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WO2001090232A2 - Procede d'obtention de composition de fluide a resistance au feu renforcee - Google Patents

Procede d'obtention de composition de fluide a resistance au feu renforcee Download PDF

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Publication number
WO2001090232A2
WO2001090232A2 PCT/US2001/015583 US0115583W WO0190232A2 WO 2001090232 A2 WO2001090232 A2 WO 2001090232A2 US 0115583 W US0115583 W US 0115583W WO 0190232 A2 WO0190232 A2 WO 0190232A2
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WIPO (PCT)
Prior art keywords
weight percent
antioxidant
oxide
ethylene oxide
fluid
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/US2001/015583
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English (en)
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WO2001090232A3 (fr
Inventor
George Edward Totten
Paul Lumpkin Matlock
William Lowell Brown
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.)
Union Carbide Chemicals and Plastics Technology LLC
Original Assignee
Union Carbide Chemicals and Plastics Technology LLC
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
Application filed by Union Carbide Chemicals and Plastics Technology LLC filed Critical Union Carbide Chemicals and Plastics Technology LLC
Priority to CA002409213A priority Critical patent/CA2409213A1/fr
Priority to MXPA02011573A priority patent/MXPA02011573A/es
Priority to JP2001587038A priority patent/JP2004512388A/ja
Priority to AU2001263121A priority patent/AU2001263121A1/en
Priority to BR0111114-0A priority patent/BR0111114A/pt
Priority to EP01937378A priority patent/EP1290118A2/fr
Publication of WO2001090232A2 publication Critical patent/WO2001090232A2/fr
Publication of WO2001090232A3 publication Critical patent/WO2001090232A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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    • C10N2020/01—Physico-chemical properties

Definitions

  • the present invention relates to a method for providing fluids with improved fire resistance properties. More particularly, the invention provides a method for providing anhydrous poly(alkylene-glycol)-based fluid compositions with Group 1 or Group 2 fire resistance properties, as measured by calculating a spray flammability parameter which is representative of the heat content of a fluid.
  • T f Fire point temperature (degrees Kelvin)
  • irif Mass flow rate of the fluid (grams per second).
  • S.F.P. may also be estimated according to the following equation which assumes 100 percent combustion efficiency:
  • Calculation of the estimated S.F.P. is used as a preliminary screening procedure for fire resistance. For example, if the objective is to determine if a fluid is Group 1 or Group 2, and if an S.F.P. value of significantly less than 4.0 x 10 4 is obtained, then the fluid will be certified as Group 1 by Factory Mutual without further testing. However, if the estimated S.F.P. is close to 4.0 x 10 4 then the fluid must be tested experimentally to accurately classify it in the appropriate category. A similar procedure is used to classify a fluid according to Groups 2 or Group 3
  • the present invention provides a method for providing an anhydrous poly(alkylene-glycol)- based fluid composition with at least Group 2 fire resistance properties.
  • the composition is formulated with an ethylene oxide/alkylene oxide weight percent ratio and/or an amount of antioxidant sufficient to provide the fluid composition with a spray flammability parameter of less than 8.0 x 10 4 .
  • the invention provides a method for providing an anhydrous poly(alkylene-glycol)-based fluid composition with at least Group 2 fire resistance, characterized by the step of:
  • composition with at least one of an ethylene oxide/alkylene oxide weight percent ratio and an amount of antioxidant sufficient to provide the fluid composition with a spray flammability parameter of less than 8.0 x 10 4 .
  • the invention further provides a method for providing a hydraulic system with at least Group 2 fire resistant properties, characterized by the step of:
  • anhydrous poly(alkylene-glycol)-based hydraulic fluid formulated with at least one of an ethylene oxide/alkylene oxide weight percent ratio and an amount of antioxidant sufficient to provide the fluid with a spray flammability parameter of less than
  • the invention further provides a method for providing a heat treatment system for metal working with at least Group 2 fire resistant properties characterized by the step of:
  • anhydrous poly(alkylene-glycol)-based quenchant formulated with at least one of an ethylene oxide/alkylene oxide weight percent ratio and an amount of antioxidant sufficient to provide the quenchant with a spray flammability parameter of less than 8.0 x lO 4 .
  • Anhydrous poly(alkylene-glycol)-based fluid compositions comprise polymers of poly(alkylene-glycols) (PAG's) which are made from the reaction of alkylene oxide monomers and a nucleophilic starter, usually an alcohol. These polymers are represented by the following general formula: R' R" where:
  • Z an alcohol starter with 1-20 carbon atoms, including methanol, ethanol, propanol, isopropanol, butanol, glycerine, and sucrose.
  • Z may also be an amine starter such as ammonia, monoethanolamine, triethanolamine, and diethanolamine;
  • R', R" H, CH 3 , any aryl or C 2 -C 16 alkyl group in any combination resulting in a block or random structure;
  • R"' H, CH 3 , any aryl, ester, or C 2 -C 16 alkyl group;
  • n 5-500; and
  • x 1-6
  • any PAG-polymer having this general formula may be used in formulating fluid compositions in accordance with the present invention
  • these fluid compositions are usually formulated using ethylene oxide and/or alkylene oxide polymers.
  • the ethylene oxide can range from 0 to 100 weight percent of the oxide feed, with the balance being the alkylene oxide monomer(s), typically propylene oxide, although other oxides such as butylene oxide or styrene oxide can also be used.
  • the sequencing of the oxide monomers can be either random or block.
  • fluid compositions are provided with at least Group 2 fire resistance by providing the composition with an ethylene oxide/alkylene oxide weight percent ratio of from 0:1 to 1:0.
  • the composition includes at least 0.1 weight percent antioxidant, preferably from 0.5 to 10 weight percent antioxidant, and most preferably from 1 to 2 weight percent antioxidant.
  • the fluid composition is provided with Group 1 fire resistance, that is, with an ethylene oxide/alkylene oxide weight percent ratio and/or an amount of antioxidant sufficient to provide a spray flammability parameter of less than or equal to 4.0 x 10 .
  • Group 1 fire resistance is provided by formulating the composition with an ethylene oxide/propylene oxide ratio of at least 2:1 to 1:0.
  • Group 1 fire resistance is provided by formulating the composition with an ethylene oxide/propylene oxide weight percent ratio of from 1 :3 to 3:1 and with 1 weight percent to 2 weight percent of antioxidant.
  • borderline Group 1 /Group 2 fire resistance is provided by formulating the composition with an ethylene oxide/propylene oxide weight percent ratio of 0:1 and from 1 to 2 weight percent of antioxidant.
  • Fluids formulated according to the method of the invention can be used in a number of industrial and commercial applications where the risk of fire is a critical concern.
  • hydraulic system failures have, in a number of instances, resulted in serious fires accompanied by loss of life.
  • hydraulic fluids must not only have superior high pressure and lubricating properties, but these fluids must also provide fire resistance in those applications where a significant risk of fire would result from an hydraulic system failure.
  • Quenchant fluids used in heat treating systems for metalworking applications also present a significant risk of fire. This is particularly the case with marquenching fluids, which are used for the high-temperature heat treatment of crack-sensitive steel alloys.
  • Anhydrous poly(alkylene-glycol)-based fluid compositions formulated according to the invention are particularly suitable for use as hydraulic fluids. These compositions not only provide superior high pressure and fire resistant properties, but can also provide superior lubrication. In addition, it is possible to formulate fire resistant anhydrous (PAG-based hydraulic fluids which also exhibit good biodegradabihty and low aquatic toxicity.
  • the fluid compositions taught by the invention are also excellent quenchants and are therefore particularly suitable for use in heat treating applications. These compositions have quenching properties equivalent to those of the specially formulated mineral oil quenchants typically used in the art and provide the important advantage of being fire resistant.
  • the compositions can also formulated to be water soluble or biodegradable and to provide significantly lower sludging tendencies as compared to mineral oil quenchants.
  • Fluid compositions formulated in accordance with the invention may also include additional components depending on the particular industrial or commercial application for which the fluid will be used. Accordingly, these compositions may include, for example, lubricity modifiers, corrosion inhibitors (both ferrous and non-ferrous types), anti-wear agents, extreme-pressure modifiers, dyes, biocides, anti-foaming agents, wetting agents, viscosity modifiers, thermal stability agents and detergents.
  • anhydrous poly(alkylene-glycol) (PAG)-based fluid composition significantly impacts the fire resistance properties of the composition. More specifically, it has been discovered that by increasing the ethylene oxide content of an anhydrous PAG-based fluid composition, the S.F.P. of the composition is lowered. It has also been discovered that the addition of one or more antioxidants to an anhydrous PAG-based fluid composition reduces the S.F.P. of the composition, regardless of the ethylene oxide/alkylene oxide weight percent ratio of the composition. The S.F.P. lowering effect provided by the antioxidant is dependent on the structure of the antioxidant and its concentration in the fluid composition, at least up to a certain concentration level. As noted previously, one or more antioxidants may be used to provide the desired level of fire resistance.
  • each fluid composition consists of a base fluid having a specified ethylene oxide/propylene oxide (EQ/PO) weight percent ratio, or such a base fluid together with an antioxidant.
  • EQ/PO ethylene oxide/propylene oxide
  • This base fluid also includes Ortholeum 535 (0.25 wt. % of base fluid) and Tolytriazole (0.01 wt. % of base fluid).
  • UCON Lubricant LB-285 is an alcohol-started polymer of propylene oxide having a viscosity of 285 Saybolt Universal Seconds (SUS) at 38 ° C. This polymer is available from Union Carbide Corporation, Danbury, CT.
  • UCON Lubricant LB- 165 is an alcohol-started polymer of propylene oxide having a viscosity of 165 SUS at 38 C. This polymer is available from Union Carbide Corporation, Danbury, CT.
  • UCON Lubricant 50-HP-260 is an alcohol-started copolymer containing equal amounts by weight of ethylene oxide and propylene oxide.
  • the copolymer has a viscosity of 260 SUS at
  • CARBO WAX TPEG-990 is a glycerin-started polymer of ethylene oxide which has a molecular weight of 990 grams per mole.
  • CARBOWAX TPEG-990 is available from Union Carbide Corporation, Danbury, CT.
  • Example 2 shows that increasing the ethylene oxide content of an anhydrous PAG-based fluid composition enhances the fire resistance properties of the fluid.
  • Examples 15, which contains 100 weight percent of ethylene oxide and which does not include an antioxidant has an S.F.P. of 3.02 x 10 . Accordingly, this PAG-based fluid composition exhibits Group 1 fire resistance properties.
  • Example 2 also does not include an antioxidant and has an ethylene oxide/propylene oxide weight percent ratio of 1:1.
  • Example 2 has an S.F.P. of 4.71 x 10 4 and is therefore classified only as a Group 2 fire resistant fluid. However, the S.F.P. of the Example 2 composition is significantly lower than that of the Example 3 composition which is 100 weight percent propylene oxide.
  • Group 1 and Group 2 fire resistance can be provided in an anhydrous PAG-based fluid composition solely by controlling the ethylene oxide to alkylene oxide weight percent ratio of the fluid.
  • These fluids have been used in the past as hydraulic fluids; however, fire resistance was achieved either by incorporating water in the fluid or by adding an agent which controls the droplet size of the fluid, as disclosed in U.S. Patent No. 5,141,663.
  • Incorporating water in an hydraulic fluid presents several disadvantages. These fluids generally exhibit inferior hydraulic pump performance as compared to anhydrous fluids, and they exhibit poor lubrication protection and a much greater potential for cavitation.
  • the anhydrous PAG-based fluid disclosed in the '663 patent overcomes these disadvantages.
  • the composition requires the addition of an agent to control the droplet size of the fluid. Only by employing such an agent can the droplet size and distribution of the fluid as it is sprayed from a nozzle be controlled to provide acceptable fire resistance.
  • Quenchants including water soluble polymers are known in the art. However, these quenchants are often characterized by excessive cooling rates sufficient to causes cracking of steel. Moreover, vaporization of the water in these quenchants can contaminate heat treating atmospheres. The use of anhydrous fluid compositions eliminates these potentially severe problems.
  • Anhydrous PAG-based fluid compositions containing 100 weight percent of ethylene oxide have been used in the past as quenchants on a very limited basis. However, neither the superior fire resistance properties of these fluids nor the fact that fire resistance could be provided by controlling the ethylene oxide content of the fluid was appreciated by those skilled in the art.
  • Group 1 or Group 2 fire resistance is achieved by providing a sufficiently favorable ethylene oxide to propylene oxide weight percent ratio. More specifically, Group 1 fire resistance is achieved by providing an anhydrous PAG- based fluid with an ethylene oxide/propylene oxide weight percent ratio of at least 2:1. Anhydrous PAG-based fluid compositions having an ethylene oxide/propylene oxide weight percent ratio of at least 1:1 exhibit Group 2 fire resistance.
  • the data in Table 2 demonstrate that the fire resistance properties of an anhydrous PAG-based fluid composition are enhanced by the addition of one or more antioxidants, regardless of the ethylene oxide/propylene oxide weight percent ratio of the composition. Moreover, the data show that the addition of antioxidant to an anhydrous PAG-based fluid composition provides Group 2 fire resistance even where the composition contains 100 wt. percent of propylene oxide. In particular, the results shown for Examples 3, 5-8 and 10 demonstrate that fire resistant properties approaching very close to Group 1 fire resistance can be provided by the addition of a sufficient amount of an appropriate antioxidant or combination of antioxidants.
  • Antioxidant structure plays an important role in the S.F.P. lowering effect.
  • Several classes of antioxidants have been found to be particularly effective in improving the fire resistant properties of PAG-based fluids.
  • the preferred antioxidants include, phenolic antioxidants, phenol formaldehyde resins containing bisphenol A as a termonomer, amine-based antioxidants such as phenyl- ⁇ -napthylamine (PANA), phenothiazine, and mixtures of these antioxidants.
  • PANA phenyl- ⁇ -napthylamine
  • phenothiazine phenothiazine
  • the invention is not limited to these antioxidants and that other antioxidants known in the art may also be employed.
  • phosphite functional antioxidants such as triphenyl phosphite may be employed; however, the S.F.P lowering effect of these antioxidants are generally inferior to the effect provided by the preferred antioxidants noted above.
  • Examples 3, 5-8 and 10 demonstrate the effect of antioxidant structure on S.F.P. reduction. All of these examples employ the same anhydrous PAG-based fluid containing 100 wt. percent of propylene glycol.
  • the data show that phenothiazine was the most effective antioxidant evaluated in the study (Example 7).
  • PANA an amine-based antioxidant
  • IRGANOX E-3201 a phenolic-based antioxidant available from Ciba Specialties Chemicals Corporation, Tarrytown, NY were both equally effective in reducing the S.F.P. of the base fluid (Examples 5 and 13).
  • Triphenyl phosphite Example 10 was the least effective of the antioxidants examined.
  • Other effective antioxidants include IRGANOX L-06 and IRGANOX 1010, both of which are amine-based antioxidants available from Ciba Specialties Chemicals Corporation, Tarrytown, NY.
  • Example 2 With respect to antioxidant concentration, the results in Table 2 indicate that the S.F.P. lowering effect provided by the antioxidant is apparent only up to a certain concentration of antioxidant in the fluid composition. Additional levels of antioxidant provide only a marginal improvement in the fire resistance properties of the composition.
  • Examples 3-5 all comprise the same anhydrous PAG-based fluid but contain varying amounts of the antioxidant N-phenyl alpha naphthylamine (PANA).
  • Examples 4 and 5 have considerably lower S.F.P. as compared to Example 3, which does not contain any antioxidant. However, doubling the antioxidant concentration from 1 wt. percent in Example 4 to 2 wt. percent in Example 5 provides only a marginal improvement in fire resistance.
  • the fire resistance provided by the antioxidant increases as the ethylene oxide content of the fluid composition increases.
  • the lowest S.F.P. results were obtained with PAG-based compositions containing 100 wt. percent ethylene oxide together with an antioxidant, as shown by Example 11.
  • Slightly higher S.F.P.'s, but still Group 1 fire resistance was provided by the use of an antioxidant in a fluid composition containing only 50 wt. percent ethylene oxide.
  • at least 2 wt. percent of antioxidant is preferred.
  • the fluid composition is characterized by an ethylene oxide/propylene oxide wt. percent ratio of from 1 :3 to 3:1
  • the composition preferably includes from 1 wt. percent to 2 wt. percent of the antioxidant.
  • Equation II may be used to provide a estimated S.F.P. that closely approximates the experimentally derived value.
  • anhydrous PAG-based fluid compositions prepared according to the method of the invention may be used as fire resistant hydraulic fluids, quenchants and lubricating fluids.
  • fluids prepared by the method taught by the invention may be used in a wide variety of industrial and commercial applications where fluid compositions having Group 1 or Group 2 fire resistance are required.

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Abstract

La présente invention concerne un procédé pour l'obtention d'une composition fluide à base de poly(alkylène-glycol) présentant les propriétés de résistance au feu du groupe 1 et du groupe 2. Selon ce procédé, la composition fluide est formulée avec rapport en pourcentage de masse entre oxyde d'éthylène et oxyde d'alkylène et/ou une quantité d'antioxydant qui suffisent pour maintenir le coefficient d'inflammabilité en pulvérisation en dessous de 8,0 x 104. Ces compositions conviennent pour des fluides hydrauliques et des fluides d'extinction, ainsi que pour d'autres applications industrielles et commerciales nécessitant des fluides à résistance au feu renforcée.
PCT/US2001/015583 2000-05-25 2001-05-15 Procede d'obtention de composition de fluide a resistance au feu renforcee Ceased WO2001090232A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002409213A CA2409213A1 (fr) 2000-05-25 2001-05-15 Procede d'obtention de composition de fluide a resistance au feu renforcee
MXPA02011573A MXPA02011573A (es) 2000-05-25 2001-05-15 Un metodo para proveer una composicion fluida con resistencia mejorada al fuego.
JP2001587038A JP2004512388A (ja) 2000-05-25 2001-05-15 耐火性が改良された流体組成物を与える方法
AU2001263121A AU2001263121A1 (en) 2000-05-25 2001-05-15 A method for providing a fluid composition with improved fire resistance
BR0111114-0A BR0111114A (pt) 2000-05-25 2001-05-15 Método para obter uma composição fluida com maior resistência a fogo
EP01937378A EP1290118A2 (fr) 2000-05-25 2001-05-15 Procede d'obtention de composition de fluide a resistance au feu renforcee

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US09/578,960 2000-05-25

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004053031A3 (fr) * 2002-12-09 2004-09-30 Union Carbide Chem Plastic Compositions de fluide hydraulique anhydre
WO2008143648A3 (fr) * 2006-12-05 2009-01-15 Basf Corp Composition fluide ayant une excellente résistance à l'incendie
JP5899599B1 (ja) * 2015-02-09 2016-04-06 株式会社Moresco 潤滑剤組成物及びその利用、並びに脂肪族エーテル化合物
WO2016089991A1 (fr) 2014-12-04 2016-06-09 The Lubrizol Corporation Fluide à haute conductivité pour applications de compresseur d'air
WO2016129148A1 (fr) * 2015-02-09 2016-08-18 株式会社Moresco Composition lubrifiante, son utilisation et composé éther aliphatique
CN107406796A (zh) * 2015-03-30 2017-11-28 出光兴产株式会社 冷冻机润滑油和冷冻机用混合组合物
US20180094206A1 (en) 2015-03-30 2018-04-05 Idemitsu Kosan Co., Ltd. Refrigerator lubricating oil and mixed composition for refrigerator

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1227061B (it) * 1988-09-13 1991-03-14 Lubritalia Spa Fluidi idrodinamici di sicurezza resistenti alla propagazione della fiamma e con elevata temperatura di autoaccensione e procedimento per la loro preparazione.

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004053031A3 (fr) * 2002-12-09 2004-09-30 Union Carbide Chem Plastic Compositions de fluide hydraulique anhydre
WO2008143648A3 (fr) * 2006-12-05 2009-01-15 Basf Corp Composition fluide ayant une excellente résistance à l'incendie
WO2016089991A1 (fr) 2014-12-04 2016-06-09 The Lubrizol Corporation Fluide à haute conductivité pour applications de compresseur d'air
US9920274B2 (en) 2015-02-09 2018-03-20 Moresco Corporation Lubricant composition, use thereof and aliphatic ether compound
WO2016129148A1 (fr) * 2015-02-09 2016-08-18 株式会社Moresco Composition lubrifiante, son utilisation et composé éther aliphatique
JP5899599B1 (ja) * 2015-02-09 2016-04-06 株式会社Moresco 潤滑剤組成物及びその利用、並びに脂肪族エーテル化合物
CN107406796A (zh) * 2015-03-30 2017-11-28 出光兴产株式会社 冷冻机润滑油和冷冻机用混合组合物
US20180094206A1 (en) 2015-03-30 2018-04-05 Idemitsu Kosan Co., Ltd. Refrigerator lubricating oil and mixed composition for refrigerator
EP3279297A4 (fr) * 2015-03-30 2018-10-31 Idemitsu Kosan Co.,Ltd. Huile lubrifiante pour réfrigérateur et composition mixte pour réfrigérateur
EP3279296A4 (fr) * 2015-03-30 2018-10-31 Idemitsu Kosan Co.,Ltd. Huile lubrifiante et composition mixte pour appareil réfrigérant
US10544380B2 (en) 2015-03-30 2020-01-28 Idemitsu Kosan Co., Ltd. Refrigerator lubricating oil and mixed composition for refrigerator
US10781396B2 (en) 2015-03-30 2020-09-22 Idemitsu Kosan Co., Ltd. Refrigerator lubricating oil and mixed composition for refrigerator
CN107406796B (zh) * 2015-03-30 2020-10-16 出光兴产株式会社 冷冻机润滑油和冷冻机用混合组合物

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WO2001090232A3 (fr) 2002-03-28
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CA2409213A1 (fr) 2001-11-29
JP2004512388A (ja) 2004-04-22
AU2001263121A1 (en) 2001-12-03
MXPA02011573A (es) 2003-06-06

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