtures on the basis of iron or stainless steel
US20060091579A1 (en) * 2004-11-04 2006-05-04 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Liquid and its use for the preparation of hard metals
US7531022B2 (en) * 2004-11-04 2009-05-12 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Liquid and its use for the preparation of hard metals
US20070200088A1 (en) * 2006-02-10 2007-08-30 Ann Wehner Heat transfer compositions comprising renewably-based biodegradable 1,3-propanediol
US7988883B2 (en) 2006-02-10 2011-08-02 Dupont Tate & Lyle Bio Products Company, Llc Heat transfer compositions comprising renewably-based biodegradable 1,3-propanediol
WO2022034534A1 (en) * 2020-08-13 2022-02-17 Toyota Jidosha Kabushiki Kaisha Coolant composition and concentrated coolant composition
EP4117085A1 (en) * 2021-07-07 2023-01-11 Basf Se Novel coolant with low electrical conductivity
WO2023280659A1 (en) * 2021-07-07 2023-01-12 Basf Se Novel coolant with low electrical conductivity

Also Published As

Publication number Publication date
BRPI0406870A (pt) 2006-01-03
NO20053744L (no) 2005-10-14
CN1751108A (zh) 2006-03-22
ATE550402T1 (de) 2012-04-15
CA2514103A1 (en) 2004-08-05
ZA200505811B (en) 2006-09-27
WO2004065516A1 (de) 2004-08-05
EP1594937A1 (de) 2005-11-16
PL378018A1 (pl) 2006-02-20
MXPA05007703A (es) 2005-09-30
DE10302093A1 (de) 2004-07-29
AU2004205757A1 (en) 2004-08-05
NO20053744D0 (no) 2005-08-04
CN100372907C (zh) 2008-03-05
EP1594937B1 (de) 2012-03-21

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Owner name: BASF AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WENDEROTH, BERND;HILLERNS, FRANK;KORMANN, CLAUDIUS;AND OTHERS;REEL/FRAME:017511/0208

Effective date: 20050701

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION