US 20040O86650A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2004/0086650 A1 Behr et al. (43) Pub. Date: May 6, 2004

(54) PERFLUOALKYL HALOALKYL Related U.S. Application Data AND COMPOSITIONS AND APPLICATIONS THEREOF (62) Division of application No. 09/231,203, filed on Jan. 14, 1999, now Pat. No. 6,653,512, which is a division (75) Inventors: Frederick E. Behr, Woodbury, MN of application No. 08/931,105, filed on Sep. 15, 1997, (US); Richard M. Flynn, Mahtomedi, now Pat. No. 6,552,090. MN (US) Publication Classification Correspondence Address: 3M INNOVATIVE PROPERTIES COMPANY (51) Int. Cl." ...... B05D 3/02 PO BOX 33427 (52) U.S. Cl...... 427/384 ST. PAUL, MN 55133-3427 (US) (57) ABSTRACT (73) Assignee: 3M Innovative Properties Company Described are compositions comprising perfluoroalkyl haloalkyl ethers and, optionally, Surfactant; uses for perfluo (21) Appl. No.: 10/689,110 roalkyl haloalkyl compounds and compositions thereof, optionally comprising Surfactant; and perfluoroalkyl (22) Filed: Oct. 20, 2003 haloalkyl ethers. US 2004/0O8665.0 A1 May 6, 2004

PERFLUOALKYL HALOALKYL ETHERS AND substitutes will also be low in toxicity, have no measurable COMPOSITIONS AND APPLICATIONS THEREOF flash points (as determined by ASTM D3278-89), have acceptable thermal and chemical Stability for use in a given CROSS-REFERENCE TO RELATED application, and have short atmospheric lifetimes and low APPLICATION global warming potentials. Many compounds have been proposed as Substitutes for Such chlorinated compounds in a 0001) This is a divisional of U.S. Ser. No. 09/231,203, number of different uses and applications. Still, there filed Jan. 14, 1999, now allowed; which is a divisional of remains a need for chemical compounds capable of replac U.S. Ser. No. 08/931,105, filed Sep. 15, 1997, issued as U.S. ing past commonly used chlorinated compounds and that Pat. No. 6,552,090. exhibit one or more of Such useful chemical or physical 0002 The present invention relates to perfluoroalkyl properties. haloalkyl ether compounds, to compositions containing Such compounds, and to the use of Such compounds and compo SUMMARY OF THE INVENTION Sitions. 0007 Perfluoroalkyl haloalkyl ether compounds have been discovered which can be useful by themselves and in BACKGROUND chemical compositions for purposes including but not lim 0003 Chlorinated chemicals (e.g., chlorofluorocarbons, ited to use as e.g., in cleaning processes Such as dry and hydrochlorofluorocarbons) have been used in the past as cleaning processes, water removal processes, and in coating Solvents within a number of Specialized industrial applica processes. The ethers have a haloalkyl component and a tions. For instance, chlorinated chemicals are known to be perfluorinated alkyl component, and exhibit useful and useful within cleaning applications, including dry cleaning, advantageous properties. These perfluoroalkyl haloalkyl wherein contaminated articles are washed (e.g., immersed in ethers can exhibit, for example, one or more of the following or otherwise contacted) to remove the contaminant. The physical or chemical properties: useful boiling points, high chlorinated chemicals can be used as liquids or vapors, and Solvency, acceptable toxicity properties, chemical and ther at ambient or elevated temperatures (often in cleaning mal Stability, low OZone depletion characteristics, and pref applications accompanied by ultraSonic agitation). Other erably, Substantially no flash point. Additionally, the pres applications wherein chlorinated chemicals are known to be ence of at least one on the haloalkyl component useful include using chlorinated chemicals as coating or allows for degradation of the compound, and reduces its deposition solvents, for the removal of water from Sub long-term presence in the atmosphere. Strates, as a thermal media for heat transfer applications, as 0008 An aspect of the invention relates to a chemical a blowing agent for polymeric foams, as a fire-extinguishing composition containing a perfluoroalkyl haloalkyl ether agent, and as a coolant/lubricant in metal working applica compound and a Surfactant. The perfluoroalkyl haloalkyl tions. compound can be described generally by the formula: 0004. A major concern relating to the use of such chlo R-O-R rinated chemicals is the tendency (especially when used at an elevated temperature) for vapor loss into the atmosphere, 0009 wherein R is perfluoroalkyl and R is haloalkyl. causing pollution. Although care can be exercised to mini Preferred such compounds include those of the formula: mize Such losses (e.g., through good equipment design and vapor recovery Systems), most practical applications result 0010 wherein R is a perfluoroalkyl preferably having at in the loSS of at least Some vapor into the atmosphere. least about 3 , most preferably from about 3 to 15 0005 Popular chlorinated chemicals that have been use carbons, and optionally containing a catenary heteroatom ful in the past (e.g., as cleaning Solvents) include 1,1,2- such as N or O; Xpreferably is from about 1 to 6; y is at least trichloro-1,2,2-trifluoroethane and 1,1,1-trichloroethane. one; W is in the range from 0 to about 2, X is a halogen These are useful alone or in admixture with one or more chosen from bromine, iodine, and ; Z is at least one; co-Solvents Such as aliphatic or other low molecular and W--y+Z is equal to 2x+1. weight polar compounds. These particular chlorinated com 0011) Another aspect of the invention relates to a process pounds were initially believed to be environmentally benign, for removing contaminants from a Substrate. The process but have now been linked to depletion of the earth's ozone. includes the Step of contacting the Substrate with a compo According to the Montreal Protocol and its attendant amend Sition comprising a perfluoroalkyl haloalkyl ether. The per ments, production of Such Solvents has been discontinued in fluoroalkyl haloalkyl ether can be of the formula: the U.S. (see, e.g., P. S. Zurer, “Looming Ban on Production of CFCs, Halons Spurs Switch to Substitutes,” Chemical & R-O-R; Engineering News, page 12, Nov. 15, 1993). 0012 wherein R is perfluoroalkyl and R is haloalkyl. Preferred such compounds include those of the formula: 0006 Thus, there has developed a need for substitutes or replacements for chlorinated chemicals that have been com monly used in the past. Such substitutes should exhibit one 0013 wherein R is a perfluoroalkyl preferably having at or more useful chemical or physical properties including a least about 3 carbons, most preferably from about 3 to 15 low OZone depletion potential, a boiling range Suitable for carbons, and optionally containing a catenary heteroatom cleaning applications, and high Solvency, i.e., the such as N or O; x is from about 1 to 6; y is at least one; w ability to readily dissolve or disperse organic and/or inor is in the range from 0 to about 2, X is a halogen chosen from ganic contaminants, Such as water, hydrocarbon-based com bromine, iodine, and chlorine; Z is at least one, and W-y+Z pounds, and fluorocarbon-based compounds. Preferably, is equal to 2x+1. US 2004/0O8665.0 A1 May 6, 2004

0.014. Yet another aspect of the invention relates to per component, compounds also referred to as perfluoroalkyl fluoroalkyl haloalkyl ethers, including n-CF,OCHCl, haloalkyl ethers (also referred to herein as “the ether” or “the n-CFOCHCl, and those of the general formula: ethers'). These perfluoroalkyl haloalkyl ethers can generally R-O-CHFX, be described by the formula: 0.015 wherein R is a perfluoroalkyl having at least 4 carbons and optionally containing a catenary heteroatom such as N or O; x is preferably from 1 to 2; y is at least one; 0022 wherein Rf is perfluoroalkyl and R is haloalkyl. w can be in the range from 0 to about 2, X is a halogen chosen from bromine, iodine, and chlorine; Z is at least one; 0023 Preferably, the ethers can exhibit one or more and W-y+Z is equal to 2x+1. Specific Such perfluoroalkyl useful chemical and physical properties including a boiling haloalkyl ether compounds include those of the formulas point in the range from about 25 C. to about 200 C., more c-CFOCHFXx - y w1 azs c-CF, CFOCHFXx, y - w/ azs and preferably from about 25 C. to about 125 C.; essentially no CFOCHF.X. Specific compounds include measurable flash point as determined by ASTM D3278-89; CFOCHCl, CFOCHCl, CFOCHBr, CFOCHI, acceptable toxicological properties, and high Solvency. CFOCHCICH, and CFOCHCHCl. 0024. The perfluorinated component R can be any per 0016 Yet another aspect of the invention relates to per fluorinated group able to provide a perfluoroalkyl haloalkyl fluoroalkyl haloalkyl ethers wherein the perfluoroalkyl com ether with one or more useful chemical or physical proper ponent comprises a catenary nitrogen; i.e., wherein the ties as defined herein. Useful Rf groups are described, for perfluoroalkyl component comprises a perfluorinated amine. example, in Assignee's copending U. S. Pat. No. 5,962,390, Ether-containing perfluorinated amines can be generally and incorporated herein by reference. The RF group can be described by the formula: linear, branched, cyclic, or any combination thereof, and can optionally contain one or more catenary heteroatoms Such as 0017 wherein R is a haloalkyl; R and Rare indepen or nitrogen. Examples of preferred Rf groups include dently Straight or branched perfluoroalkyl groups preferably linear or branched perfluoroalkyls having from 3 to about 15 having from 1 to 6 carbons, or are independently Straight or carbons, and perfluorocycloalkyl-containing perfluoroalkyls branched perfluoroalkylene groups preferably having from 2 having from 5 to about 15 carbons. Rf groups containing a to about 4 carbons, the perfluoroalkylene groups being perfluorocycloalkyl group can optionally contain one or bonded to each other to form a ring, and R is a linear or more Substituents, e.g., one or more perfluoroalkyl, the branched perfluoroalkylene preferably having from about 1 substituent preferably having from 1 to about 4 carbons. to 6 atoms, wherein R, R and Rican optionally (and independently) contain one or more catenary heteroa 0025 Examples of R groups comprising a catenary het toms. Preferably R' and R, when perfluoroalkyl, have eroatom include perfluoroamine groupS. Preferred perfluo from 1 to about 3 carbon atoms, and when perfluoroalkylene roamine groups include those represented by the formula have from 2 to 3 carbon atoms; R preferably has from 1 to about 3 carbon atom. Also preferably, R contains from 1 to about 6 carbons, more preferably from about 1 to 2 carbons. 0026 wherein Rf' and R are independently straight or 0.018. As used within the present description when refer branched perfluoroalkyl groups preferably having from ring to the claimed perfluoroalkyl haloalkyl ethers, terms about 1 to 6 carbons, or are independently Straight or will be given the following meanings: branched perfluoroalkylene groups preferably having from 0019 “haloalkyl” refers to an alkyl radical wherein about 2 to 4 carbons, the perfluoroalkylene groups being at least one of the alkyl has been replaced bonded to each other to form a ring; R is a linear or with a halogen chosen from chlorine, bromine, or branched perfluoroalkylene having from about 1 to 6 carbon iodine, atoms; and wherein R, R and Rican optionally (and 0020 “perfluoro-” refers to chemical groups such as independently) contain one or more catenary heteroatoms. alkyl groups in which essentially all of the carbon bonded hydrogen has been replaced by fluorine. 0027 Most preferably, Rf can be a linear or branched Perfluorinated compounds Such as perfluoroalkyl perfluoroalkyl group having from 3 to about 10 carbons, a groups are generally the product of a fluorination perfluorocycloalkyl-containing perfluoroalkyl group having process (e.g. electrochemical fluorination using, for from 5 to about 10 carbons, a perfluorocycloalkyl group example anhydrous HF as a Source of fluorine, or having from about 5 to 6 carbons, or a perfluoroamine group direct fluorination using elemental fluorine) and typi having from 4 to 11 carbons. Perfluorocycloalkyl groups can cally comprise a mixture of one or more perfluoro optionally and preferably be substituted with perfluoroalkyl alkyl isomers and one or more hydride-containing groups, e.g., with one or more perfluoromethyl groups compounds due to incomplete replacement of hydro gen by fluorine. Minor amounts (e.g., less than 5%, 0028 Non-limiting examples of R groups include the or less than 1% by weight) of such residual hydride following: content in the perfluoroalkyl groups are therefore within this definition. DETAILED DESCRIPTION 0021 Compounds of the invention include ether com ()- CF- (CFS)NCF pounds having a perfluoroalkyl component and a haloalkyl US 2004/0O8665.0 A1 May 6, 2004

preferably in the range from 0 to about 2, X is a halogen -continued chosen from bromine, iodine, and chlorine; Z is at least one; CFCFCF and W--y+Z equals 2X+1. 0031 Preferred perfluoroalkyl haloalkyl ethers include a-(r)- CF those described by the formula: R-O-CH,FX, CF-CF-CF 0032 wherein R, X, H, Y, W, X, and Z are as defined. (r)- 0033 Specific such perfluoroalkyl haloalkyl compounds include: ()- (CF) - CF- CF7 CF V CF-CF-CF- CF CF ()- OCHCl2 ()- OCH2Cl CF CF CF V V CF-CF- CF-CF-CF-CF CFOCHCI CFOCHCI CFCFCFOCHCl2 CF CF CF CF CF CF V V CF- CFOCF, CFOCFCF CFCFCFOCH2Cl2 CFCFOCHCl2 CFCFOCHCI CF CF CF CF CFCFCFCFOCHCl2 CFCFCFCFOCH2Cl2 fr–V (CF3)3C- CFOCFOCFCF CF (-)-cate (-)-crocic, CFO(CF) - O F (CF)- n = 14 CF CF CFCFOCHBr CFCFCFCFOCH2Br CFCFOCHI ( F (CF)- n = 14 K F N(CF)- n = 14 CF CF CF V (CF)N(CF)- (CF3)N(CF2)2- (C2Fs)2NCF2CF2 CFCFCFCFOCHI CFCFOCHCICH, CFSNCFCFCF- (CF).NCFCFCF CF CF CFCFCFCFOCHCCH ( F NCFCFCFOCHCl2 O F secret- (CFO)N(CF)- V - or, K F NCFCFCFOCH2Cl / CF CF (CFS)N(CF) c-(e) co V CF CF-CF(CFS)OCHCl2 CF CF-N F N(CF)- O F N(CF)- 0034 Perfluoroalkyl haloalkyl ethers of the invention can be prepared by methods known in the chemical art. AS an CF example, a perfluoroalkyl haloalkyl ether can be prepared by first preparing a perfluoroalkyl alkyl ether, and then halo 0029. The haloalkyl component, R., of the perfluoroalkyl genating the alkyl component to produce a desired perfluo haloalkyl ether can be any alkyl group Substituted with at roalkyl haloalkyl ether. Perfluoroalkyl alkyl ethers can be least one halogen chosen from chlorine, iodine, or bromine, prepared by a number of chemical Synthesis methods gen and at least one hydrogen. Optionally, the haloalkyl group erally known and described in the chemical art. For can also contain one or more fluorines, e.g., from 0 to about example, perfluoroalkyl alkyl ethers can be prepared by 2 fluorines. Preferred haloalkyls include those of the for alkylation of perfluorinated alkoxides prepared by the reac mula: tion of a perfluoro acyl halide (e.g., perfluorinated acyl fluoride or perfluoro acyl chloride), a perfluoroketone, a perfluoro ester, a perfluoro carbonate or a perfluorocarboxy 0030 wherein X is preferably in the range from about 1 lic acid anhydride, with an anhydrous alkali metal fluoride to 6, more preferably from about 1 to 2; y is at least 1; W is (e.g., potassium fluoride or cesium fluoride) or anhydrous US 2004/0O8665.0 A1 May 6, 2004

Silver fluoride in an anhydrous, polar, aprotic Solvent See, such as acetonitrile; alkyl amides such as N,N-dimethylfor e.g., U.S. Pat. No. 3,549,711 (Merrill); U.S. Pat. Nos. mamide, N,N-diethylformamide, and N-methylpyrrolidone; 6,380,419 and 5,750,797. alkyl sulfoxides such as dimethyl sulfoxide; alkylsulfones 0035. According to one reaction scheme, a perfluoro acyl Such as dimethylsulfone, tetramethylene Sulfone, and other fluoride is treated with an anhydrous alkali metal fluoride in Sulfolanes, oxazolidones Such as N-methyl-2-oxazolidone; an anhydrous, polar, aprotic Solvent to generate an interme and mixtures thereof. diate perfluoroalkoxide which is alkylated to produce a 0042 Perfluorinated acyl fluorides can be prepared by perfluoroalkyl alkyl ether. electrochemical fluorination of the corresponding hydrocar bon carboxylic acid (or a derivative thereof), using either anhydrous hydrogen fluoride (Simons ECF) or KF2HF R, COF - KF- (RCFOK' RX 1. - R, CFOR (Phillips ECF) as the electrolyte. Such methods are known in the fluorochemical art. Perfluorinated acyl fluorides and perfluorinated ketones can also be prepared by dissociation of perfluorinated carboxylic acid esters which can be pre 0036). In this scheme, RCF corresponds to Rf as defined pared from the corresponding hydrocarbon or partially above. If desired, a perfluoro acyl chloride, perfluorocar fluorinated carboxylic acid esters by direct fluorination with boxylic acid anhydride, perfluoro ester, or perfluoro carbon fluorine gas. Dissociation can be achieved by contacting the ate may be substituted for the fluoride. R X" is an alkylating perfluorinated ester with a Source of fluoride ion under agent wherein R is a hydrocarbon which can be halogenated reacting conditions (see U.S. Pat. No. 3,900,372 (Childs), to produce the above-defined haloalkyl R., and X is a the description of which is incorporated herein by refer leaving group which can be, for example, an alkylsulfate, ence), or by combining the ester with at least one initiating alkyl fluoroSulfate, a halide, alkyl Sulfonate or alkyl tosylate. reagent Selected from the group consisting of gaseous, Examples of Suitable alkylating agents include dialkyl Sul non-hydroxylic nucleophiles, liquid, non-hydroxylic fates (e.g., dimethyl Sulfate), alkyl halides (e.g., methyl nucleophiles, and mixtures of at least one non-hydroxylic iodide), alkyl p-toluenesulfonates (e.g., methyl p-toluene nucleophile (gaseous, liquid, or Solid) and at least one Sulfonate), alkyl perfluoroalkanesulfonates (e.g., methyl per Solvent which is inert to acylating agents. See also U.S. Pat. fluoromethaneSulfonate), methyl fluorosulfate, and the like. No. 5,466,877 (Moore), incorporated herein by reference. 0037. In a second reaction scheme, a perfluoroketone can 0043 Perfluoroalkyl alkyl ethers can be halogenated, be converted to a desired perfluoroalkyl alkyl ether. The e.g., chlorinated, by methods generally known in the chemi perfluoroketone is reacted with anhydrous alkali metal fluo cal art, to produce a perfluoroalkyl haloalkyl ether. For ride to generate an intermediate Secondary perfluoroalkOX instance, perfluoroalkyl alkyl ethers can be chlorinated by ide which is alkylated to produce a perfluoroalkyl alkyl photochemical methods, by irradiating the perfluoroalkyl ether. alkyl ether with ultraviolet (UV) radiation in the presence of gaseous chlorine. An example of Such a reaction shown for i-CFOCH, is as follows: RCOF" RR"CFOR CEgOCCl3 0044) Different amounts of each reaction product will be 0038. In this scheme R-X" is as defined, and RF and R." present depending on a number of factors involved in the are independently perfluoroalkyl groupS. Such that R and reaction, e.g., reaction conditions and relative amounts of R" preferably have in combination 3 to 15 carbons. each reactant. Such methods are described, for example, in RR"CF corresponds to Rf as defined. U.S. Pat. No. 3.962,460 (Croix et al.). 0039. Alternatively, a fluorinated tertiary can be 0045 According to another halogenation method, chlo allowed to react with a base, e.g., potassium hydroxide or rination of a perfluoroalkyl alkyl ether can be accomplished , to produce a perfluorinated tertiary alkOX using a free radical catalyst Such as 2,2-azobisisobutyroni ide which can then be alkylated by reaction with alkylating trile (AIBN, available from Aldrich Chemical). In such a agent. System the free radical catalyst is believed to decompose to produce one or more free radicals which react with elemen tal chlorine to give a chlorine radical (Cl). The chlorine radical abstracts hydrogen from a perfluoroalkyl alkyl ether to yield an ether radical, which in turn reacts with a molecule of elemental chlorine to yield a new chlorine radical and a 0040. In this scheme R-X" is as defined, and Rf, R.", molecule of perfluoroalkyl chloroalkyl ether. and R" are independently perfluoroalkyl groups Such that 0046) The chlorine of a perfluoroalkyl haloalkyl ether can R, R", and R" preferably have in combination, 3 to 15 be replaced with a different halogen, e.g., bromine or iodine, carbons. RR"R"C corresponds to Rf as defined. to convert the perfluoroalkyl chloroalkyl ether to an analo 0041) Suitable anhydrous, polar, aprotic solvents for use gous perfluoroalkyl bromo- or iodoalkyl ether. Such meth in the above reaction Schemes include acyclic etherS Such as ods of replacing a chlorine with bromine or iodine are very diethyl ether, ethylene glycol dimethyl ether, and diethylene well known in the organic chemistry art, Such as with the glycol dimethyl ether; carboxylic acid esterS Such as methyl Finkelstein reaction, (H. Finkelstein, Ber. 43 1528 (1910)). formate, ethyl formate, methyl acetate, diethyl carbonate, 0047 The perfluoroalkyl haloalkyl ethers can be useful propylene carbonate, and ethylene carbonate; alkyl nitriles and can be used either alone or within a chemical compo US 2004/0O8665.0 A1 May 6, 2004

Sition in admixture with one or more other ethers or other flash point. Of course the exact amounts of ether and ingredients Such as Surfactant, co-Solvent, or both. co-Solvent will depend on many factors, including the Spe cific application for which the composition is intended, the 0.048 Suitable surfactants include those surfactants that identity of each of the ether and the co-Solvent, the presence are compatible with (e.g., Soluble or dispersible in) the ether of other ingredients Such as a Surfactant, etc., and even the to a useful degree. Although the particular Surfactant chosen operating conditions under which the composition is will depend on the desired application, useful Surfactants expected to be used. Still, by way of Specific example, generally will affect one or more of the Surface tension, preferred cleaning compositions include from about 50 to 99 wetting ability, and/or HLB of the composition. In cleaning parts by weight perfluoroalkyl haloalkyl ether per 100 parts applications, preferred Surfactants can promote removal of a by weight of combined ether and co-Solvent, with a pre contaminant by dissolving, dispersing or otherwise displac ferred amount of ether per cosolvent being from about 75 to ing the contaminant. 99 parts by weight ether per 100 parts by weight of com 0049. One useful class of surfactants includes nonionic bined ether and co-Solvent. Surfactants, especially those having a hydrophilic-lipophilic balance (HLB) of less than about 14. Examples include 0053. The cleaning process of the invention can be ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated accomplished by contacting a contaminated Substrate with fatty acids, alkylaryl Sulfonates, glycerol esters, ethoxylated the above-described ether or a composition comprising the fluoroalcohols, and fluorinated Sulfonamides or carboxam ether, to disperse, dissolve, or otherwise displace contami ides. Mixtures of Surfactants having complementary prop nants. AS used herein, the term “contaminant generally erties may be used in which one Surfactant is added to a refers to any matter contacting a Substrate, that can be cleaning composition to promote oily Soil removal and desirously displaced from the Substrate, at least in part, by contact with one or more of the above-identified ethers or a another added to promote water-Soluble Soil removal. composition containing Such ether. For example, contami 0050. The Surfactant, if used, can be present in a com nants generally include materials. Such as light hydrocarbon position in any amount considered to be effective for a Substances, higher molecular weight hydrocarbon Sub desired application. Generally, Surfactant can be present in stances Such as mineral oils and greases, fluorocarbon an amount leSS than about 10 weight percent of the compo Substances including perfluoropolyethers, bromotrifluoroet Sition, and is preferably present in a range from about 0.1 to hylene oligomers (gyroscope fluids), chlorotrifluoroethylene 5.0 wt.%, more preferably from about 0.2 to 2.0 wt.% of oligomers (hydraulic fluids, lubricants); Silicone oils and the composition. greases, Solder fluxes; particulates; Soils, Substances, or 0051 A co-solvent can be included in the composition to materials that can accumulate on leather, Silk, fabrics as modify or enhance the physical or chemical properties of the prepared into clothes, and other fiber and textile Substrate composition, including Solvency and flash point, for a par materials, and other Such Substances. ticular use. Useful co-Solvents include alcohols, ethers, 0054 The substrate can be of any nature and composi including cycloalkanes, alkenes, perfluorocarbons, tion, and can be inorganic or organic. Representative perfluorinated tertiary amines, perfluoroethers, esters, examples of useful Substrates include metals, ceramics, ketones, aromatics, siloxanes, hydrochlorocarbons, hydro glass, polycarbonate; polystyrene; acrylonitrile-butadiene chlorofluorocarbons, and hydrofluorocarbons. Representa Styrene copolymer, Synthetic nonwoven materials, natural tive specifically useful examples of co-Solvents which can fibers (and fabrics derived therefrom) such as cotton, silk, be used in combination with the ether within a cleaning fur, Suede, leather, linen, and wool, Synthetic fibers (and composition include , ethanol, isopropanol, t-butyl fabrics) Such as polyester, rayon, acrylics, nylon, and blends alcohol, isobutyl alcohol, methyl t-butyl ether, methyl thereof, fabrics comprising a blend of natural and Synthetic t-amyl ether, 1,2-dimethoxyethane, cyclohexane, 2,2,4-tri fibers, and composites of the foregoing materials. methylpentane, n-decane, terpenes (e.g., a-pinene, cam phene, and limonene), trans-1,2-dichloroethylene, methyl 0055. In a general sense, the cleaning process of the cyclopentane, decalin, methyl decanoate, t-butyl acetate, invention is accomplished by contacting a Substrate with a ethyl acetate, diethyl phthalate, 2-butanone, methyl isobutyl composition containing a perfluoroalkyl haloalkyl ether ketone, toluene, p-chlorobenzotrifluoride, trifluorotoluene, (either alone or in admixture with other ingredients), to hexamethyl disiloxane, octamethyl trisiloxane, perfluoro displace a contaminant. The composition can be used in hexane, perfluoroheptane, perfluorooctane, perfluorotributy either the gaseous or the liquid State (or both), and with any lamine, perfluoro-N-methyl morpholine, perfluoro-2-butyl of the known techniques for contacting a Substrate to a Oxacyclopentane, methylene chloride, chlorocyclohexane, cleaning composition. For example, a liquid cleaning com 1-chlorobutane, 1,1-dichloro-1-lifluoroethane, 1,1,1-trif position can be sprayed or brushed onto the Substrate, a luoro-2,2-dichloroethane, 1,1,1,2,2-pentafluoro-3,3-dichlo gaseous cleaning composition can be blown acroSS a Sub ropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3- Strate, or a Substrate can be immersed in either a gaseous or dihydroperfluoropentane, 1,1,1,2,2,4-hexafluorobutane, a liquid composition. Optionally, elevated temperatures, 1-trifluoromethyl-1,2,2-trifluorocyclobutane, 3-methyl-1,1, ultraSonic energy, and/or agitation can be used to facilitate 2,2-tetrafluorocyclob 1-hydropentadecafluoroheptane, 1,3- the process. Various different Solvent cleaning techniques bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)ben are described by B. N. Ellis in Cleaning and Contamination Zene, and bromopropane. of Electronics Components and Assemblies, at pages 182-94 0.052 Co-solvent can be included in the composition in (1986). any useful weight ratio (as defined by the weight of the ether 0056 Specific applications of the process exist wherein to co-solvent), and can preferably be included in an amount certain contaminants can be displaced or cleaned from Such that the resulting composition exhibits essentially no particular Substrates. As a first example, the composition and US 2004/0O8665.0 A1 May 6, 2004 proceSS can be useful in the precision cleaning of electronic ropolyether, hydrocarbon, and Silicone lubricants, amor components (e.g., circuit boards), optical or magnetic media, phous copolymers of tetrafluoroethylene; and medical devices. To displace water from a Substrate Such polytetrafluoroethylene, and combinations thereof as a circuit board the cleaning process can be carried out by contacting the Surface of the Substrate with a liquid cleaning 0061 The coating substrate can be any of the substrates composition which preferably contains a non-ionic Surfac described above for cleaning applications, or it can be any tant. The Wet Substrate is immersed in the liquid composition other type of natural or Synthetic Substrate, e.g., in the form and agitated therein, the displaced water is separated from of a film, a non-woven material, or any other material the liquid composition, and the resulting water-free Substrate desired to be coated with a coating material. The coating is removed from the liquid composition. Further description process can be particularly useful for coating magnetic hard of these types of processes, and the Substrates that can be disks or electrical connectors with perfluoropolyether lubri treated, are described in U.S. Pat. No. 5,125,978 (Flynn et cants, or medical devices with Silicone lubricants. al.) and in U.S. Pat. No. 3,903,012 (Brandreth), the descrip 0062) To form a coating composition the components of tions of which are incorporated herein by reference. the composition (i.e., the ether, the coating material, and any co-dispersant or co-solvent) can be combined by any con 0057. As another specific application, the process is ventional mixing technique used for dissolving, dispersing, particularly useful in the Solvent-type processes of cleaning or emulsifying coating materials, e.g., by mechanical agita fabric and garments, etc., including the process generally tion, ultraSonic agitation, manual agitation, and the like. The known as dry cleaning. According to Such process, contami components can be combined in any ratio depending upon nants can be removed from fiber and textile Substrates. This the desired thickness of the coating, but the coating material type of cleaning proceSS can be carried out by contacting the preferably constitute from about 0.1 to about 10 weight fiber or textile with the composition at ambient or elevated percent of the coating composition for most coating appli temperatures. The contaminated Substrate can be agitated to promote the dissolution, dispersion, or displacement of Soil cations. contaminants using any conventional agitation means 0063. The coating process can be carried out by applying including Shaking, Stirring and ultraSonic agitation. When the coating composition to a coating Substrate using any the textile is Sufficiently cleaned, the composition may be conventional technique. For example, the composition can removed (e.g. by decantation), the textile optionally rinsed be brushed or sprayed (e.g., as an aeroSol) onto the Substrate, using fresh cleaning composition or any conventional dry or the substrate can be spin-coated. Preferably, the substrate cleaning Solvent to ensure Soil removal and prevent rede is coated by immersion in the composition. Immersion can position, and the textile can be dried, for example, by be carried out at any Suitable temperature and can be air-drying with or without added heat. maintained for any convenient length of time. 0.058. The perfluoroalkyl haloalkyl ethers can be useful not only in cleaning applications, but also in coating depo EXAMPLES Sition, where the ether functions as a carrier for a coating 0064 All compounds prepared have had their structures material to enable deposition of the coating material on the confirmed by gc-ms and H and 'F nmr as appropriate. Surface of a Substrate. The invention thus also provides a coating composition and a process for depositing a coating Examples 1 on a Substrate Surface. 0059. The coating process comprises the step of applying Preparation of n-CF,OCH2Cl and n-CF,OCHCl to at least a portion of a coating Substrate a coating (e.g., in the form of a film) of a liquid coating composition com 0065. A 500 mL flask equipped with a magnetic stir bar, prising (a) a perfluoroalkyl haloalkyl ether according to the gas inlet tube, condenser, and thermometer was charged with description above, and (b) at least one coating material CF,OCH (158 g., 0.79 mole). The flask was illuminated which is soluble or dispersible in the composition. The with two fluorescent bulbs (BLAK-RAYTM, 254 nm), as an coating composition can further comprise one or more initial aliquot of chlorine gas (~3.5 g) was passed through a co-dispersants or co-solvents (as defined Supra, preferably gas trap into the flask. After a short initiation period, the those having boiling points below about 125 C.) and/or one evolution of HCl was noted and the temperature slowly or more additives (e.g., Surfactants, coloring agents, Stabi increased. A total of 56.1 g (0.79 mole) chlorine was added. lizers, anti-oxidants, flame retardants, and the like). Prefer When conversion was essentially complete, as measured by ably, the process further comprises the Step of removing the gas chromatography, the reaction mixture was washed with ether and optional co-Solvent from the coating by, e.g., acqueous KOH and then brine. allowing evaporation (which can be aided by the application 0066 Gas liquid chromatography revealed the following of, e.g., heat or Vacuum). composition of the product mixture: unreacted Starting mate 0060 Coating materials which can be deposited by the rial n-CFOCH (6% area percent), n-CFOCHCl (66%) proceSS include pigments, lubricants, Stabilizers, adhesives, and n-CFOCHCl (27%),and n-CFOCC1 (1). Unless anti-oxidants, dyes, polymers, pharmaceuticals, release otherwise Specified, all Such chromatography percents are in agents, inorganic oxides, and the like, and combinations area percent. thereof, examples include titanium dioxide, iron oxides, 0067. The product mixture was distilled through a con magnesium oxide, perfluoropolyethers, polysiloxanes, centric tube fractionation unit (available from Ace Glass) to Stearic acid, acrylic adhesives, polytetrafluoroethylene, remove the Starting material. The residue was then distilled amorphous copolymers of tetrafluoroethylene, and combi through a 36 inch spinning band distillation column (avail nations thereof. Preferred coating materials include perfluo able through B/R Instrument Corporation) and US 2004/0O8665.0 A1 May 6, 2004 n-CFOCHCl (purity of 99.5%, b.r.=59.4-59.8 °C.) and liquid (21.2 g) after separation of the lower aqueous phase FOCHCl, (purity of 99.5%, b.p. =67.7 °C.) was iso and washing with water. This liquid was distilled using a ated. concentric tube column to yield a fraction boiling at 96-97 C., which was revealed by gle to be 97.1 wt.% of the desired Example 2 compound, CFOCHBr (14.2g, 67% yield). The structure was confirmed by gc-ms and H and 'F NMR, which Preparation of CFOCH2Cl and CFOCHCl determined that the isomer ratio was about 96/4 normal to 0068. Using essentially the procedure of Example 1, iso-CF. CFOCH (701.5g, 2.81 mole of approximately 69/31% iso Example 6 to normal ratio) was contacted with chlorine gas (199.2g, 2.81 mole) over a period of about four hours under photo 0073. Using essentially the procedure of Example 1, chemical illumination. AS before, the ether was contacted perfluorocyclohexylmethyl methyl ether, c-CFCFOCH, with an initial aliquot of about 10 g chlorine gas and containing Several other compounds, predominately perfluo illuminated until the color of the chlorine gas had vanished romethylcyclopentyl isomers, (134g, 0.37 mole) was con before proceeding with the rest of the addition. tacted with chlorine gas under UV illumination. Total chlo rine was 26.3 g (0.37 mole). The reaction mixture was 0069 GLC at the conclusion of the addition showed the washed with aqueous KOH, water, and the dried over following: CFOCH (5%), CFOCHCl (65%) and NaSO, to yield 147g of product mixture. This was distilled CFOCHCl (29%) and C.F.OCHCl, (0.2%) The reaction to give a main cut of 141-142 C., which was determined by Solution was washed first with dilute aqueous potassium gems, H and 'F NMR to be a mixture of 73% cyclohexyl hydroxide, and then with water, and distilled using a and 23% methylcyclopentyl isomers and containing both 40-plate perforated plate column to yield CFOCHCl, monochloro and dichloro ethers with a ratio of mono to b.p.-87° C. and CFOCHCl, b.p. =96° C. in purities of dichloro isomers of 70/30. about 99%. Example 7 Example 3 Preparation of CFOCHCCH Preparation of a Mixture of CFOCH2Cl and 0074. Using essentially the procedure of Example 1, CFOCHF CFOCH-CH (131.2g, 0.5 mole, isomer ration/i=95:5) 0070 A pressure vessel was charged with CFOCHCI was contacted with chlorine gas (35.3 g, 0.5 mole) under UV (75 g, 0.26 mole, isomer ratio i?n=69:31), potassium fluo illumination. The reaction mixture was washed with aque ride (16.8 g., 0.29 mole) and phase transfer catalyst ous KOH and dried over NaSO to yield 140.1 g of clear AdogenTM 464 (7 g, methyltrialkyl-C8 to C10 ammonium liquid. The product was distilled using a concentric tube chloride available from Aldrich Chemical Company), in column to give a main fraction boiling at 94 C. to yield the anhydrous diglyme (150 g) and was heated to 150° C. for desired compound CFOCHCICH (97% purity, 65% yield Slightly more than four hours. The reactor was cooled, water with a normal to iso ratio of 94/6). The structure was was added, and the contents azeotropically distilled to yield confirmed by gc-ms, H and 'F NMR. In addition to the 49.6 grams of reaction product. The reaction product was desired product, NMR of a fraction boiling at 113-115 C. determined by gle to be a mixture of Starting material was found to contain CFOCHCHCl, CFOCCICH, CFOCHCHCl, and C.F.OCHCICH.Cl in the ratio of (68.5%) and the monofluoride (26.9%). 49/35/5/11. Four other chlorinated products were identified Example 4 comprising the remainder of the Sample. Example 8 Preparation of CFOCHI 0071) CFOCHCl (50 g, 0.175 mole, isomer ration/i= Preparation of CFOCH2Cl and CFOCHCl 95:5) was combined with sodium iodide (52.5g, 0.38 mole) Using Free Radical Initiator in acetone (200 g) and heated to reflux overnight. Water was 0075 A flask equipped with a dry ice condenser, added and the acetone distilled from the reaction vessel mechanical Stirrer, gas inlet and thermometer was charged using a Dean-Stark apparatus. The product was washed with with CFOCH (666 g., 3.33 mole, approximately 9:1 iso to water to remove residual acetone. Glc of the residue (52.6 g) normal) and VAZO 64TM (4 g). The mixture was heated to revealed it to be 82.6 wt. % of the desired product 60° C. and chlorine bubbled through the stirred solution in CFOCHI, which was further purified by distillation. The small portions. After the addition of 147 g of chlorine, an distillation fraction boiling at 110-115 C. was found to be additional 1 gram of VAZO 64TM was added and heating 97.8 wt.% of the desired product with a 96/4 normal to iso continued. The reaction mixture was then washed with water ratio. and aq. KHCO, and dried over NaSO. GLC of the product mixture revealed CFOCH (24%), CFOCHCl (62.5%) Example 5 and CFOCHCl (10.3%) Preparation of CFOCHBr Example 9 0072 CFOCHI (31.2g, 0.081 mole, Example 5) was Preparation of c-CFON(CF).OCH2Cl and combined with LiBr in anhydrous dimethyl formamide (100 c-CF, N(CF),OCHCl, mL) and stirred at room temperature overnight. Water was 0076. The starting material for the chlorination reaction added and the product azeotropically distilled to yield a clear was prepared according to the procedure described in PCT US 2004/0O8665.0 A1 May 6, 2004

published application No. WO 96/22356, Example 4. The reaction mixture is gently heated until the ether chloride Starting material was a mixture of perfluoropiperidinyl begins to distill from the reaction mixture. The nonafluo (83%); perfluoro-3-methylpyrrolidinyl (9.3%) and per robutaneSulfonates are prepared by reaction of the corre fluoro-2-methylpyrrolidinyl (4.2%) with 3.8% ring-opened sponding alcohol with nonafluorobutaneSulfonyl fluoride in aminoether. The remaining 1% were hydride containing the presence of triethylamine as described in Savu, U.S. Pat. materials. Using the procedure of Example 1, perfluoropi No. 5,550,273 the disclosure of which is herein incorporated peridinylpropyl methyl ether (composition noted above) (28 by reference. In this manner the following ether chlorides g=62.9 mmole) was reacted with chlorine (20g, 281.7 were prepared. mmole, excess) added in aliquots of about four grams each in the presence of VAZO-64TM (about 0.2 g) at 60° C. The 0080 CFOCFCH.C. B. P=55-56° C. reaction was monitored by gle until the Starting material was 0081) CFO(CFO)CFCHCl B. P=62 C. reduced to about 6% of the reaction mixture. The product was washed with water and distilled using the concentric 0082 CFOCFOCFCHCl B. P=164-6° C. tube column to afford a product of bp=167° C. "H and 'F NMR revealed the distilled product to be a 70/30 mole ratio Solvency Properties of mono to dichlorides. 0083) A number of ethers were tested for their ability to dissolve hydrocarbons of increasing molecular weight, Example 10 according to the procedure described in U.S. Pat. No. 5,275,669 (Van Der Puy et al.), the description of which is Preparation of 2-Trifluoromethyl 3-Chloromethoxy incorporated herein by reference. The data shown in the Perfluoropentane and 2-Trifluoromethyl following table were obtained by determining the largest 3-Dichloromethoxy Perfluoropentane normal hydrocarbon which was Soluble in a particu 0077. The starting material, CFCOCF(CF), was pre lar ether at a level of 50 percent by volume (i.e., 50% by pared by the method of Smith et al. J. Am. ChemSoc. 84 volume hydrocarbon was dissolved in 50% by volume 4285 (1962) using hexafluoropropylene and pentafluoropro ether). The numbers in the Table correspond with the carbon pionyl fluoride. A mixture of 2-trifluoromethyl-perfluoro-3- number of the largest Soluble alkane, e.g., “8” refers to pentanone (105.3 gms. 0.333 moles) in anhydrous diglyme octane. Measurements were taken at room temperature and (220gms), anhydrous potassium fluoride (27.1 gms, 0.467 at the boiling point of the ether. The following table sum moles), Adogen TM464(7 gms) and dimethyl sulfate(46.2 marizes the physical properties and Solvency data. gms, 0.37 moles) was heated overnight at 45° C. Upon completion of the reaction, the mixture was cooled and aqueous potassium hydroxide was added slowly to the HC Solvency Ozone reaction mixture and Stirred for 1 hr at ambient temperature. Number at RT Depletion The pH was found to between 6 and 7. The mixture was Compound Boiling Point and BP Potential heated to azeotropically distill the product from the reaction CFOCHCI 59.6°C. 15/20 O.O13 mixture. The product (CFCF(OCH)CF(CF), (91.6 gms) CFOCHCl, 67.7°C. 17/>28 O.O24 was collected and analyzed using gle (97% purity) and used i-CFOCHCI 87° C. 13/21 in the Subsequent chlorination reaction without further puri i-CFOCHCl, 96° C. 17/>28 c-CFCFOCH2Cl and 141-142 C. 12f fication. c-CFCFOCHCl, i-CFOCHBr 97° C. 17f- O.21 0078 Into a 100 ml three-necked round bottom flask i-CFOCHI 113° C. equipped with a Dry Ice-isopropanol condenser, thermom i-CFOCHCCH 94° C. 15/- eter, and inlet gas tube was placed 44 gms of 2-trifluorom c-CSFN(CF).OCH2Cl and 144-147 C. 10f ethyl 3-methoxy perfluoropentane along with a Small c-CSFN(CF).OCHCl, amount of VAZO 64TM (approx 0.1 gms). The mixture was (70:30) degassed with dry nitrogen and heated to 70° C. while CFOCFCH.Cl 55-56° C. 8f gaseous chlorine was introduced through the fritted glass gas CFO(CFO)CFCH.Cl 62° C. 8f inlet. A Sample was taken after 5 gms of chlorine had been * 69% iso-CF and 31% in-CF ° Obtained as a mixture of 73% cyclohexyl and 23% methylcyclopentyl added and was determined by gc/ms to be the Starting isomers with a ratio mono to dichloro isomers of 70/30. material and 17% of the desired 2-trifluoromethyl 3-chlo * Ozone Depletion Potential is described in Scientific Assessment of romethoxy perfluoropentane. Continued addition of chlorine Stratospheric Ozone: Volume 2, Appendix: AFEAS Report, Section VIII, for a theoretical amount of one mole chlorine per mole of Ozone Depletion Potentials (1989). ether gave a mixture of 57% starting material, 37.6% monochloroether and 3.1% dichloroether. The product was isolated by quenching the reaction mixture with water, phase What is claimed is: Separation of the lower product phase, followed by Subse 1. Perfluoroalkyl haloalkyl ethers having the formula: quent washing with Saturated potassium bicarbonate to yield 50.9 gms of a clear colorless liquid. wherein R is a haloalkyl; R and R are independently Straight or branched perfluoroalkyl groups, or, are inde Examples 11-13 pendently Straight or branched perfluoroalkylene 0079 Compounds of the type ROCFCHCl were pre groups bonded together to form a ring; R a linear or pared by reaction of the corresponding nonafluorobutane branched perfluoroalkylene, and R', R., and R can sulfonate (ROCFCHOSOCF) with lithium chloride in optionally and independently contain one or more dimethylformamide as Solvent at elevated temperature. The catenary heteroatoms. US 2004/0O8665.0 A1 May 6, 2004

2. The perfluoroalkyl haloalkyl ethers of claim 1, wherein 5. A proceSS for removing contaminants from a Substrate, R" and R are straight or branched perfluoroalkyl groups the proceSS comprising the Step of contacting the Substrate comprising from 1 to 6 carbons, or are Straight or branched with a composition comprising a perfluoroalkyl haloalkyl perfluoroalkylene groups preferably comprising from 2 to ether of claim 1. about 4 carbons bonded to each other to form a ring, and R. 6. The process of claim 5, wherein the composition further is a linear or branched perfluoroalkylene having from about comprises a Surfactant. 1 to 6 carbon atoms, wherein R, R and Rican optionally 7. A coating process comprising the Steps of applying to and independently contain one or more catenary heteroat a coating Substrate liquid coating composition comprising OS. the perfluoroalkyl haloalkyl ether of claim 1 and at least one 3. Perfluoroalkyl haloalkyl ethers of claim 1, having the coating material which is Soluble or dispersible in the general formula: perfluoroalkyl haloalkyl ether. 8. The process of claim 1 wherein Said coating material is wherein Rf is a perfluoroalkyl, X is in the range from 1 to Selected from the group of perfluoropolyether, hydrocarbon 6; y is at least one; W is in the range from 0 to about 2, and Silicone lubricants. X is a halogen chosen from bromine, iodine, and 9. The process of claim 1 wherein Said coating material chlorine; Z is at least one; and W-y+Z is equal to 2x+1. comprises from about 0.1 to about 10 weight percent of the 4. The perfluoroalkyl haloalkyl ethers of claim 3, having coating composition. the formulas c-CFN(CF).OCH.Cl and c-CSF, N(CF).OCHCl2.