WO2002064687A1 - Fluides et melanges de fluides respectueux de l'environnement - Google Patents

Fluides et melanges de fluides respectueux de l'environnement Download PDF

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Publication number
WO2002064687A1
WO2002064687A1 PCT/US2001/049701 US0149701W WO02064687A1 WO 2002064687 A1 WO2002064687 A1 WO 2002064687A1 US 0149701 W US0149701 W US 0149701W WO 02064687 A1 WO02064687 A1 WO 02064687A1
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WIPO (PCT)
Prior art keywords
fluid
methyl
pivalate
acetate
neopentyl
Prior art date
Application number
PCT/US2001/049701
Other languages
English (en)
Inventor
Albert I. Yezrielev
Richard Schlosberg
Thomas M. Larson
George Knudson
Original Assignee
Exxonmobil Chemical Patents Inc.
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Filing date
Publication date
Priority claimed from US09/711,275 external-priority patent/US6818049B1/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to JP2002565009A priority Critical patent/JP2004528407A/ja
Priority to KR10-2003-7006394A priority patent/KR20030084896A/ko
Priority to CA002428588A priority patent/CA2428588A1/fr
Publication of WO2002064687A1 publication Critical patent/WO2002064687A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen

Definitions

  • This invention relates to the selection and use of environmentally preferred fluids and fluid blends which exhibit low or reduced reactivity with respect to ozone formation. These environmentally preferred fluids and fluid blends are useful in a number of applications, particularly as industrial solvents, and allow formulators an effective means to improve the environmental performance of their formulations or products.
  • Fluid applications are broad, varied, and complex, and each application has its own set of characteristics and requirements.
  • Proper fluid selection and fluid blend development have a large impact on the success of the operation in which the fluid is used.
  • a blend of several fluids is used in order to get an appropriate evaporation profile.
  • Such a blend must also provide the appropriate solvency properties, including formulation stability, viscosity, flow/leveling, and the like.
  • the fluid blend choice also affects the properties of the dry film, such as gloss, adhesion, and the like.
  • these and other properties may further vary according to the application method (e.g., spray-on), whether the substrate is original equipment (OEM), refinished, etc., and the nature of the substrate coated.
  • fluids and fluid blends include cleaning, printing, delivery of agricultural insecticides and pesticides, extraction processes, use in adhesives, sealants, cosmetics, and drilling muds, and countless others.
  • the term "fluid” encompasses the traditional notion of a solvent, but the latter term no longer adequately describes the possible function of a fluid or blend in the countless possible operations.
  • the term "fluid” includes material that may function as one or more of a carrier, a diluent, a surface tension modifier, dispersant, and the like, as well as a material functioning as a solvent, in the traditional sense of a liquid which solvates a substance (e.g., a solute).
  • the term "industrial solvent” applies to a class of liquid organic compounds used on a large scale to perform one or more of the numerous functions of a fluid in a variety of industries. Relatively few of the large number of known organic compounds that could be used as fluids find use as industrial solvents. Fluids that are used in large quantities have heretofore been selected because they can be produced economically and have attractive safety and use characteristics in manufacturing, consumer and commercial environments. Examples of commercial solvents and their uses as industrial solvents are described in an article entitled "Solvents, IndustriaF', by Don A. Sullivan, Shell Chemical, Encyclopedia of Chemical Technology, 4th. ed., V. 22, pp. 529 - 571 (III) (1997).
  • NAAQS National Ambient Air Quality Standards
  • solvents generally belong to one of two groups depending on their reactivity toward atmospheric photochemical ozone formation: (a) Negligible reactivity organic compounds which generate about the same or less quantity of ozone as would be produced by the same weight % as ethane. These organic compounds are exempt from the definition of a VOC and are not considered to be a VOC in any solvent (fluid) composition. There are numerous such compounds exempted by the EPA from the definition of VOC. However, a majority of such exempted compounds are halogenated derivatives which can possess one or more of the following deficiencies: toxicity, ozone depletion, or waste disposal or incineration problems.
  • non-halogenated, oxygenated organic compounds such as acetone and methyl acetate
  • acetone and methyl acetate have been exempted by the EPA, but such compounds have extremely high evaporation rates and high flammability so as to reduce their applicability in numerous applications.
  • Other such organic compounds such as tertiary butyl acetate which is under exemption consideration by the EPA, while having a significantly improved flammability level and evaporation rate, may be too chemically and thermally unstable for many applications.
  • K 0H scale provides a relative scale of the reactivity of VOC with the OH radicals involved in the complex reactions that produce ozone. See, for instance, Picquet et al., Int. J. Chem. Kinet 30, 839-847 (1998); Schme et al., J. Phys. Chem. A 101, 3514-3525 (1997). Numerous other reactivity scales are known and new reactivity scales are constantly being developed. Since this is a rapidly changing area of research, the most up-to-date information is often obtained via the Internet.
  • Airsite the Atmospheric Chemistry International Research Site for Information and Technology
  • the CERT technique measures "incremental reactivities", the incremental amount of ozone that is produced when the chemical is added to an already polluted atmosphere.
  • Two experiments are conducted to measure the incremental reactivity.
  • a base case experiment measures the ozone produced in an environmental smog chamber under atmospheric conditions designed to represent a polluted atmosphere.
  • the second experiment called “the test case” adds the chemical to the "polluted” smog chamber to determine how much more ozone is produced by the newly added chemical.
  • the results of these tests under certain conditions of VOC and nitrogen oxide ratios are then used in mechanistic models to determine the Maximum Incremental Reactivities (MIR), which is a measure of ozone formation by the chemical compound in question.
  • MIR Maximum Incremental Reactivities
  • MIR values can be reported as the absolute MIR determined by the CERT method or as a relative MIR.
  • One common relative MIR scale uses the Reactive Organic Gas (ROG) in the base case as a benchmark.
  • the Absolute Reactivity ROG is 3.93 g 0 3 per gram ROG. This value is then the divisor for the absolute MIR of other VOCs, if MIR is cited relative to ROG.
  • Absolute reactivities related to the ROG with the above mentioned absolute reactivity 3.93 are provided in "Updated Maximum Incremental Reactivity Scale for Regulatory Applications", Preliminary Report to California Air Resources Board, Contract No. 95-308, William P. Carter, August 6,
  • Solvents currently viewed as essentially non-ozone producing are those which have reactivity rates in the range of ethane.
  • Ethane has a measured reactivity based on the MIR method of 0.35.
  • tertiary butyl acetate t-butyl acetate
  • VOC exempt solvents cannot be used as a one-for- one replacement for conventional solvents. Rather the formulator must balance a number of performance factors to develop an acceptable solvent or solvent blend for a particular application. Some factors are more relevant than others for specific applications. Nevertheless, many performance factors are similar for a number of applications.
  • a "non-ozone depleting" solvent comprising halogenated compounds and an aliphatic or aromatic hydrocarbon compound having 6-20 carbon atoms is disclosed in U.S. Pat. No. 5,749,956.
  • U.S. Pat. No. 5,004,480 describes a method for reducing the levels of air pollution resulting from the combustion of diesel fuel in engines comprising blending dimethyl carbonate (DMC) with diesel fuel and combusting the blended fuel in engines.
  • DMC dimethyl carbonate
  • U.S. Pat. No. 5,032,144 also discusses the addition of oxygenates, including methyl pivalate (methyl 1 ,1 ,1-trimethyl acetate) to gasoline (as octane boosters). The problems addressed by these patents do not relate to the problem of industrial solvent evaporation.
  • WO 98/42774 discloses solvent-resin compositions which "do not contribute appreciably to the formation of ground based ozone".
  • Organic solvents are selected based upon having "reaction rates with hydroxyl ion slower than ethane", and generally selected from halogenated solvents such as chlorobromomethane, methyl chloride, and the like.
  • halogenated solvents such as chlorobromomethane, methyl chloride, and the like.
  • the only non-halogenated solvents that are suggested are n-alkanes (C- ⁇ 2 - C ⁇ 8 ), methyl and t-butyl acetate, acetone, dimethoxymethane, and mineral oils.
  • n-alkanes C- ⁇ 2 - C ⁇ 8
  • methyl and t-butyl acetate acetone
  • dimethoxymethane and mineral oils.
  • the present invention is directed to environmentally preferred fluids and fluid blends, their use as industrial solvents, and to a method of reducing ozone formation in a process wherein at least a portion of a fluid eventually evaporates.
  • the fluids and fluid blends of this invention have been selected by the present inventors for their actual or potential low reactivity in the complex photochemical atmospheric reaction with molecular oxygen (0 2 ) and nitrogen oxides (NO ⁇ ) to create ozone.
  • the present invention provides a means to reduce ozone formation by photochemical atmospheric reactions from a fluid solvent composition which is intended at application conditions to at least partially evaporate into the atmosphere.
  • a fluid solvent composition which is intended at application conditions to at least partially evaporate into the atmosphere.
  • LPPF Low Polluting Potential Fluid
  • VLPPF Very Low Polluting Potential Fluid
  • NPPF Negligibly Polluting Potential Fluid
  • WAMIR ⁇ Wi * MIRL
  • WL is a weight fraction of solvent fluid component L
  • MIRL is the absolute MIR value of solvent fluid component L.
  • WAMIR will be the preferred method of measuring "ozone formation potential" or OFP.
  • the fluids and fluid blends also provide at least one other desirable performance property such as high flash point, low particulate formation, suitable evaporation rates, suitable solvency, low toxicity, high thermal stability, and chemical inertness with respect to non-ozone producing reactions, particularly with respect to acids which may be present in coating formulations.
  • at least one other desirable performance property such as high flash point, low particulate formation, suitable evaporation rates, suitable solvency, low toxicity, high thermal stability, and chemical inertness with respect to non-ozone producing reactions, particularly with respect to acids which may be present in coating formulations.
  • the present invention is also directed to a method of reducing ozone formation from atmospheric photochemical reactions in an application wherein a fluid eventually evaporates, at least partially, into the atmosphere, comprising replacing at least a portion of a fluid having a relatively higher MIR with a fluid having a relatively lower MIR.
  • the present invention offers its greatest benefit from the standpoint of safety and health in large-scale industrial or commercial processes, particularly industrial coating processes or in formulations used in large quantities overall, albeit on a small scale for each individual use, e.g., by a consumer, such as in household paints, cosmetics, and the like.
  • the ordinary artisan can readily differentiate between what is an industrial scale, pilot plant scale, and laboratory scale processes.
  • Still another object of the present invention includes the selection of fluids and/or fluid blends providing low reactivity in ozone formation having compatibility with a wide range of organic compounds of different polarity and molecular weights to make the fluids and/or fluid blends suitable for a wide range of compositions. It is yet another object of the present invention to provide a method of reducing ozone formation caused by the release into the troposphere of a fluid or fluid blend in a process utilizing the fluid or fluid blend, comprising replacing at least a portion of the fluid with another fluid having a lower MIR.
  • a further object is to provide a method of reducing ground-based ozone formation due to fluid evaporation without resorting to expensive control equipment to capture all fluid emission into the environment.
  • Another object is to provide solvents that reduce ground base ozone formation without the use of halogenated solvents and their associated toxicity, incineration, and waste disposal issues.
  • the present invention is directed to An industrial formulation- fluid system comprising one or more organic volatile formulation-fluids including a fluid F being substantially free from unsaturated carbon- carbon bonds or aromatic groups.
  • Fluid F is preferably selected from the group consisting of: carbonates, acetates, dioxalanes, pivalates, isobutyrates, propionates, pentanoates, hexanoates, nonanoates, nitriles and mixtures of any two or more thereof, wherein fluid F is present in an amount such that the formulation-fluid system exhibits a reduction in ozone formation in an amount of at least 10%, preferably at least 25%, and more preferably at least 50% less than that of the formulation-fluid system without fluid F.
  • fluid F has an ozone formation potential (OFP) (in accordance with the Absolute MIR scale in units of g. ozone/g. fluid F) of ⁇ 1.5.
  • Fluid F preferably comprises an oxygen-containing functional group or a nitrogen-containing functional group.
  • the oxygen- containing functional group is preferably selected from the groups consisting of: -ROCOOR', -COOR and -ROR', and the nitrogen- containing functional group is -RCN, wherein R and R' are both selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, isobutyl, tertiary butyl, neopentyl and 2,4,4-trimethylpentyl.
  • hydrocarbyl moieties R and R' have, collectively, a ratio of methyl hydrogen to non-methyl hydrogen of either (1) greater than 1 , (2) greater than 5, or (3) greater than or equal to 9.
  • Fluid F preferably comprises a compound selected from the group consisting of: dimethyl carbonate, methyl pivalate, methyl ethyl carbonate; methyl isopropyl carbonate; methyl neopentyl carbonate; methyl tertiary butyl carbonate; diisopropyl carbonate; neopentyl acetate; ethylene glycol diacetate; 1 ,2-propylene glycol diacetate; 1 ,3- propylene glycol diacetate; 1 ,2-butylene glycol diacetate; 1 ,3-butylene glycol diacetate; 2,3-butylene glycol diacetate; neopentyl glycol diacetate; methyl propionate, ethyl propionate, isopropyl propionate and n-propyl propionate, 2,2-dimethyl dioxolane; 2,2,4-trimethyl dioxolane; 2,2,4,5-tetramethyl dioxolane; ethy
  • the present invention also includes an industrial formulation- fluid system comprising one or more organic volatile formulation-fluids including a fluid F being substantially free from unsaturated carbon- carbon bonds or aromatic groups, wherein fluid F is selected from the group consisting of: carbonates, acetates, dioxalanes, pivalates, isobutyrates, propionates, pentanoates, hexanoates, nonanoates, nitriles and mixtures of any two or more thereof, and wherein fluid F is present in an amount such that the formulation-fluid system has an ozone formation potential (OFP) that is at least 10% less than that of the formulation-fluid system without fluid F.
  • OFP ozone formation potential
  • the present invention also pertains to a non-combustion process utilizing a process fluid or composition comprising a first fluid wherein at least some of the first fluid evaporates into the atmosphere, wherein the process involves replacing at least a portion of the first fluid with a second fluid, i.e., fluid F, wherein fluid F has an ozone formation potential (OFP) (in accordance with the Absolute MIR scale in units of g. ozone/g. fluid F) of ⁇ 1.5 and is present in an amount such that the process fluid has an OFP that is at least 10% less than that of the process fluid without fluid F, thereby decreasing ozone formation from atmospheric photochemical reactions resulting from performance of the process.
  • the process fluid according to the present invention preferably acts as a solvent, carrier, diluent, surface tension modifier, or any combination thereof, in the process. Moreover, the process fluid does not contain a halocarbon.
  • the present invention also pertains to a composition
  • a composition comprising: (1 ) a first fluid wherein at least some of the first fluid evaporates into the atmosphere; and (2) a second fluid comprising an oxygen- containing functional group or a nitrogen-containing functional group and being substantially free from unsaturated carbon-carbon bonds or aromatic groups.
  • the second fluid being selected from the group consisting of carbonates, acetates, dioxalanes, pivalates, isobutyrates, pentanoates, hexanoates, nonanoates, nitriles and mixtures of any two or more thereof, wherein the second fluid has an ozone formation potential (OFP) (in accordance with the Absolute MIR scale in units of g. ozone/g.
  • OFFP ozone formation potential
  • the fluid F of ⁇ 1.5 and is present in an amount such that the composition has an OFP of, or reduces ozone formation by, at least 10% less than that of the composition without the second fluid.
  • the fluids used in accordance with this invention have been selected for their low or reduced ozone formation potential (as reflected in their low or reduced MIR).
  • the ozone formation potential of a composition or fluid solvent may be determined by any scientifically recognized or peer reviewed method including but not limited to, the MIR scale, the K 0H scale, smog chamber studies, and modeling studies such as those performed by Dr. William P. L. Carter. Most references in the description of the present invention will be to the Absolute MIR scale measured in grams ozone produced/gram of fluid solvent.
  • low MIR is meant that the fluids have an MIR similar to or less than 1.5 gram of ozone per gram of the solvent fluid.
  • reduced MIR is meant that, in a process according to the present invention, a first fluid is replaced, in whole or in part, by a second fluid, the second fluid having an MIR lower than the first fluid.
  • the MIR is preferably determined by smog chamber studies, modeling studies, or a combination thereof, but is more preferably determined by "incremental reactivity", and still more preferably by the
  • the MIR of a fluid used in this invention is preferably less than or equal to 1.5 gram of ozone per gram of solvent fluid, more preferably less than or equal to 1.0 gram of ozone per gram of solvent fluid, and most preferably less than or equal to 0.5 gram of ozone per gram of solvent fluid, but the benefits of the present invention are realized if ozone formation is reduced by replacing a first fluid with a second fluid, in whole or in part, wherein the MIR of the second fluid is reduced from that of the first fluid, even if the second fluid has an MIR greater than 1.5 gram of ozone per gram of solvent fluid.
  • the fluid according to the present invention have an MIR less than or equal to 1.50 and more preferably less than or equal to 1.00, still more preferably less than or equal to 0.50.
  • the reactivity in ozone formation is preferably equal to or less than that of acetone and even more preferably equal to or less than that of ethane, by whatever scale or method is used, but most preferably by the MIR scale.
  • the fluid used in a composition according to the present invention will have an MIR less than or equal to 0.50, even more preferably less than or equal to 0.35.
  • Specifically preferred fluids according to the present invention include: dialkyl carbonates, such as dimethyl carbonate (DMC), methyl ethyl carbonate, methyl isopropyl carbonate, methyl sec-butyl carbonate, methyl t-butyl carbonate, methyl neopentyl carbonate, and diisopropyl carbonate; alkyl acetates, such as neopentyl acetate, ethylene glycol diacetate, 1 ,2-propylene glycol diacetate, 1 ,3-propylene glycol diacetate, 1 ,2-butylene glycol diacetate, 1 ,3-butylene glycol diacetate, 2,3-butylene glycol diacetate, neopentyl glycol diacetate; dioxolanes such as 2,2-dimethyl dioxolane, 2,2,4-trimethyl dioxolane, 2,2,4, 5-tetra methyl dioxolane; pivalates such as methyl pival
  • isobutyrate compounds such as isopropyl isobutyrate, neopentyl isobutyrate, and neopentyl glycol mono isobutyrate
  • propionate compounds such as methyl propionate, ethyl propionate, isopropyl propionate and n-propyl propionate
  • TMPN 2,2,4,4-tetramethyl pentanonitrile
  • isopropyl neononanoate pivalonitrile
  • methyl 2,2,4,4-tetramethyl pentanoate methyl neononanoate
  • methyl 3,5,5 trimethyl hexanoate Other preferred fluids are oxygenated (oxygen containing) organic compounds substantially free of moieties containing unsaturated carbon-carbon bonds or aromatic groups.
  • the weighted average MIR of the fluids in a composition according to the present invention will also have the perferred, more preferred, and most preferred MIR levels as discussed above.
  • the weight average MIR be reduced 10%, more preferably 25%, still more preferably 50%, from the MIR calculated prior to the fluid replacement.
  • the Low Polluting Potential Fluids LPPF
  • Very Low Polluting Potential Fluids VLPPF
  • LPPF Low Polluting Potential Fluids
  • VLPPF Very Low Polluting Potential Fluids
  • Negligibly Polluting Potential Fluids as described herein will provide at least one other desirable performance property such as high flash point low particulate formation, suitable evaporation rates, suitable solvency, low toxicity, high thermal stability, and chemical inertness.
  • the fluid or blends have two or more of these performance attributes, and so on, so that the most preferred fluid or fluid blend has all of these performance attributes.
  • the flash point of a fluid according to the present invention is preferably at least -6.1 °C or higher, more preferably greater than +6.0°C, even more preferably greater than 15°C, still more preferably greater than 25°C, yet even more preferably greater than 37.8°C, aYid most preferably greater than 60°C.
  • a fluid or blend e.g., ASTM D92-
  • the flash point of the blend may be the flash point of the more volatile component, in the instance where the flash points of the individual components differ markedly or where the more volatile component is the predominant component.
  • the flash point of the blend may be in between the flash points of the individual components.
  • flash point will refer to the flash point experimentally determined for a single fluid or a blend, as applicable.
  • the fluid or blend thereof, according to the present invention should preferably not contribute measurably to particulate formation of particulates having a size diameter below 2.5 ⁇ m - referred to as
  • the fluid selected to replace a previously-used solvent will be one that also reduces particulate matter to less than or equal to 65 ⁇ g/m 3 , and more preferably less than or equal to 50 ⁇ g/m 3 , when measured over a 24-hour period, preferably spatially averaged over all monitors in a given geographic area.
  • the evaporation rate should be suitable for the intended purpose.
  • the fluid according to the present invention will be used to replace, at least in part, a fluid which is environmentally disadvantaged, meaning it has a reactivity in ozone formation greater than 1.5 in Absolute MIR units.
  • the present invention is related to fluids and fluid blends that at least partially evaporate into the atmosphere during or after their application.
  • the use of fluids of the present invention is preferred when >25% of the fluid is evaporated, more preferably when >50% of the fluid is evaporated, more preferably when >80% of the fluid is evaporated, more preferably when >95% of the fluid is evaporated, and most preferably when >99% of the fluid is evaporated.
  • a fluid according to the present invention replaces, at least in part, another fluid not according to the present invention
  • the fluid replaced has an evaporative rate ranging from that of MEK (methyl ethyl ketone) to less than that of n-butyl acetate.
  • MEK methyl ethyl ketone
  • the fluid or fluid blend according to the present invention may act in the traditional manner of a solvent by dissolving completely the intended solute or it may act to disperse the solute, or it may act otherwise as a fluid defined above. It is important that the solvency of the fluid be adequate for the intended purpose. In addition to the required solvency, the formulated product must be of a viscosity to enable facile application.
  • Toxicity relates to the adverse effect that chemicals have on living organisms.
  • One way to measure the toxic effects of a chemical is to measure the dose-effect relationship; the dose is usually measured in mg of chemical per kg of body mass. This is typically done experimentally by administering the chemical to mice or rats at several doses in the lethal range and plotting the logarithm of the dose versus the percentage of the population killed by the chemical.
  • the dose lethal to 50% of the test population is called the median lethal dose (LD50) and is typically used as a guide for the toxicity of a chemical. See, for instance, Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 24, pp. 456-490.
  • LD50 median lethal dose
  • the fluid or fluid blend according to the present invention have an oral rat LD50 of >500 mg/kg, more preferably >1000 mg/kg, still more preferably >2,000 mg/kg, even more preferably >3,000 mg/kg, and most preferably >5,000 mg/kg.
  • the fluid or blend should also cause no toxicity problems by dermal or inhalation routes and should also not be an eye or skin irritant, as measured by OSHA or European Union (EU) standards.
  • Inertness refers to the lack of a tendency to undergo decomposition with other materials in the fluid system. It may include, for example, inertness towards acids or bases, but particularly to acid catalysts, which are typically present in coating compositions. It is preferred that the fluid being replaced have an MIR greater than that of acetone. In another embodiment, the incremental reactivity, based on the MIR scale, of the fluid being replaced is preferably >0.50, still more preferably >0.1.00, and most preferably >1.50. In another embodiment, it is critical that in a process of reducing tropospheric ozone formation according to the present invention, the fluid replaced have a greater MIR than the fluid added, that is, the fluid according to the present invention. Of course it is to be recognized that only a portion of the higher MIR fluid need be replaced, thus obtaining a blend, in order to achieve the ozone formation reduction.
  • the fluid being replaced may have an acceptable MIR, but be unacceptable with respect to one or more of the aforementioned performance attributes of flash point or flammability, particulate formation, evaporation rate, solvency, toxicity, thermal stability, or inertness.
  • the appropriate addition of DMC or "replacement" of acetone) provided for an improvement in at least one of these attributes.
  • fluids which are replaced by fluids according to the present invention include aromatic and aliphatic hydrocarbon fluids such as: branched C ⁇ -Cg alkanes, straight chain alkanes, cycloaliphatic C ⁇ -Cio hydrocarbons, natural hydrocarbons (alpha or beta pinenes, or turpentines, etc.), ethanol, propanol and higher nontertiary alcohols, C 3 and higher ethers, ether alcohols, ether alcohol acetates, ethyl ethoxy propionate, C 5 and higher ketones, cyclic ketones, etc., C + aromatic hydrocarbons; halocarbons, particularly chlorinated and brominated hydrocarbons; and ethers such as cyclic ethers such as tetrahydrofuran (THF),.
  • aromatic and aliphatic hydrocarbon fluids such as: branched C ⁇ -Cg alkanes, straight chain alkanes, cycloaliphatic C ⁇ -Cio hydrocarbons
  • a fluid according to the present invention for a currently used industrial solvent examples include: in any application, but particularly coatings applications, DMC or methyl pivalate for toluene, xylene, or t-butyl acetate; methyl isopropyl carbonate (MIPC) for xylene or methyl isobutyl ketone (MIBK); and diisopropyl carbonate (DIPC) for methyl amyl ketone (MAK), propylene glycol monomethyl ether acetate (PMAc), or ethyl ethoxy propionate (EEP); in any application, but particularly consumer product applications DMC, MIPC, or DIPC for hydrocarbons; in any application but particularly agricultural applications, DIPC for aromatic fluids; in any application but particularly
  • the fluids and blends according to the present invention may be used in any process using a fluid, and particularly those process wherein at least a portion of the fluid evaporates and even more particularly wherein at least a portion evaporates into the atmosphere.
  • Preferred processes are those utilizing the fluid as one or more of a carrier, diluent, dispersant, solvent, and the like, include processes wherein the fluid functions as an inert reaction medium in which other compounds react; as a heat-transfer fluid removing heat of reaction; to improve workability of a manufacturing process; as a viscosity reducer to thin coatings to application viscosity; as an extraction fluid to separate one material from another by selective dissolution; as a tackifier or to improve adhesion to a substrate for better bonding; as a dissolving medium to prepare solutions of polymers, resins, and other substances; to suspend or disperse pigments and other particulates; and the like.
  • the process be a stationary process and also preferred that the process be a non-combustion process. It is particularly beneficial if the fluid according to the present invention be used to replace at least a portion of a traditional industrial solvent in a process using a large amount of fluid, e.g., a process using 1000 lb/year (500 kg/year), even more preferably 5 tons/year (5000 kg/yr), still more preferably 50 tons/year (50,000 kg/yr), and most preferably one million lbs/year (500,000 kg/yr). In a preferred embodiment, the process wherein the aforementioned fluid replacement occurs is on the scale of at least pilot plant-scale or greater.
  • the process in which a fluid or blend according to the present invention is used or in which at least one fluid according to the present invention replaces, at least partially, a fluid having a higher MIR be a process in which the fluid is intended to evaporate, such as in a coating process.
  • the fluid is intended to evaporate, it is preferred that at least 10% of the fluid or fluids evaporate, more preferably 20% of the fluids, and so on, so that it is most preferable if >99% of the fluid or fluids present in the coating evaporate.
  • one of the greatest environmental benefits of replacing a currently-used industrial solvent with a solvent according to the present invention will be realized if performed in a geographic area where monitoring for ozone and particulate matter formation occurs, and more particularly in geographic areas defined by a city and its contiguous area populated by at least 500,000 persons, and wherein the replacement of at least a portion of the currently-used industrial solvent with a fluid according to the present invention causes at least one of:
  • At least one fluid A having a low MIR preferably similar to or less than or equal to 1.50, more preferably less than or equal to 1.00, , yet still more preferably wherein the MIR is less than or equal to 0.50 and still even more preferably less than or equal to 0.35; and (b) at least one fluid B characterized by having at least one unsuitable attribute selected from: (i) high MIR, preferably measured by the MIR scale, e.g., having an MIR>0.50, more preferably >1.00, and yet even more preferably >1.50; (ii) low flash point, preferably less than or equal to 37.8°C, more preferably less than or equal to 25°C, even more preferably less than or equal to 15°C, yet even more preferably less than or equal to 6.0°C, and most preferably less than -6.1 °C; (iii) formation of 2.5 PM particulates (e.g., wherein said process, using fluid B, produces 2.5 PM greater than 65 micrograms per cubic
  • Preferred examples of fluid B include aromatic and aliphatic hydrocarbon fluids such as toluene and xylenes; alcohols such as ethanol, n-butyl alcohol, n-propyl alcohol, and sec-butanol; esters such as ethyl ethoxy propionate propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone (MEK), C 5 -C 10 linear ketones, cyclic ketones; halocarbons, particularly chlorinated and brominated hydrocarbons; cyclic ethers such as THF, and non-cyclic ethers such as methyl tert-butyl ether (MTBE).
  • aromatic and aliphatic hydrocarbon fluids such as toluene and xylenes
  • alcohols such as ethanol, n-butyl alcohol, n-propyl alcohol, and sec-butanol
  • esters such as ethyl ethoxy propionate
  • the solvents selected according to the present invention can be used in blends with each other as well as in blends with other solvents (e.g., solvents B, above), different from the solvents of the present invention.
  • solvents B e.g., solvents B, above
  • all solvents included in the blend have MIR reactivity ⁇ 0.50 or less
  • the solvent blends also will have low atmospheric photochemical reactivity with MIR of about 0.50 and less.
  • solvent blends can have an MIR in the range of ethane or acetone, even though one component may exceed that range, and therefore in terms of reactivity toward ozone formation behave as exempt solvents.
  • the range of reactivities in exempt solvents allows a selection of fluids with extremely low reactivity, with MIR number in range of ⁇ 0.35 and more suitably ⁇ 0.24.
  • These fluids can be blended not only with fluids with reactivity based on MIR of -0.50 or less but, with appropriately selected fluids with MIR numbers >0.50 and at certain ratios still form fluid compositions with weighted reactivity about 0.50 or less.
  • These blends can significantly expand the range of properties of solvent compositions and provide formulators with necessary flexibility for different applications.
  • MIR reactivity ⁇ 0.50 and at least one solvent with MIR >0.50 which have their weighted reactivity about 0.50 or less is one very important part of the present invention.
  • Blends of these solvents with other solvents with MIR >0.50 resulting in weighted MIR of about 0.50 or less for the blend are preferred solvents according to the present invention.
  • some of the most interesting blends are the blends of at least one solvent with MIR reactivity ⁇ 0.50 and with at least one with MIR reactivity >0.50, which can be generated with the solvents from the list of the present invention.
  • the present invention offers fluids and fluid blends for use in a variety of industrial applications such as paints and other coatings, adhesives, sealants, agricultural chemicals, cleaning solution, consumer products such as cosmetics, pharmaceuticals, drilling muds, extraction, reaction diluents, inks, metalworking fluids, etc.
  • dimethyl carbonate and methyl pivalate are dimethyl carbonate and methyl pivalate.
  • Table 1 demonstrates the extremely low relative reactivities - significantly lower than both acetone and ethane - of dimethyl carbonate and methyl pivalate. This data shows that these two compounds satisfy the EPA requirements for exempt solvents in accordance with current VOC regulations and demonstrating extremely low reactivity for the possible future reactivity based rules. Additionally, DMC is shown to be one of the lowest reactivity compounds among all currently known oxygenated compounds.
  • Table 2a shows the conversion of a portion of the data in Table 1 into Absolute Maximum Incremental Reactivities for the dimethyl carbonate and methyl pivalate.
  • Absolute Ozone Formation for different levels of NO x in ROG is highest for highest level of NO ⁇ scenario (MIR) and lowest for lowest level of NO x scenario (EBIR).
  • MIR NO ⁇ scenario
  • EBIR NO x scenario
  • Absolute Reactivity in atmospheric photochemical ozone formation for tested compounds is highest for MIR scenario and lowest for EBIR scenario.
  • This data demonstrates the outstanding value as Low Polluting Potential Fluids (LPPF), Very Low Polluting Potential Fluid (VLPPF), and Negligibly Polluting Potential Fluid (NPPF).
  • LPPF Low Polluting Potential Fluids
  • VLPPF Very Low Polluting Potential Fluid
  • NPPF Negligibly Polluting Potential Fluid
  • Table 2b shows both compounds as having acceptable flash points, boiling temperatures, evaporation rates, low toxicity, good solvency and overall outstanding performance as versatile environmentally preferred exempt, extremely low ozone formation fluids (solvents) for a very wide range of applications.
  • dimethyl carbonate is highly preferable and can be blended with another organic solvent, even one having an Absolute MIR greater than 0.50 to form a solvent system that would still have an Absolute MIR of less than 0.50.
  • DMC blended with another organic solvent would also exhibit other desirable environmental properties because DMC has a relatively high flash point and low toxicity.
  • the Relative MIR of DMC is calculated to be 0.02, using the SAPRC97 model.
  • LPPF Low Polluting Potential Fluids
  • VLPPF Very Low Polluting Potential Fluids
  • NPPF Negligibly Polluting Potential Fluids
  • the most preferred use of the fluids according to the present invention is with any process wherein the reduction of ozone formation is desired, and more particularly in consumer products, and coatings such as auto refinishing, architectural and industrial coatings and paints.
  • Paints and coatings comprise the largest single category of traditional solvent consumption, accounting for nearly half the solvents used. Fluids serve multiple functions in paints and coatings, including solubility, wetting, viscosity reduction, adhesion promotion, and gloss enhancement. Fluids dissolve the resins, dyes and pigments used in the coating formulations. Also, prior to application, it is common practice to add solvent thinner to attain the desired viscosity for the particular application. Solvents begin to evaporate as soon as the coating materials are applied. As the solvent evaporates, film formation occurs and a continuous, compact film develops. Single solvents are sometimes used in coatings formulations, but most formulations are blends of several solvents.
  • the solvent system includes a slow-evaporating active solvent that remains in the film for an extended period to enhance the film's gloss and smoothness. Because of evaporation and the large amounts of solvents used in coatings, there is a significant amount of VOC emissions into the atmosphere.
  • Resins which may be incorporated into compositions comprising fluids according to the present invention include acrylic, alkyd, polyester, epoxy, silicone, cellulosic and derivatives thereof (e.g., nitrocellulosic and cellulosic esters), PVC, and isocyanate-based resins. Numerous pigments may also be incorporated into compositions according to the present invention, and it is within the skill of the ordinary artisan to determine proper selection of the resin and pigment, depending on the end use of the coating.
  • One of the cleaning applications is cold solvent cleaning which is used to degrease metal parts and other objects in many operations.
  • Mineral spirits have been popular in cold cleaning, but are being supplanted by higher flash point hydrocarbon solvents due to emissions and flammability concerns.
  • Efforts to eliminate organic solvents entirely from cleaning compositions have not been successful because aqueous cleaners do not have the performance properties that make organic solvent based cleaners so desirable.
  • This invention allows formulators the option to seek the use of solvents with very low reactivity as environmentally preferred products meeting environmental concerns and customer performance concerns.
  • An application that is suitable to the low toxicity, high flash point and low reactivity in ozone formation fluids according to the present invention is agricultural products. Pesticides are frequently applied as emulsifiable concentrates. The active insecticide or herbicide is dissolved in a hydrocarbon solvent which also contains an emulsifier. Hydrocarbon solvent selection is critical for this application. It can seriously impact the efficiency of the formulation. The solvent should have adequate solvency for the pesticide, promote good dispersion when diluted with water, have low toxicity and a flash point high enough to minimize flammability hazards.
  • Extraction processes used for separating one substance from another, are commonly employed in the pharmaceutical and food processing industries.
  • Oilseed extraction is a widely used extraction process.
  • Extraction-grade hexane is a common solvent used to extract oil from soybeans, cottonseed, corn, peanuts, and other oil seeds to produce edible oils and meal used for animal feed supplements.
  • Low toxicity, high flash point, low MIR fluids and fluid blends of the present invention can be useful in such industries.
  • Fluid Blends Having Negligible Reactivity Tables A and B below demonstrate fluid solvent blends may be created using (a) negligibly low reactivity fluid solvents and (b) low to very low reactivity fluid solvent in ratios which provide Weight Average MIR reactivity for the total solvent blend of ⁇ 0.45 and therefore providing ozone formation similar to individual fluid solvents with negligibly low reactivity in atmospheric ozone formation.
  • the blends shown in Tables A and B possess characteristics such as better evaporation profiles, flash points, as compared to the individual fluids.
  • Table A the column with methyl acetate shows the minimum methyl acetate content that will provide negligible reactivity to the blend. As shown, all blends with increased methyl acetate content will result in reduced reactivity in ozone formation. However, a main interest in blends with reduced methyl acetate content that maintain negligible reactivity is in an increased flash point of the blend. As seen from Table A, especially advantageous are the two blends with the very low reactivity fluid solvents from the present invention, diisopropyl carbonate and ethyl pivalate which require the lowest levels of methyl acetate. This concept of blending the negligible reactivity compounds with low and very low reactivity secondary fluids that can provide Weight Average MIR less than 0.5 is also subject of this invention.
  • components selected from the list of the present invention provide especially desireable attributes to a finished solvent blend with reduced or negligible reactivity in atmospheric photochemical ozone formation.
  • Table B which utilizes blends with DMC as the negligible reactivity component.
  • DMC allows a high level of the use of the second fluid while maintaining a low MIR while still providing a fluid solvent with an increased flash point from the second fluid by itself.
  • the flash points of each of the composition blends in Table B are > + 6 °C and the majority of them have flash points > + 15 °C.
  • a representative solvent/resin system was chosen to evaluate the sensitivity of a system to solvent changes and evaporation rate differences. Sequential changes to the solvent system were made, and the impact on resin solubility and evaporation rate profile was determined.
  • the initial system consisted of 30 wt% Acryloid B-66 resin (an acrylic resin available from Rohm & Haas) in a fluid mixture comprised of 40 wt% MEK (methyl ethyl ketone), 40 wt% MIBK (methyl isobutyl ketone), and 20 wt% Exxate® 600 (a C& alkyl acetate available from Exxon Chemical Company). DMC was substituted in increments for MIBK, while keeping the rest of the system constant.
  • Acryloid B-66 resin an acrylic resin available from Rohm & Haas
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • Exxate® 600 a C& alkyl acetate available from Exxon Chemical Company
  • a solvent blend of 40 wt% MEK, 35 wt% MIBK, 5 wt% DMC and 20 wt% Exxate® 600 was evaluated, and so on until the final solvent blend consisted of 40 wt% MEK, 0 wt% MIBK, 40 wt% DMC and 20 wt% Exxate® 600. This same procedure was repeated substituting DMC for MEK, methyl pivalate for MIBK, and methyl pivalate for MEK, while keeping the rest of the solvent system the same.
  • the reduction in MIR is calculated using the known values of 1.34 for MEK, 4.68 for MIBK, and determined values of 0.079 for DMC and 0.236 for methyl pivalate (MP).
  • Acrylic solvent systems were prepared to test the stability of dimethyl carbonate to acid catalysts, which are commonly present in coating compositions.
  • the formulations contained 29.9 wt% DMC,
  • the decomposition products of tert butyl acetate, isobutylene and acetic acid have MIRs of 6.81 and 0.67 respectively. This results in a weight average reactivity of the decomposition products of tert. butyl acetate to be 3.64 grams of ozone produced per gram of decomposition products versus 0.21 per tert butyl acetate. Such decomposition products would not be considered negligible or low reactivity compounds.
  • Johcryl 504 410.62 gr. (80% cone, in xylene)
  • Ti0 2 (TiPure R-960) 360.68 gr.
  • This Composition had the following formula const
  • Example 3a Using the same control formulation as in Example 3 above, dimethyl carbonate was substituted for the xylene in the formulation.
  • the replacement solvent composition was as follows:
  • DMC Negligibly Polluting Potential Fluid solvent
  • 29.9% VOC reduction calculated to be 1.95 lb/gal - a very strong VOC reduction which would be difficult to achieve by conventional reformulation.
  • the surface tension, flash point, and evaporation profile were calculated to be:
  • Example 3b Using the same control formulation as in Example 3 above, methyl pivalate (MP) was substituted for the xylene in the formulation.
  • the replacement solvent composition was as follows: MP 29.9 wt. %
  • the Wt. Avg. MIR reactivity was calculated for the solvent composition to be 1.312. Multiplying the MIR by the VOC of 2.78 lb/gal, it is calculated to be 3.65 lbs. of ozone per gal. of solid coating or 63.3% reduction in ozone formation as compared with control composition.
  • LPPF Low Polluting Potential Fluids
  • VLPPF Very Low Polluting Potential Fluids
  • NPPF Negligibly Polluting Potential Fluids
  • VLPPF Very Low Polluting Potential Fluids
  • Example 3c Using the same control formulation as in Example 3 above, the replacement solvent composition substituted DMC for the xylene, DIPC for the MAK, and a partial substitution of Amyl Acetate with DIPC.
  • Example 3d Using the same control formulation as in Example 3 above, the replacement solvent composition substituted MP for the xylene, DIPC for the MAK, and a partial substitution of Amyl Acetate with DIPC.
  • Examples 3c and 3d demonstrate important opportunities to reduce ozone formation through the substitution of high reactivity conventional components of the solvent (fluid) composition exclusively with the Negligibly Polluting Potential and Very Low Polluting Potential fluids from the present invention.
  • an important objective of the present invention is the combinations with other known Low Polluting Potential or Very Low Polluting Potential fluid solvents with Negligibly Polluting Potential, Very
  • HMMM hexamethoxymethylmelamine
  • CymelTM 303 acid (or blocked acid) catalysts
  • This material cannot be effectively substituted with a non-hydroxyl bearing solvent.
  • the alcohol functional components can be substituted with methanol and or isopropanol. These hydroxyl functional components have very low reactivity in atmospheric photochemical ozone formation. Due to the toxicity concerns regarding methanol, the preferred choice is isopropanol.
  • the quantity of the alcohols can vary and needs to be optimized for specific formulations, however, mole per mole ratio can be used as a starting point for optimization.
  • Example 3e Using the same control formulation as in Example 3 above, the replacement solvent composition substituted DMC for the xylene, DIPC for the MAK, a partial substitution of Amyl Acetate with DIPC, and IPA for the N-Butanol.
  • Solvent Composition substituted DMC for the xylene, DIPC for the MAK, a partial substitution of Amyl Acetate with DIPC, and IPA for the N-Butanol.
  • Flash Point Deg. C 38.4 (Deg. F 101.1 )
  • Example 3f Using the same control formulation as in Example 3 above, the replacement solvent composition substituted MP for the xylene, DIPC for the MAK, a partial substitution of Amyl Acetate with DIPC, and IPA for the N-Butanol. Solvent Composition: MP 29.9 wt. %
  • the VOC for the composition is 1.95.
  • Flash Point Deg. C 34.1 (Deg. F 93.4)
  • the data also demonstrates acceptable Evaporation Profile and overall good properties for the coating composition.
  • Example 3g Using the same control formulation as in Example 3 above, the replacement solvent composition substituted acetone, a solvent having an MIR similar to the Negligibly Polluting Potential Fluids of the present invention, for the xylene.
  • Solvent Composition Acetone 29.9 wt. %
  • the data demonstrates an unacceptable flash point reduction and a very fast evaporation rate, up to 50% of evaporation, which makes the solvent composition unacceptable for commercial applications.
  • the VOC of the coating composition is 1.95 lb/gal., which is the same as Examples 3a-3f, but the flash point and evaporation rate prevent the use of the acetone as an acceptable Negligibly Polluting Potential Fluid of the present invention in an industrial application.
  • a cold-cleaning solvent comprising about 10-60 wt% fluorocarbon, about 1-30 wt% of a chlorinated solvent, and about 10-40 wt% of an oxygenated organic solvent is disclosed in U.S. 5,552,080.
  • the oxygenated organic solvent is preferably n-butanol or isopropanol, but may be also selected from numerous other oxygenated organic fluids, including DMC.
  • fluids from to the present invention may be used in the aforementioned cleaning composition to reduce tropospheric ozone formation, which is the opposite phenomenon from ozone depletion. This is completely unexpected.
  • the present invention also contemplate a blend of, for instance, 50/50 n-butanol/DMC or 50/50 n-butanoI/MP, as a cold cleaning solvent useful in reducing ground-based ozone formation. This is a second unexpected result provided by the present invention.
  • the delivery of seed coatings including insecticides and other pesticides, and agents attenuating the growth of plants (e.g., hormones) is extremely valuable to the agricultural industry.
  • OSIT method Organic Solvent Infusion Technique
  • the solvents are generally highly volatile solvents such as xylene, acetone, methylene chloride
  • Fluids with negligibly low MIR reactivity values can be produced using specific chemical compounds (as it demonstrated in literature and in the present invention) and by proper blending with extremely low MIR reactivity organic compounds, preferably methyl acetate and, especially DMC.
  • the blends not only significantly expand the range of negligibly reactive compounds, but also expand the range of properties, and, especially, evaporation profile, which is always significantly wider for blends, than for individual compounds. This is a principal advantage of blends that are deemed Negligibly Polluting Potential Fluids.
  • Negligibly Polluting Potential Fluids of the present invention provide potential for very significant VOC reduction of the typical solvent compositions.
  • reduction of ozone formation with the substitution a part of any solvent with the Negligibly Polluting Potential Fluids of the present invention is disproportionately greater than VOC reduction (-65% versus -30%).
  • the data demonstrate that VOC is a very poor indicator of ozone formation and can provide misleading data concerning actual ozone formation.
  • a first preferred embodiment which is a composition, optionally suitable for a coatings application, comprising at least one fluid, preferably an organic fluid, more preferably a liquid organic fluid, still more preferably a liquid organic fluid which is an oxygenated hydrocarbon, said fluid having a low MIR, preferably similar to or lower than that of acetone and more preferably less than that of ethane.
  • the composition comprises, includes, consists or consists essentially of a fluid selected from: dialkyl carbonates, such as dimethyl carbonate (DMC), methyl ethyl carbonate, methyl isopropyl carbonate, methyl sec-butyl carbonate, methyl t-butyl carbonate, methyl neopentyl carbonate, and diisopropyl carbonate; alkyl acetates, such as neopentyl acetate, ethylene glycol diacetate, 1 ,2-propylene glycol diacetate, 1 ,3-propylene glycol diacetate, 1 ,2-butylene glycol diacetate, 1 ,3-butylene glycol diacetate, 2,3-butylene glycol diacetate, neopentyl glycol diacetate; dioxolanes such as 2,2-dimethyl dioxolane, 2,2,4-trimethyl dioxolane, 2,2,4,5-tetra methyl dio
  • the composition is used in a stationary, non- combustion process, on an industrial scale, said composition also including a second fluid, wherein the second fluid has a high MIR, greater than that of acetone, and more preferably an MIR scale of >1.00; and even more preferably wherein the composition further includes at least one resin and yet still more preferably wherein the composition further comprises a pigment.
  • composition suitable for coating a substrate comprising one of the aforementioned fluids having a low MIR in the first embodiment above, preferably dimethyl carbonate, methyl pivalate, t- butyl pivalate, or a mixture thereof, and at least one solute, wherein the solute is preferably selected from the group consisting of resins, pigments, and mixtures thereof; and optionally also wherein the composition does not contain a halocarbon, more preferably wherein the composition contains less than 1000 ppm of any chlorocarbon or bromocarbon; and also optionally wherein the composition is not used in a combustion process, and also optionally wherein the fluid has at least one of the following attributes: i) an MIR equal to or less than 1.5 gr of ozone produced/gr of fluid solvent; ii) a flash point of at least -6.1 °C, or the even more preferable flash points set forth herein above; iii) a toxicity level wherein oral rat LD50 is better than at least
  • 500 mg/kg i.e. greater than 1000 mg/kg, or more preferably greater than 2000 mg/kg, or the even more preferable toxicity levels set forth above; iv) a low formation of particulates less than 2.5 ⁇ m, where "low formation” is defined as less than 65 micrograms per cubic meter measured over a 24 hour period or more preferably less than 50 micrograms per cubic meter, measure over the same period; and v) an evaporation rate up to12 relative to normal butyl acetate.
  • DMC or methyl pivalate or the mixture thereof is present in an amount sufficient to bring the weight average MIR of a composition to below 1.50 and more preferably below 1.00, yet still more preferably below 0.50, still even more preferably below 0.31 , and in another embodiment wherein the amount of DMC or methyl pivalate is at least 10 percent by volume, more preferably in the amount of more than 25 percent by volume, still more preferably in the amount of at least 50 percent by volume of the organic liquid in the composition, and most preferably wherein the fluid is a paint mixture containing a pigment, or mixture thereof.
  • this preferred embodiment relates to a non-combustion process utilizing a process fluid comprising a first fluid wherein at least some of the first fluid evaporates into the atmosphere, the improvement comprising replacing at least a portion the first fluid with a second fluid selected from dimethyl carbonate, methyl pivalate, or a mixture thereof, thereby decreasing ozone formation from atmospheric photochemical reactions; and also more preferable embodiments including: where the process fluid acts as a solvent, carrier, diluent, surface tension modifier, or any combination thereof, in the process; where the process fluid does not contain a halocarbon; where the decreasing ozone formation is based on a calculation using an MIR scale; where the process is a stationary industrial process; where the replacing results in at least one of the following improvements: i) an MIR at least 10% less than the MIR of the process fluid prior to the replacing; ii) the flash point or a weighted average flash point of the process fluid increasing to above -6.1 °C; iii) a reduced
  • a second preferred embodiment is a method of selecting a fluid system used in an industrial process or for a composition manufactured by an industrial process, comprising selecting at least one fluid having a low OFP as set forth above in the first preferred embodiment, either specifically, e.g., as in DMC, or generally, e.g., with reference to ozone formation, MIR, and the like, preferably having an MIR ⁇ 1.00, , more preferably ⁇ 0.50, still more preferably ⁇ 0.35, and most preferably ⁇ 0.24; and also a second fluid, not having a low OFP, preferably having an MIR>1.00, or in an embodiment selected from hydrocarbon fluids such as toluene and xylenes; alcohols such as methanol, isopropyl alcohol, diacetone alcohol, and sec-butanol; esters such as ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, isoamyl isobutyrate,
  • the improvement comprising decreasing the contribution of the process to ground-based ozone formation by substituting for at least a portion of the fluid used a fluid according to the present invention, and preferably selected from any one or more of the low MIR fluids set forth in the first embodiment above, and even more preferred wherein the final fluid used in the process is a blend as set forth in the second preferred embodiment, and particularly wherein the process is one set forth herein and even more preferably wherein the process is a coating process, an extraction process, a drilling process, or the process is one used to produce a consumer product, such as a pharmaceutical or cosmetic, and preferably wherein the decrease in contribution of the process to ground-based ozone formation is such that the MIR of the process fluid, whether it be a single fluid or blend, decreases from >1.50 to less than or equal to 1.50, more preferably from >1.50 to less than or equal to 1.00, even more preferably from >1.50 to less than
  • a flash point that is higher than that of the system without fluid F
  • a toxicity level that is higher (less toxic) than that of the system without fluid F
  • a formation of particulates having a diameter less than 2.5um (microns) at a density (when measured over a 24-hour period) that is lower than that of the system without fluid F
  • the fluid F being a volatile organic compound containing an oxygen moiety and being substantially free from moieties containing unsaturated carbon-carbon bonds or aromatic groups, and being selected from carbonates, acetates, pivalates, isobutyrates, pentanoates, hexanoates, nonanoates and nitriles.
  • the fluid F has an OFP (measured on the Absolute MIR scale in units of g. ozone/g. fluid ) of (1 ) ⁇ 1.5 or (2) ⁇ 1.0 or (3) ⁇ 0.5 and/or the OFP of the fluid system resulting from use of fluid F has an OFP (Absolute MIR scale in units of g. ozone/g. system) of (1 ) ⁇ 1.5 or (2) ⁇ 1.0 or (3) ⁇ 0.5.
  • the resulting fluid system preferably comprises from (1) 10 to 90 wt. % or (2) 20 to 80 wt. % or (3) 25 to 75 wt. % of fluid F.
  • the property (b) conferred on the system is selected from: i) a flash point that is (1) above - 6.1 °C or (2) above 15°C or (3) above 38°C or (4) above 60°C; ii) a toxicity level that is (on the oral rate LD 50 scale in units of mg/kg) (1 ) > 500 or (2) > 1000 or (3) > 2000 or (4) > 3000 or (5) > 5000; iii) a formation of particulates having a diameter less that 2.5 urn (microns) at a density (when measured over a 24-hour period) that is (1) below 65 mg/m3 or (2) below 50 mg/m3; and iv) an evaporative rate relative to that of n-butyl acetate in the range of (1 ) 5-3 or (2) 3-2 or (3) 2-1 or (4) 1.0-0.3 or (5) 0.3-0.1.
  • a flash point that is (1) above - 6.1 °C or (2) above 15°C or (3) above 38°C or (4) above 60°
  • More than one fluid F may be used.
  • the industrial process e.g., one using more than 500 kg of fluid system per year
  • examples of the industrial process include coating applications, cleaning applications, extraction processes, application of agricultural chemicals, printing ink applications, tackification processes, heat-transfer processes or dissolution processes.
  • Such process may comprise evaporation into the atmosphere of a proportion of the fluid system that is (1 ) > 10% or (2) > 20% or (3) > 50% or (4) > 75% or (5) > 90% or (6) > 99%.
  • fluid F is a compound the hydrocarbyl moieties of which are selected from methyl and/or ethyl and/or isopropyl.
  • fluid F comprises hydrocarbyl moieties which have, collectively, a ratio of methyl hydrogens to non-methyl hydrogens that is (1 ) greater than 1 , or (2) greater than 5 or (3) greater than or equal to 9.
  • an industrial formulation-fluid system comprising one or more organic volatile formulation-fluids including a fluid F being a compound containing an oxygen moiety and being substantially free from moieties containing unsaturated carbon- carbon bonds or aromatic groups, the fluid F being selected from the group consisting of carbonates, acetates, pivalates, isobutyrates, propionates, pentanoates, hexanoates, nonanoates, nitriles and mixtures of any two or more thereof, which fluid F has an ozone formation potential (OFP) (in accordance with the Absolute MIR scale in units of g.
  • OFFP ozone formation potential
  • ozone/g. fluid F ⁇ 1.5 and is present in an amount such that the formulation-fluid system has an OFP that is at least 10% less than that of the formulation-fluid system without fluid F.
  • the amount of fluid F is such that the OFP of the system is (1) at least 25% or (2) at least 50% of the OFP of the system without fluid F.
  • fluid F comprises hydrocarbyl moieties which have, collectively, a ratio of methyl hydrogen to non-methyl hydrogen (1 ) greater than 1 or (2) greater than 5 or (3) greater than or equal to 9.
  • Propionates according to the present invention can be prepared by converting ethylene to propionaldehyde via rhodium catalyzed hydroformylation, and thereafter trimerizing the propionaldehyde via two aldol condensations to form a C 9 product which is hydrogenated to the desired product, e.g., 2,4-dimethyl heptanol.
  • a desired product e.g., 2,4-dimethyl heptanol.
  • Derivatives of propionic acid (CH 3 CH 2 COOH) are readily made via conventional esterification technology.
  • reaction with methanol would provide methyl propionate (CH 3 CH2COOCH3), with ethyl alcohol one obtains ethyl propionate CH 3 CH 2 COOCH 2 CH 3 ), with isopropyl alcohol one obtains isopropyl propionate (CH 3 CH2COOCH[CH 3 ] 2 ), and with n- propyl alcohol one obtains propyl Propionate (CH3CH2COOCH2CH2CH3).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un système de fluide de formulation industriel qui renferme un ou plusieurs fluides de formulation volatiles organiques comprenant un fluide F étant un composé contenant soit un groupe fonctionnel à teneur en oxygène ou en azote et sensiblement exempt de liaisons non saturées carbone-carbone ou de groupes aromatiques. Le fluide F est sélectionné dans le groupe constitué par des carbonates, des acétates, des dioxalanes, des pivalates, des isobutyrates, des pentanoates, des propionates, des hexanoates, des nonanoates, des nitriles et des mélanges d'au moins deux des éléments précités, de façon que le fluide F présente une réduction de formation d'ozone d'une quantité au moins 10% inférieure à celle du présent système sans fluide F. Le fluide F possède en outre un potentiel de formation d'ozone (OFP) (conformément à l'échelle absolue MIR réactivités additionnelles maximales- en unités de g. d'ozone/g. de fluide F) ≤ 1,5.
PCT/US2001/049701 2000-11-10 2001-11-07 Fluides et melanges de fluides respectueux de l'environnement WO2002064687A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2002565009A JP2004528407A (ja) 2000-11-10 2001-11-07 環境的に好ましい流体及び流体ブレンド
KR10-2003-7006394A KR20030084896A (ko) 2000-11-10 2001-11-07 환경적으로 바람직한 유체 및 유체 혼합물
CA002428588A CA2428588A1 (fr) 2000-11-10 2001-11-07 Fluides et melanges de fluides respectueux de l'environnement

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/711,275 2000-11-10
US09/711,275 US6818049B1 (en) 1998-05-05 2000-11-10 Environmentally preferred fluids and fluid blends

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WO2002064687A1 true WO2002064687A1 (fr) 2002-08-22

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018502A2 (fr) * 2000-09-01 2002-03-07 Huntsman Petrochemical Corporation Compositions de degraissage
US6818049B1 (en) 1998-05-05 2004-11-16 Exxonmobil Chemical Patents Inc. Environmentally preferred fluids and fluid blends
EP2964371A4 (fr) * 2013-03-08 2016-09-07 Tbf Environmental Technology Inc Formulations de solvants
WO2017001365A1 (fr) * 2015-06-30 2017-01-05 Shell Internationale Research Maatschappij B.V. Procédé de dégraissage d'une installation chimique
CN114910610A (zh) * 2022-05-16 2022-08-16 华南理工大学 一种基于挥发性有机物损耗测量的臭氧生成潜势评估方法
US11484935B2 (en) 2017-07-18 2022-11-01 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057217A1 (fr) * 1998-05-05 1999-11-11 Exxon Chemical Patents Inc. Fluides et melanges de fluides plus respectueux de l'environnement

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057217A1 (fr) * 1998-05-05 1999-11-11 Exxon Chemical Patents Inc. Fluides et melanges de fluides plus respectueux de l'environnement

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6818049B1 (en) 1998-05-05 2004-11-16 Exxonmobil Chemical Patents Inc. Environmentally preferred fluids and fluid blends
WO2002018502A2 (fr) * 2000-09-01 2002-03-07 Huntsman Petrochemical Corporation Compositions de degraissage
WO2002018502A3 (fr) * 2000-09-01 2003-08-21 Huntsman Spec Chem Corp Compositions de degraissage
EP2964371A4 (fr) * 2013-03-08 2016-09-07 Tbf Environmental Technology Inc Formulations de solvants
WO2017001365A1 (fr) * 2015-06-30 2017-01-05 Shell Internationale Research Maatschappij B.V. Procédé de dégraissage d'une installation chimique
CN107820520A (zh) * 2015-06-30 2018-03-20 国际壳牌研究有限公司 用于去除化学设备的油污的方法
CN107820520B (zh) * 2015-06-30 2019-07-19 国际壳牌研究有限公司 用于去除化学设备的油污的方法
US11484935B2 (en) 2017-07-18 2022-11-01 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers
US11712736B2 (en) 2017-07-18 2023-08-01 Ha-International, Llc Compositions and methods for refractory coatings with ester carriers
CN114910610A (zh) * 2022-05-16 2022-08-16 华南理工大学 一种基于挥发性有机物损耗测量的臭氧生成潜势评估方法

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KR20030084896A (ko) 2003-11-01
CA2428588A1 (fr) 2002-08-22

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