JP2003527446A - Azeotropic and azeotropic compositions of 1-bromopropane and dichloropentafluoropropane - Google Patents

Abstract

  (57) [Summary]   A washing and degreasing solvent containing 1-bromopropane and dichloropentafluoropropane. Preferably, dichloropentafluoropropane is obtained by combining 3,3-dichloro-1,1,1,2,2-pentafluoropropane with 1,3-dichloro-1,1,2,2,3-pentafluoropropane. Consists essentially of a mixture. Washing and degreasing solvents optionally include stabilizers and cosolvents to improve the chemical and physical properties of the washing solvent. Stabilizers and cosolvents include alcohols, ketones, ethers, acetals, nitroalkanes, epoxides, amines, saturated hydrocarbons, alkenes, alkynes and ethers. The solvent composition of the present invention is useful for cleaning a wide variety of products having metal, cloth, ceramic and plastic surfaces.

Description

Detailed Description of the Invention

REFERENCE TO RELATED APPLICATION This application claims priority to co-pending US Provisional Application No. 60 / 052,006 filed Jul. 9, 1997 by Richard J. DeGroot.

FIELD OF THE INVENTION The present invention relates to cleaning solvents containing hydrochlorofluorocarbons and 1-bromopropane, and to methods of cleaning articles with cleaning solvent compositions. More specifically, the present invention relates to dichloropentafluoropropane and 1-
It relates to azeotropic and non-azeotropic cleaning solvents containing bromopropane and to a method for cleaning articles having a metal, plastic, ceramic or cloth surface.

[0003] Continued attempts to background electronic components and electronic circuit board of the invention attempts to miniaturize, are demanded stringent process requirements. Electronic circuit boards are becoming more densely integrated with increasingly sophisticated fine electronic circuits and microchips. These electronic boards and components often require multi-step manufacturing methods. Residues from previous process steps that may adversely affect the performance of subsequent steps or electronic circuits must be removed before the circuit board proceeds to the next processing station. It is important to thoroughly clean the electronic board and included circuits after manufacture to prevent build-up of solder, flux, flux residues, and other particles that adversely affect the functionality of the electronic circuit.

Hydrochlorofluorocarbons (HCFCs) are widely used as cleaning and degreasing solvents for electronic boards and for a wide variety of other products having cloth, plastic, elastomer, metal and ceramic parts or surfaces. Used. HCF
Group C indicates the ability to clean electronic and mechanical parts. Ideally, the wash solvent is non-toxic, environmentally friendly, low boiling, nonflammable, and inexpensive. Furthermore,
To be efficient, the solvent must be such that organic residues, such as flux and flux residues, are present on the circuit board without damaging the circuits and other electronic components present on the board being cleaned. It must have a high degree of solvation ability to dissolve, solubilize and entrain things. The physical and chemical properties of the washing solvent are
Adjust CFCs by mixing with other organic solvents to ensure safe, efficient,
And a solvent having a solvating capacity sufficient to clean the part at a commercially acceptable cost. Certain solvent mixtures may initially provide essentially desirable properties: non-toxic, low boiling point, low cost and high solvating ability, but in practice the mixture may be unsuitable.

Most solvent mixtures are separated during use, especially when the solvent is heated during the washing process or during solvent recovery. That is, the low boiling point components collect in the vapor phase, and the high boiling point components collect in the liquid phase. Separation of the mixture results in a solvent lacking one or more of its components. The solvent does not have the same properties as the original solvent mixture. For example, the solvent often vaporizes the solvent composition in a vapor defluxing or vapor degreasing system when heated to the boiling point. The vaporized solvent condenses on components such as circuit boards that are inserted into the system. When the separation occurs, the composition of the vaporized solvent differs from the liquid solvent in the solvent reservoir. Separation produces a solution that can adversely affect the safety and effectiveness of the wash operation. Thus, it would be advantageous to provide a non-separable solvent to ensure safe and effective cleaning and degreasing operations.

It is also advantageous to minimize separation during solvent recovery to reduce efficiency and degreasing costs. The solvent is often recovered by distilling the used or contaminated solution to provide a substantially pure solvent that can be reused. Separation occurs during recovery, so one or more of the original components must be added to the recovered solvent to maintain the original solvent composition.

Azeotropic mixtures are combinations of solvents that do not separate; they do not separate but exhibit the properties of a single pure compound. Thus, they maintain a constant composition during evaporation or distillation. The azeotropic mixture exhibits a maximum boiling point or a minimum boiling point. These properties are important when solvent compositions are used to remove solder flux and other organic residues from electronic components or greases and oils from mechanical components. Azeotropic mixtures are particularly desirable in vapor degreasing operations where vaporized solvents are used as cleaning solutions. In addition, the azeotropic or azeotrope-like composition allows the solvent to be recovered without the need to add one or more components to maintain the desired solvent composition.

SUMMARY OF THE INVENTION The present invention provides a solvent composition comprising dichloropentafluoropropane and 1-bromopropane. Preferably, the dichloropentafluoropropane is substantially 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3- It consists of pentafluoropropane. 1
A specific solvent composition of -bromopropane and dichloropentafluoropropane is
Provided are azeotropic or azeotrope-like compositions that are particularly useful in steam degreasing and steam defluxing operations. Optionally, the solvent composition comprises stabilizers and cosolvents such as alcohols, ketones, ethers, acetals, nitroalkanes, epoxides, amines, and saturated and unsaturated hydrocarbons. The azeotropic or azeotrope-like composition is determined to be present when the dichloropentafluoropropane, 1-bromopropane, stabilizer and cosolvent are mixed in the specified proportions. A mixture of 1-bromopropane, dichloropentafluoropropane, a stabilizer and a cosolvent is
Provide a cleaning solution with a high degree of solvation, low boiling point and low toxicity.

The present invention also provides a method for cleaning products having cloth, metal, plastic and ceramic surfaces using a solvent composition comprising dichloropentafluoropropane and 1-bromopropane. Optionally, the solvent composition comprises stabilizers and cosolvents to improve stability and the solvating ability of the wash solvent. The solvent can be any of the known or conventional methods used to solvate and carry grease, oil, and other particles adhering to the surface of an article, such as electronic components,
It is applied to articles such as metal products, plastic products, ceramic articles or textiles. Removal of contaminated solvent results in a washed product suitable for further processing or shipping to the consumer.

[0010] DETAILED DESCRIPTION OF THE INVENTION The present invention is a high degree of solvation capability, provides low toxicity, cleaning and degreasing solvents having a low environmental risk and low-boiling, and a dichloropentafluoropropane and 1-bromopropane It relates to a solvent composition. Preferably, the solvent composition is an azeotropic or azeotrope-like composition of dichloropentafluoropropane and 1-bromopropane. However, because the physical and chemical properties of the cleaning solvent can be adjusted by mixing dichloropentafluoropropane and 1-bromopropane in various proportions, the solvent composition is azeotropic and azeotrope-like. In addition to the above substances, those having a concentration of dichloropentafluoropropane and 1-bromopropane are also included. The non-azeotropic solvent composition is useful when solvent separation is not an issue, or when the wash process or solvent recovery does not separate the solvent.

Optionally, the solvent composition comprises one or more stabilizer components and, for example, an alcohol,
Includes cosolvents such as ketones, ethers, acetals, nitroalkanes, epoxides, amines, and saturated and unsaturated hydrocarbons. Preferably, the mixture of dichloropentafluoropropane, 1-bromopropane and one or more of stabilizers and cosolvents provides a solvent composition that is an azeotropic or azeotrope-like composition. The solvent composition prepared in accordance with the present invention provides a cleaning and degreasing solvent that is useful for cleaning a wide variety of articles having fabric, metal, ceramic, plastic and elastomeric surfaces.

For the purposes of the present invention, an azeotropic composition is defined as a constant-boiling liquid mixture consisting of two or more substances which exhibit the physical properties of a single compound, where the liquid partial fraction The vapor produced by evaporation or distillation has a composition that is substantially the same as a liquid (ie, the mixture distills with substantially no change in composition). Constant boiling compositions characterized as azeotrope exhibit either a maximum or minimum boiling point compared to the boiling point of a non-azeotrope of the same material. The present invention contemplates a mixture of dichloropentafluoropropane, 1-bromopropane, and optionally one or more stabilizers and cosolvents in an azeotrope.

By azeotrope-like composition is meant that the composition of the compound has a concentration that can (even if slightly) vary from the concentration found in the azeotrope composition. Thus, the concentrations of dichloropentafluoropropane, 1-bromopropane, and added stabilizers and cosolvents contained in the azeotrope-like composition are those found in the azeotrope formed therebetween. Can be somewhat different and maintain the composition within the scope of the invention. The boiling points of the azeotrope-like compositions are substantially the same as the boiling points of their corresponding azeotrope compositions, preferably, the azeotrope-like compositions are at ambient pressure at their corresponding azeotrope compositions. It boils at a temperature within about 2 ° C. of boiling at the same pressure.

Further, a composition of dichloropentafluoropropane, 1-bromopropane, and additional stabilizers and cosolvents that provides a distillate that is an azeotropic or azeotrope-like composition when fractionated. It is within the scope of the invention even when the concentrations of dichloropentafluoropropane, 1-bromopropane, added stabilizer and cosolvent differ from those of the azeotropic or azeotrope-like composition. Preferably, the concentration of dichloropentafluoropropane, 1-bromopropane, and added stabilizers and cosolvents of the composition is about 10% by weight with respect to the concentration of the azeotropic or azeotrope-like composition. The following, more preferably, differ by less than about 5% by weight.

Solvating ability refers to the property of a composition in its liquid state to dissolve solid or semi-solid substances and yet be miscible with liquids, including gums, greases and gels. At the molecular level, solvation means dispersing molecules of the substance with solvent molecules. Solubility and miscibility need not be complete, ie insoluble or miscible with the material. However, as the amount of solvent composition added to the support is increased by repeated application of a substantially uncontaminated solvent, each increase in the amount of solvent, or each substantially uncontaminated solvent, is increased. It will be appreciated that with continued application of, the solubility of the substance will increase. One method for assessing the solvating ability of a solvent is the Kauri Butanol Val of a hydrocarbon solvent.
ue) to determine the Kauri-butanol number as described in ASTM D1133-94 Standard Test Method.

The solvent composition of the present invention includes an azeotropic composition or an azeotrope-like composition containing dichloropentafluoropropane. Preferably, the dichloropentafluoropropane is substantially 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,
It consists of 3-dichloro-1,1,2,2,3-pentafluoropropane, or a mixture thereof. Dichloropentafluoropropane is commercially available from various sources. 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1
, 3-dichloro-1,1,2,2,3-pentafluoropropane weight ratio 45
: 55 mixture is commercially available from Asahi under the trade name AK 225. Dichloropentafluoropropane is low boiling, non-toxic, non-flammable, and generally chemically stable to most supports.

The solvent composition also includes 1-bromopropane, which is commercially available from Great Lakes Chemical Corporation. This halogenated solvent has a low boiling point, is inexpensive, and is considered to be less harmful to the atmospheric ozone layer than chlorofluorocarbon. Importantly, 1-bromopropane is non-toxic, unlike many other halogenated alkanes. For example, 2-bromopropane is considered to be extremely toxic to both humans and animals. Furthermore, 1-bromopropane is
It has a very high solvation capacity as demonstrated by a Kauri-butanol number of 125.

1-Bromopropane provides an excellent cleaning solvent for metal parts, but its high solvating capacity limits its application for plastics and elastomers: 1-Bromopropane is a plastic surface Tends to erode or partially dissolve. Mixtures of 1-bromopropane with less aggressive solvents such as hydrochlorofluorocarbons counteract this deleterious effect on plastics and elastomers, while at the same time allowing the mixture to solvate the hydrochlorofluorocarbons. Will increase. The final solvent formulation is
It is very effective in cleaning a wide variety of articles having metal, ceramic, cloth and plastic surfaces.

The solvent composition also includes a non-azeotropic composition of dichloropentafluoropropane and 1-bromopropane. Non-azeotropic solvent compositions are useful for certain applications where cleaning solvent separation is not a major consideration. The solvent composition comprises 1-bromopropane and about 1 wt% to about 99 wt% dichloropentafluoropropane, preferably about 10 wt% to about 90 wt%, more preferably about 30 wt% to about 70 wt%. % Included.

The mixture of 1-bromopropane and dichloropentafluoropropane provides a solvent composition with high solvation ability. By choosing the solvent composition well, it is possible to prepare a wash solution with a lower solvating capacity than 1-bromopropane but a higher solvating capacity than dichloropentafluoropropane. The solvent of the present invention is 1
-Bromopropane from about 1% to about 99%, preferably from about 10% to about 9%.
0 wt%, more preferably about 30 wt% to about 70 wt%. The solvent composition of the present invention is about 32 to about 124, preferably about 45 to about 105, more preferably about 65.
A wash solvent having a Kauri-butanol number of about 95 is provided.

Optionally, the solvent composition comprises a stabilizer and a cosolvent. The inclusion of these stabilizers and cosolvents improves the physical and chemical properties of the solvent composition. Stabilizers are added to suppress metal-induced decomposition of halogenated hydrocarbons. Often, reactive metals such as aluminum, magnesium, copper, zinc, iron, titanium, tin and alloys thereof induce decomposition of halogenated hydrocarbons such as 1-bromopropane and hydrochlorofluorocarbons. Typically, these metals induce the hydrolysis and / or dehydrohalogenation of alkyl halides to give metal halides, halide salts and halide acids as some of the degrading species. The production of these decomposed species is harmful to metal parts. Metal bromides, and some of the metal salts, are formed from metal ions extracted from the metal surface, and hydrobromic acid corrodes the metal severely, further exacerbating the problem. Thus, the added stabilizer stabilizes the halogenated solvent in the liquid and vapor states against deterioration in the presence of these metals and inhibits the formation of metal complexes and the formation of decomposition products of the solvent. And suppresses the attack on the metal by the acidic decomposition products of the solvent. Stabilizers included as an optional component of the solvent composition include alcohols, ketones, ethers, acetals, nitroalkanes, epoxides, amines, mixtures of these stabilizers, and the like.

Alcohols that can be added to the solvent include, for example: ethyl alcohol,
Propyl alcohol, isopropyl alcohol, tertiary butyl alcohol, tertiary amyl alcohol, secondary butyl alcohol, phenols such as phenol, p
-Cresol, m-cresol, o-cresol, amino alcohols such as monoethanolamine, diethanolamine, triethanolamine, acetylene alcohols such as methylbutynol, methylpentinol, benzotriazole, and mixtures of alcohols, It is not limited to them.

Typical ketones useful in the present invention include: acetone, methyl ethyl ketone (M
EK), 2-propanone (diethyl ketone), 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2 -Methyl-3-heptanone,
A mixture of 2-methyl-2-butanone, 2-methyl-3-pentanone, 2-nonanone, and various ketones can be mentioned.

Specific ethers that can be added to the stabilized solvent include, for example:
Diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, 1,4-dioxane, 1,3-dioxalane, trioxane, γ-butyrolactone, tetrahydrofuran, dialkyl ether of ethylene glycol, for example, dimethyl ethylene glycol ether, diethyl ethylene glycol. Ethers and monoalkyl ethylene glycol ethers sold under the trade name CELLOSOLVE having 1 to 10 carbon atoms, such as methyl cellosolve, ethyl cellosolve, and isopropyl cellosolve. These ethers are added to the solvent either alone or as a mixture of two or more.

Examples of the acetal suitable for the present invention include dimethyl acetal and diethyl acetal of the above ketones. Typical nitroalkanes useful in the present invention include: nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobutane, and mixtures of nitroalkanes.

Specific examples of epoxides useful in the present invention include, for example: epichlorohydrin, epibromohydrin, propylene oxide, 1,2-butylene oxide, 2
, 3-butylene oxide, cyclohexene oxide, glycidyl methyl ether, glycidyl methacrylate, pentene oxide, cyclopentene oxide, and cyclohexene oxide. The epoxide is added to the stabilizing solvent alone or as a mixture of two or more kinds.

Non-nucleophilic amines are preferred, and secondary and tertiary amines are desirable. By way of example, amines useful in the present invention include: hexylamine, octylamine,
2-ethylhexylamine, dodecylamine, ethylbutylamine, hexylmethylamine, butyloctylamine, dibutylamine, octadecylmethylamine, triethylamine, tributylamine, diethyloctylamine, tetradecyldimethylamine, dibutylamine; diisobutylamine, diisopropylamine, pentyl Amine, N-methylmorpholine, isopropylamine, cyclohexylamine, butylamine, isobutylamine, dipropylamine, 2,2,2
6,6-Tetramethylpiperidine, N, N-dimethyl-p-phenylamine, N
, N-diethyl-p-phenylamine, diethylamine, aniline, ethylenediamine, propylenediamine, triethylamine, tetraethylenepentamine,
Included are benzylamine, dibenzylamine, diphenylamine, and diethylhydroxyamine. These amines are useful alone or as a mixture of two or more kinds.

Cosolvents include, for example: alkanes, alkenes, alkynes, alcohols, ketones, esters, terpenes, as well as various aliphatic mixtures including mineral spirits, VM & P Naaptha solvents and Stoddard solvents. Can be mentioned.
Many of the above stabilizers are also considered to be cosolvents. Cosolvents are added to modify the solvating ability of the solvent composition. Thus, for example, alcohols and ketones can be added to weaken the solvating ability of 1-bromopropane. The cosolvent also provides the solvent with a higher degree of polar and hydrogen bonding properties, thereby
The solvent can effectively remove ionic or polar contaminants. Moreover, these co-solvents are often cheaper than dichloropentafluoropropane, limiting the costs associated with preparing and using solvent formulations.

The solvent composition is prepared by mixing 1-bromopropane and dichloropentafluoropropane in an amount sufficient to provide the desired wash solvent having a particular concentration or desired Kauributanol number. The order of addition of the ingredients is not critical to the invention. Stabilizers and cosolvents are added when desired. In addition, less than half the amount of surfactant can be included. Typical surfactants useful in the present invention include ionic and nonionic surfactants such as sulfonate salts, phosphonate salts, carboxylate salts, fatty acids, alkylphenols, glycols, esters and amides. Surfactants also include ionic and nonionic water-substituted compounds such as tetraalkylammonium sulfonates, phosphates, carboxylates and bromide salts, aliphatic aminoalkanols, fluorinated aminoalkanols, and chlorofluorinated aminoalkanols. Can be mentioned. Also, the order of addition is not critical to the invention.

The solvent composition of the present invention is suitable for cleaning articles having cloth, metal, ceramic, plastic and elastomer surfaces. The solvent composition may be applied by any method known or conventional for cleaning or degreasing products. For example, the surface of the article can be wiped with an absorbent medium containing the solvent composition, eg, a solvent saturated cloth. The product can be submerged or partially submerged in the dip tank. The solvent in the dip tank can be hot or cold and the article can be submerged for a continuous period of time that does not induce decomposition of the solvent. Moreover, the article, dip tank and related parts are intact in the process. Alternatively, the solvent can be sprayed onto or on the article, or the article can be washed in a vapor degreasing chamber having a liquid or vaporized solvent composition.

When the solvent is applied as a vapor, the solvent is typically heated in a solvent reservoir to vaporize the solvent. The vaporized solvent then condenses on the article surface.
The condensed solvent solvates or entrains grease, oil, dirt, and other unwanted particles present on the article surface. The contaminated solvent flows into the solvent reservoir which carries the dissolved and entrained material to the solvent reservoir. Only the solvent evaporates, leaving grease, oil, and dirt in the reservoir. The article is continuously flushed with a non-contaminating solvent.

Hereinafter, the present invention will be further described with reference to examples, but the examples are not intended to limit the present invention. Example 1. Azeotropic composition of dichloropentafluoropropane and 1-bromopropane 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3
-Dichloro-1,1,2,2,3-pentafluoropropane weight ratio 45-
55 dichloropentafluoropropane mixture and a sufficient amount of 1-bromopropane were mixed to obtain a solvent composition of 50% by weight of dichloropentafluoropropane and 50% by weight of 1-bromopropane. The solvent composition was placed in a Perkin Elmer model 151 Annular Still (200 theoretical plate capacity) and heated to reflux. After the refluxing solvent reaches equilibrium,
Three distillate samples were collected at a reflux to takeoff ratio of 10: 1. The sample was analyzed by gas chromatography to determine the relative concentrations of dichloropentafluoropropane and 1-bromopropane. The results are shown in Table 1.

[0033]

[Table 1]

Analysis of the data listed in Table 1 shows that an azeotropic or azeotrope-like composition could be present for the solvent blend of dichloropentafluoropropane and 1-bromopropane. The azeotropic composition is a mixture of 3,3-dichloro-1,1,1,2.
, 2-pentafluoropropane and 9-wt% 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and 7.0 wt% 1-bromopropane Was confirmed and prepared by distillation. The solvent mixture was heated to reflux and allowed to equilibrate. About 10 wt% of distillate fractions were collected using a reflux to withdrawal ratio of 10: 1. Head and pot temperatures were read directly to 0.1 ° C. The results are listed in Table 2. Analysis of the data in Table 2 reveals the presence of the azeotropic composition. The azeotropic composition was mixed 3
, 3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane about 92% by weight, and 1-bromopropane about 8 It consists essentially of wt.% And has a boiling point of about 53 ° C.

[0035]

[Table 2]

Example 2. Dichloropentafluoropropane, 1-bromopropane, and mixed solvents formulation containing two tromethane 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1 , 2,2,3-Pentafluoropropane (weight ratio 45:55) by about 33% by weight, 1-bromopropane by about 33% by weight and nitromethane by about 33% by weight were prepared. About 100 g of the resulting solvent was first distilled in a Perkin Elmer Model 151 Annular Still to determine if a ternary azeotropic composition could be present. Three 10s obtained from this initial distillation
A gram fraction was collected at a reflux to draw ratio of 10: 1. Based on these preliminary results, mixed 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane 75.3g
A solvent blend consisting of 1.2 g of nitromethane and 26.3 g of 1-bromopropane was prepared. This solvent formulation was distilled on a Perkin Elmer Model 151 annular distiller as described in Example 1. The solvent formulation is heated to reflux,
Equilibrated. About 10% by weight distillate fraction was collected at a reflux to withdrawal ratio of 10: 1. Head and pot temperatures were read directly to 0.1 ° C. The results obtained from this distillation are listed in Table 3.

[0037]

[Table 3]

Even when the results listed in Table 3 are analyzed, 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3 -The presence of azeotropic and azeotrope-like compositions consisting of pentafluoropropane, 1-bromopropane and nitromethane is not confirmed. However, dichloropentafluoropropane, nitromethane and 1-bromopropane are co-distilled to provide a solvent formulation that does not significantly concentrate one or more components in the liquid or vapor state.

Example 3. As an azeotropic composition, 3,3-dichloro-1,1,1,2,2-Bae printer fluoro propane and 1,3-dichloro-1,1,2,2,3 Pentafuru Oropuropan, 1-bromopropane , And solvent blends containing methanol 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3
-Dichloro-1,1,2,2,3-pentafluoropropane (weight ratio 45:55
), 33 wt%, 1-bromopropane 33 wt%, and methanol 33 wt% were prepared. Distillation of this first solvent blend was carried out as in Example 1. Based on the results of the initial distillation, mixed 3,3-dichloro-1,1
, 1,2,2-Pentafluoropropane and 1,3-dichloro-1,1,2,2
A second solvent formulation containing 62 g of 3-pentafluoropropane (45:55 weight ratio), 28.3 g of 1-bromopropane and 11.8 g of methanol was prepared.
The solvent mixture was distilled on a Perkin Elmer Model 151 annular distiller.
The solvent formulation was heated to reflux and allowed to equilibrate. About 10% by weight distillate fraction,
Collected at a reflux to withdrawal ratio of 10: 1. Head and pot temperatures were read directly to 0.1 ° C. The results obtained from this distillation are listed in Table 4. When the results in Table 4 are analyzed, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3
It can be seen that there is an azeotropic composition between dichloro-1,1,2,2,3-pentafluoropropane, 1-bromopropane and methanol. This azeotropic composition comprises about 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane mixed. 7
6.9% by weight, 1-bromopropane about 7.2% by weight, and methanol about 11.
It consists essentially of 7% by weight and boils at about 47 ° C.

[0040]

[Table 4]

[0041] Example 4.3,3- dichloro-1,1,1,2,2-pentafluoro propane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1- Azeotropic composition consisting of bromopropane and acetone mixed 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3- A solvent blend containing 33% by weight of pentafluoropropane (45:55 by weight), 33% by weight of 1-bromopropane, and 33% by weight of acetone was prepared and Perkin-Elmer® as described in Example 1. It was distilled using a model 151 / annular still. Based on the results from this initial distillation, the mixed 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-penta 25 fluoropropane
． A second solvent formulation was prepared containing 7 g, 27.0 g of 1-bromopropane and 48 g of acetone. This solvent blend was distilled on a Perkin Elmer Model 151 annular distiller. The solvent formulation was heated to reflux and allowed to equilibrate. About 10% by weight
The distillate fraction of was collected at a reflux to withdrawal ratio of 10: 1. Head and pot temperatures were read directly to 0.1 ° C. The results obtained from this distillation are listed in Table 5. Analysis of the results showed that the mixed 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane were about 14. 4% by weight, about 22.5% by weight of 1-bromopropane and about 65 of acetone
． It can be seen that there is an azeotropic composition having a boiling point of about 56 ° C., consisting essentially of 6% by weight.

[0042]

[Table 5]

[Procedure amendment]

[Submission date] January 14, 2000 (2000.1.14)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

10. Substantially consisting only of said dichloropentafluoropropane, 1-bromopropane and methanol which, when fractionally distilled, provides a fractional distillate which is an azeotropic or azeotrope-like composition, 9. The composition of claim 8 wherein the concentration of said dichloropentafluoropropane, 1-bromopropane and methanol differs from the concentration of said azeotropic or azeotrope-like composition by no more than about 10% by weight.

11. stabilizer composition of claim 7 wherein the C ₃ ~ C ₉ ketones.

12. The dichloropentafluoropropane, 1-bromopropane and ternary azeotropic composition of a ketone or ternary azeotrope-like composition only consisting substantially of composition of claim 11.

Wherein said dichloropentafluoropropane about 11% to
The composition of claim 11 comprising about 36% by weight, about 20% to about 27% by weight 1-bromopropane, and about 45% to about 74% by weight acetone.

14. Substantially consisting only of said dichloropentafluoropropane, 1-bromopropane and acetone which, when fractionally distilled, provides a fractional distillate which is an azeotropic or azeotrope-like composition. 12. The composition of claim 11, wherein the concentration of the dichloropentafluoropropane, 1-bromopropane and acetone differs from the concentration of the azeotropic or azeotrope-like composition by no more than about 10% by weight.

15. stabilizer composition of claim 7, comprising a C ₁ -C ₄ nitroalkane.

16. The dichloropentafluoropropane of about 85% to about 92% by weight, the 1-bromopropane of about 6% to about 16% by weight, and the nitromethane of about 1% to about 7% by weight. 15. The composition according to 15 .

17. A method of cleaning an article, the article comprising 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro having a boiling point of about 54 ° C. 1,1,2,2,3 and dichloropentafluoropropane consisting essentially only of a mixture of pentafluoropropane, said method comprising the step of contacting a solvent composition comprising 1-bromopropane.

18. The solvent composition The method of claim 17 further comprising the dichloropentafluoropropane about 10 wt% to about 90 wt%.

19. solvent composition The method of claim 17 further comprising the dichloropentafluoropropane about 30 wt% to about 70 wt%.

20. The method of claim 17 , wherein the solvent composition further comprises a stabilizer selected from the group consisting of alcohols, ketones, acetals, nitroalkanes, epoxides, amines, ethers and mixtures thereof.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Contents of correction]

[0035]

[Table 2]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SZ, UG, ZW), EA (AM , AZ, BY, KG, KZ, MD, RU, TJ, TM) , AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, D K, EE, ES, FI, GB, GE, GH, GM, HR , HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, L V, MD, MG, MK, MN, MW, MX, NO, NZ , PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, U S, UZ, VN, YU, ZW (71) Applicant Post Office Box 2200,             Highway 52 N.W. W. , West               Lafayette, Indiana             47906, United States o             f America (72) Inventor Degrute, Richard Jay             47906, Indiana, United States             Est Lafayette, Hope Court               2170 F-term (reference) 4H003 BA12 DA02 DA05 DA09 DA12                       DA15 DB02 EB03 EB04 EB12                       ED26 ED28 ED29 ED30 FA16                       FA46                 4K053 PA01 QA04 QA07 RA04 RA08                       RA31 RA32 RA38 RA40 RA41                       RA42 RA45 RA49 RA51 RA52                       RA64 TA13

Claims (21)

[Claims] 1. A mixture of 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane. A solvent composition containing dichloropentafluoropropane and 1-bromopropane. 2. The composition of claim 1, wherein the dichloropentafluoropropane comprises from about 10% to about 90% by weight. 3. The composition of claim 2, wherein the dichloropentafluoropropane comprises from about 30% to about 70% by weight. 4. The composition of claim 1 comprising an azeotropic or azeotrope-like composition of 1-bromopropane and said dichloropentafluoropropane. 5. Dichloropentafluoropropane and 1-bromopropane, which, when subjected to fractional distillation, provide a fractional distillate that is an azeotropic composition or an azeotrope-like composition. The composition of claim 1 wherein the concentrations of fluoropropane and 1-bromopropane differ from those of the azeotropic or azeotrope-like composition by no more than about 10% by weight. 6. The composition of claim 1 comprising 1% to about 12% by weight of 1-bromopropane. 7. The composition of claim 1 further comprising a stabilizer selected from the group consisting of alcohols, ketones, acetals, nitroalkanes, epoxides, amines, ethers and mixtures thereof. 8. The composition of claim 7, wherein the stabilizer is a C _{1 to} C ₅ alcohol. 9. The composition of claim 8 comprising a ternary azeotropic or ternary azeotrope-like composition of said dichloropentafluoropropane, 1-bromopropane, and alcohol. 10. About 56% to about 81% by weight of said dichloropentafluoropropane, about 6% to about 11% by weight of 1-bromopropane, and about 9% to about 29% by weight of methanol. Item 8. The composition according to Item 8. 11. Substantially consisting of said dichloropentafluoropropane, 1-bromopropane and methanol, which, when fractionally distilled, provides a fractional distillate which is an azeotropic or azeotrope-like composition. The composition of claim 8 wherein the concentrations of dichloropentafluoropropane, 1-bromopropane and methanol differ from the concentration of the azeotropic or azeotrope-like composition by no more than about 10% by weight. 12. The composition of claim 7, wherein the stabilizer is a C ₃ to C ₉ ketone. 13. The composition of claim 12 comprising a ternary azeotrope or ternary azeotrope-like composition of said dichloropentafluoropropane, 1-bromopropane and a ketone. 14. The dichloropentafluoropropane in an amount of about 11% by weight.
13. The composition of claim 12, comprising about 36% by weight, about 20% to about 27% by weight 1-bromopropane, and about 45% to about 74% by weight acetone. 15. Substantially consisting of said dichloropentafluoropropane, 1-bromopropane and acetone which, when fractionated, provides a fractional distillate which is an azeotropic or azeotrope-like composition. 13. The composition of claim 12, wherein the concentration of dichloropentafluoropropane, 1-bromopropane and acetone differs from the concentration of the azeotropic or azeotrope-like composition by no more than about 10% by weight. 16. The composition of claim 8 wherein the stabilizer comprises a C _{1 to} C ₄ nitroalkane. 17. The dichloropentafluoropropane of about 85% to about 92% by weight, the 1-bromopropane of about 6% to about 16% by weight, and the nitromethane of about 1% to about 7% by weight. 16. The composition according to 16. 18. A method of cleaning an article, the article comprising 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro having a boiling point of about 54 ° C. A process as described above comprising the step of contacting with a solvent composition comprising dichloropentafluoropropane consisting essentially of a mixture with 1,1,2,2,3-pentafluoropropane and 1-bromopropane. 19. The method of claim 18, wherein the solvent composition comprises from about 10% to about 90% by weight of said dichloropentafluoropropane. 20. The method of claim 18, wherein the solvent composition comprises about 30% to about 70% by weight of said dichloropentafluoropropane. 21. The method of claim 18, wherein the solvent composition further comprises a stabilizer selected from the group consisting of alcohols, ketones, acetals, nitroalkanes, epoxides, amines, ethers and mixtures thereof.