CA2160700A1

CA2160700A1 - Lubricants containing perfluorocyclobutane rings

Info

Publication number: CA2160700A1
Application number: CA002160700A
Authority: CA
Inventors: David A. Babb; Ted A. Morgan
Original assignee: Individual
Current assignee: Dow Chemical Co
Priority date: 1993-04-26
Filing date: 1994-04-19
Publication date: 1994-11-10
Also published as: EP0696309A1; WO1994025547A1; US5364547A; JPH08509765A

Abstract

A new lubricant comprises at least one compound having a perfluorocyclobutane group, preferably a perfluorovinyl aryl ether. The lubricant is conveniently applied from solvents which are not chlorofluorocarbons and is effective at high temperatures for example, in engines and for magnetic media, either internally or topically.

Description

2 i ~ ~ 7 ~ O PCT/US94/04274 LUBRICANTS CONTAINING PERFLUOROCYCLOBUTANE RINGS

The present invention is related to lubricants, more particularly lubricants useful over a large temperature range.
s Demands placed on existing lubricants are currently undergoing significant changes. Engines are being developed for automotive and aeronautic applications that have requirements dramatically different from those of enginescurrently in use. It is anticipated that these engines will operate at temperatures o exceeding 250C. and will be constructed using materiais new or different fromthose currently in use. Thus, lubricants or lubricant additives that are stable at the high use temperatures while possessing the other properties required of lubricants will be needed for these applications.

Additionally, lubricants are needed for magnetic recording media such as high density rigid disks, ultra high density floppy disks, digital audio tapes and video tapes which can be read by a magnetic recording head. In use of these media, a recording head is in very close proximity to the recording media and frequently contacts the recording media. Such contact causes wear of the thin layer of magnetic material on the recording media and shortens the useful life of the recording media. With insufficiently effective lubricants there are problemsincluding increased friction, scratching and adhesion. More efficient internal and boundary lubricant systems would be desirable.

2s Lubricants for magnetic media are known in the art, but such lubricants are generally designed for more mature counter-parts of the magnetic media such as standard audio, VHS video and standard floppy disks. Examples of such Iubricants included are described in U.S. Patent No. 4,613,548 to Lum, issued onSeptember 23, 1986, a normally liquid, low molecular weight linear or cyclic poly-fluoroalkoxy phosphazene mixtures. Such lubricants do not demonstrate solvent compatibility with a wide range of organic solvents and are not stable in water and base. A family of perfluoropolyether difunctional derivatives end capped with planar groups including certain carboxylic acids and esters, perfluoroalkyl ethers, hydroxyalkyl, and certain substituted phenyl groups are commercially available WO 94/25S47 216 0 7 0 ~ PCT/US94/04274 from Ausimont U.S.A., Inc., under the trade designation FOMBLINTM. Certain lubricants having cyclic phosphazenes substituted with fluorinated phenoxy moieties and perfluoroalkylphenoxy moieties are disclosed in U.S. Patent 5,01~,40~. Such lubricants are not stable at high temperatures (for example 5 above 100 C ) in water and base.

Lubricants which comprise fluorocarbon substances or other fluorine-containing compounds are desirable for their superior tribological properties characteristic of fluorine-containing substances. These fluorinated substances, 0 such as the FomblinTM fluids available from Montedison, or the KrytoxTM fluids and waxes available from E.l. DuPont de Nemours Co., are soluble only in Freon or Halon solvents, for example chlorofluorocarbon (CFC) solvents such as FreonTM
112 or FreonTM 114 commercially available from E.l. DuPont de Nemours Co.
Such solvents, however, are subject to regulations based on the Montreal Protocol on Substances that Deplete the Ozone Layer (1987). The term Utribologicalu used to denote substances which modify surface friction and wear properties.

It would be desirable to have a lubricant soluble in non-CFC solvents such 20 as tetrahydrofuran and acetone, yet to maintain the tribological characteristics of known fluorine-containing solvents. The lubricant is also desirably stable in the presence of water, acid and base.

The present invention is directed to lubricating polymers, preferably fluids, 25 advantageously polymeric and oligomeric, preferably dimers and/or polymers thereof, said lubricants being poly(perfluorocyclobutane aryl ether) compounds, and their use as lubricants.

The invention is further directed to lubricants comprising at least one 30 compound having a perfluorocyclobutane group, one or more of the above-described compounds.

WO 94/25!i47 2 1 6 0 7 0 ~ PCT/US94/04274 The compounds and compositions of the present invention are useful as extended temperature lubricants and as lubricants for magnetic media and in engines, particularly high-temperature engines, particularly when exposed to temperatures in excess of 200C.
s The compounds are advantageously soivent compatible, magnetic recording media lubricants. Additionally the lubricants are stable in acids, bases and water and at high temperatures, such as from 35C to 200C.

o The invention includes high density, state of the art recording media, such as high density rigid disks, ultra high density floppy disks, digital audio tape, 8 mm video tape and super VHS tape including a lubricant which may be used as an internal or topical lubricant system to minimize wear and improve overall performance, and to protect the media from damage from the reading and/or writing head of a disk assembly.

The magnetic recording media containing a lubricating amount of lubricants of the invention comprises a substrate; a magnetic recording media thereon which include (a) magnetic particles for recording information; a binder for suspending the magnetic particle and a poly(perfluorocyclobutane aryl ether); or(b) a metallic film for recording information and a poly(perfluorocyclobutane aryl ether) fluid. The media described in (a) is referred to herein as particulate media and in (b), as thin film magnetic media. The lubricants are referred to as internal and topical, respectively.
The lubricant is utilized as a topical lubricant for thin film or non-porous hard and flexible magnetic media advantageously by coating a metallic alloy lamina onto a base polymeric film (for example polyester) and applying the lubricant, preferably as a solution in a volatile solvent, to the surface. Aftersolvent evaporation, a thin lubricant layer is left absorbed or bonded to the recording lamina surface.

Alternatively, the lubricant is utilized in an internally lubricated system by preparing a lubricant containing lamina for application to a recording substrate.

The lamina is advantageously prepared by forming a dispersion of solvent, a pigment containing magnetic particles and a binder system (for example urethane-vinyl). The lamina is then applied to a base film (for example polyester, particularly polyethylene terephthalate polyester).
s This invention additionally includes a method of preparing magnetic media by forming a dispersion comprising a binder, a magnetic particle containing pigment, a lubricating amount of a poly(perfluorocyclobutane aryl ether), and a surfactant; orienting the magnetic particles by application of a magnetic field;o evaporating the solvent; and curing the polymer binder.

Also, the invention includes a method of lubricating magnetic recording media using a composition comprising at least one poly(perfluorocyclobutane arylether) compound.

The invention also includes a process of preparing a lubricating poly(perfluorocyclobutane aryl ether) composition comprising heating, to a temperature of at least 50 C and sufficient to form perfluorocyclobutane ringsfrom perfluorovinyl groups, a mixture of at least one of the following:
(a) monomers having two dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group;
(b) monomers having three or more dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group; or (c) monomers having two or more dimerizable perfluorovinyl groups and end-2s capping agents having one dimerizable perfluorovinyl group.

Recording media containing the lubricant of the present invention advantageously have improved physical and magnetic durabilities from more effective lubrication. Advantageously, there is also processability in manufacturing because the lubricants are solvent compatible in organic solvents such as toluene, acetone ethanol and tetrahydrofuran. This makes the product more practical to produce. Furthermore, the lubricants are advantageously stablein acids, bases and water.

WO 94/25547 ~ I 6 0 7 0 0 PCT/US94/04274 The poly(perfluorocyclobutane aryl ethers (hereinafter lubricant polymers) of the invention are formed by thermal reaction (dimerization) of monomers having at least one dimerizable perfluorovinyl group such that at least one perfluorocyclobutane group is formed. Whereas polyaddition of perfluorovinyl s groups to form perfluoroaliphatic polymers (like polytetrafluoroethylene), notgenerally having perfluorocyclobutane groups, takes place in the presence of free radicals or free radical generating catalysts, dimerization to form perfluorocyclobutane groups takes place thermally. When a perfluorovinyl group is dimerizable, dimerization is preferably favored over other thermal reactions o either kinetically or in equilibrium. Lubricant polymers of the invention are preferably formed by the reaction of monomers having two or more dimerizable perfluorovinyl groups with other monomers having one dimerizable perfluorovinyl group in order to prepare oligomeric compounds which are end-capped with unsubstituted or optionally inertly or reactively substituted aryl ether groups where inert substitution is any substitution which does not interfere undesirably with the formation of the polymers and their lubricating ability and reactive substitution may interfere somewhat but has an advantage of providing better adhesion of the lubricant to a surface being lubricated. Examples of reactive substituents include hydroxyl, amine, and carboxylic acid groups. A dimerizable 20 perfluorovinyl group is a perfluorovinyl group which reacts with another suchgroup to form a perfluorocyclobutane ring. Thus, resulting dimers have one and polymers have at least two perfluorocyclobutane groups, in particular, sufficient perfluorocyclobutane groups to achieve physical and tribological properties desired for specific uses of the polymers.
2~
The term ~polymer~ is used herein to refer to any compound having at least two perfluorocyclobutane groups formed from perfluorovinyl groups, and includes oligomers which have from 2 to 1000 repeating units and preferably have a molecular weight of from 300 to 600,000. Fluids used in the practice of the 30 invention are advantageously of weight average molecular weights less than 75,000, preferably from 348 to 10,000, more preferably from 348 to 3000; solid thermoplastic polymers useful as lubricants in the practice of the invention advantageously have weight average molecular weights equal to or greater than 75,000, preferably from 60,000 to 600,000, more preferably from 60,000 to WO 94125547 21 6 ~ 7 0 ~ PCT/US94/04274 200,000; cured thermoset polymers of the invention are useful when sufficiently cured to form solids, advantageously as a layer on a surface to be lubricated, the molecular weight of which layer is not measurable as weight average molecular weight and is referred to as infinite molecular weight because of crosslinking.
s Within this scope and depending on the molecular structure connecting the perfluorocyclobutyl groups, the number of perfluorocyclobutane groups can vary from as few as two up to hundreds. Additionally encompased in the invention are lubricant compositions comprising dimers of perfluorovinyl compounds, said dimers having a perfluorocyclobutane group.

The relative proportion by weight of the perfluorocyclobutane groups to the other molecular components of the resulting products can vary over a wide range of from 3 to 1 to 0.01 to 1, preferably from 3 to 1 to 0.0~ to 1 and most preferably from 1 to 1 to 0.1 to 1. High proportions of perfluorocyclobutane 15 groups are desirable, for instance, when fluorocarbon character such as low dielectric constant is beneficial in the products. Exemplary of such products are low dielectric fluids and lubricants.

The poly(perfluorocyclobutane aryl ethers) (lubricant polymers) of the 20 present invention are preferably mixtures of polymeric and dimeric compounds although lower and higher oligomers such as trimers and tetramers are optionallyused. The polymeric lubricants preferably have weight average molecular weights (Mw) corresponding to greater than 30 repeating units, more preferably greater than 3~ repeating units. In the case of fluid lubricants, the number of 25 units is preferably sufficiently small that that the lubricants are pourable liquids at room temperature and yet maintain a low volatility, usually of a Mw corresponding to less than 200 repeating units, preferably less than 100, more preferably lessthan ~0 repeating units.

Polymeric and/or oligomeric perfluorocyclobutane ring containing lubricants include linear molecular structures prepared from a mixture of monomers having two dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group; and branched molecular structures prepared from a mixture of monomers having three or more dimerizable perfluorovinyl 37,374I-F

21607~

groups and end-capping agents having one dimerizable perfluorovinyl group, or mixtures of linear and branched structures prepared from a mixture of monomers having two or more dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group. To form the linear polymers, molar 5 ratios of monomers having two dimerizable perfluorovinyl groups to end-cappingagents are advantageously from 1 :10 to 10:1, preferably from 1:5 to 5:1, more preferably from 1:4 to 4:1. The branched molecular structures are advantageously prepared from a mixture wherein the ratio of monomers having three or more dimerizable perfluorovinyl groups to end-capping agents are 10 preferably from 1:20 to 1:1.5, more preferably from 1:15 to 1:2, most preferably from 1:3 to 1:10. The mixtures of linear and branched structures are prepared from a mixture having ratios of monomers having two dimerizable perfluorovinyl groups to monomers having more than two dimerizable perfluorovinyl groups to end-capping agents advantageously of from 1:0.1:1.5 to 1:200:2000, preferably 15 from 1 :0.5:2 to 1 :100:500, more preferably from 1 :1:5 to 1:10:400. Lubricants which are prepared from the ratios stated above do not necessarily correspond tothese ratios of monomer units in the final lubricant composition, because volatile components comprising primarily the dimer of the end capping agent may optionally be removed from the lubricant by distillation or vacuum evaporation.
Linear molecular structures are advantageously easy to prepare in high yields, while the branched molecular structures often perform better as lubricants under higher temperature or higher stress conditions when compared to lubricantswhich have substantially linear molecular structures. Monomers useful in the 2s practice of the invention are suitably prepared by any method which links molecular structures having perfluorovinyl groups to other molecular structures or which forms perfluorovinyl groups. Useful syntheses are given, for instance in U.S. Patent 5,037,917.

Although any monomer having at least one dimerizable perfluorovinyl group is suitably used in the practice of the invention, perfluorovinyl aryl ethers are preferred .

WO 9412~;547 21 6 0 7 ~ ~ PCT/US94/04274 Preferably, to avoid rearrangement and facilitate polymer formation the monomers have structures such that resulting polymers have hydrocarbyl groups (preferably aromatic rings), perfluorocyclobutane rings and at least one non-carbon atom such as oxygen, silicon, boron, phosphorus, nitrogen, selenium, s tellurium and/or sulfur atom (each optionally substituted) in the backbones, preferably between the aromatic (aryl) group and the perfluorovinyl group.

The monomers preferably have a structure represented by Formula l:

CF2=CF-X-R-(X-CF=CF2)m wherein R represents an, optionally inertly substituted aromatic group; each X is independently any group which links R and a perfluorovinyl group (hereinafter linking structures) preferably an oxygen or sulfur atom, said structures being inert;
15 m+1 is the number of -X-CF=CF2 units. Advantageously, m is an integer of fromO to 3, preferably from O to 2. By "inert" it is meant that the structures or substituents do not react undesirably with perfluorovinyl groups or interfere undesirably with polymerization (perfluorocyclobutane formation) of the monomers.

R is suitably any inert molecular structure, preferably a molecular structure which facilitates formation of perfluorocyclobutane rings and/or imparts desirable physical properties to polymers or oligomers prepared from the monomers.
Preferably, at least one carbon atom of R is in the molecular chain between X's 25 and is part of an aromatic nucleus. Aromatic groups are desirable because of improved physical properties of the polymers and ease of manufacture of the monomers. For both ease of manufacture of the monomer and monomer stability, when R is aromatic, each X is preferably independently sulfur or oxygen.
The aromatic group can be any molecular structure having aromatic character, 30 advantageously having at least one six membered aromatic ring, suitably having any number of such six-membered rings fused together or connected by bonds or linking structures. R preferably has from 1 to 50 such rings, more preferably from 1 to 10 rings, more preferably containing from 6 to 25 carbon atoms, most preferably R has at least 2 to 4 aromatic rings to impart properties such as -21607~

hardness and/or stiffness to a polymer. The aromatic fragment is suitably unsubstituted or inertly substituted. Inert substituents on an aromatic R include, for instance, the inert substituents listed for R generally. Optionally R contains groups or has substituents which are inert, that is which do not undesirably interfere with the formation of perfluorocyclobutane rings from perfluorovinyl groups. Inert substituents include ether, carbonyl, ester, tertiary amide, carbonate, sulfide, sulfoxide, sulfone, nitrile, alkyl phosphonate, tertiary amine, alkyl phosphate, alkyl silyl, chlorine, bromine, fluorine, alkyl, arylalkyl, alkylaryl, cycloalkyl, fluoroalky, perfluoroalkyl, aromatic, heterocyclic, alkoxyl, and aryloxy groups, which inert substituents are suitably in any position, for instance, in a polymer backbone between X's and/or appended to such a backbone. Molecular structures R and substituents on R are advantageously fluorinated in order to increase the fluorine content of the lubricant and thereby improve it's tribological properties. This may be achieved by substituting the R group with such s substituents as fluorine, trifluoromethyl (CF3), perfluoroalkyl or perfluoroalkoxy, or pentafluorosulfanyl. Carbon-containing inert substituents on R preferably contain from 1 to 50, more preferably from 1 to 12 carbon atoms because of the stability and ease of working with monomers of lower molecular weight. R, including inert substituents preferably has a molecular weight (MW) of from 14 to 20,000, more preferably from 75 to 1~,000 and most preferably from 75 to ~,000.
These ranges include monomeric and oligomeric R groups. In the case of monomers which are other than oligomeric, R preferably has from 1 to 50, more preferably from 6 to 2~, carbon atoms because molecular weights above this reduce the contribution to properties made by the fiuorine-containing substituents when R is alkyl or aromatic hydrocarbon. As previously discussed, the nature of R as well as the perfluorocyclobutane content of the polymers can vary broadly according to the type of products desired.

Exemplary aromatic molecular fragments include, for instance, perchlorophenylene, phenylene, biphenylene, naphthylene, dichlorophenylene, benzophenone, nitrophenylene, p,p'(2,2-diphenylene propane) [-C6H4-C(CH3)2-C6H4]; p,p'-(2,2-diphenylene-1,1,1,3,3,3 hexafluoropropane), [-C6H4-C(CF3)2-C6H4-], 1,4-bis(hexafluoroisopropyl)benzene [-C(CF3)2-C6H4-C(CF3)2-], 1,3-bis(hexafluoroisopropyl)benzene [-C(CF3)2-C6H4-C(CF3)2-], 37,3741-F
~ ` 216070Q

preferably biphenylene; phenylene; 9,9'-diphenylfluorene, oxydiphenylene;
thiodiphenylene; 2,2-diphenylene propane; 2,2'-diphenylene, 1,1,1,3,3,3-hexafluoropropane; 1,1-diphenylene-1-phenylethane; naphthalene; and anthracene. Molecular weights of aromatic ring containing polymers are preferably 5 at least 1,000 .

Most preferably, at least one aromatic carbon atom of R is bonded directly to X, most preferably aromatic carbon atoms of R are bonded directly to each X
because perfluorovinyl groups bonded to X, said X being bonded to aromatic 10 groups are generally more reactive in forming perfluorocyclobutane rings.

Polymers produced from the preferred monomers preferably have a formula represented by Formula 2:

[R-X-Q-X-]V-[R'-X-Q-Xlm-[R"-X-Q-X]n[R"']p-wherein each of R, and R"' are the same or different aromatic groups referred toherein as end capping groups because they are derived from monomers having one dimerizable perfluorovinyl group; R' is a branching group derived from a 20 compound having at least'3 dimerizable perfluorovinyl groups; R" is an unbranched chain extending group derived from compounds having 2 dimerizable perfluorovinyl groups; Q is a cyclobutane group; X is defined as for Formula 1.
Subscripts v, m, n, and p are integers representing the number of groups in the brackets preceeding them such that they correspond to the general formula 2s v+p=a(m)+2 wherein "a" corresponds to the number of dimerizable perfluorvinylgroups on R' minus 2. Thus, when the number of dimerizable perfluorovinyl groups on R' is 3, the formula is v + p =m + 2, whereas when the number of dimerizable perfluorovinyl groups on R'=4, the formula is v+p=2m+2, and so on.

~~

WO 94/25547 21 6 0 7 ~ ~ PCT/US94/04274 Preferred polymers for this purpose are those having a structure represented by Formulas 3 or 4:

F ~ 'FF ~ f r-J -F o ~o_¢~

Formula 3 wherein J is H, an inert or reactive substituent. When J is a reactive group or other group capable of substantial dipolar interaction such as hydrogen bonding or strong Vander Waals forces, such groups advantageously serve to adhere the o lubricant fluid or polymer more strongly to the media surface. Substituents J are preferably selected from hydrogen, trifiuoromethyl, pentafluorosulfanyl, fluorine, perfluoroalkoxy, tetrafluoroethoxy, trifluoromethoxy, methoxy, cyano, carboxylicacid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, alkyl phosphonates, piperanyi, amino and alcohoi groups. In each case an alkyl 15 or alkoxy group preferably has from 1 to 12 carbon atoms, and an aryl group preferably has from 6 to 20 carbon atoms.

WO 94/25547 21 ~ Q 7 Q Q PCT/US94/04274 F P) (~ F ) br F

~~ F
J

-- n Formula 4 wherein K is an unsubstituted or inertly substituted hydrocarbyl group (aryl, s arylalkyl, alkylaryl, linear, branched or cyclic aliphatic), preferably selected from methyl, phenyl, or trifluoromethyl; and J is as described for Formula 3, preferably selected from hydrogen, perfluoroalkoxy, tetrafluoroethoxy, trifluoromethyl, pentafluorosulfanyl, fluorine, trifluoromethoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, alkyl lo phosphonates, piperanyl, amino and alcohol groùps.

The monomers are heated to a temperature and for a time sufficient to form perfluorocyclobutane rings. Temperatures suitable for forming perfluorocyclobutane rings differ with the structure of the monomer. In general,lS temperatures above 40C are suitable for formation of perfluorocyclobutane rings, preferably the temperature is above 50C, more preferably above 100C, because these temperatures result in formation of the rings at successively faster rates. Temperatures above 4~0C are preferably avoided because perfluorocyclobutane groups are generally thermally unstable above such wo 94/25s47 21 6 0 7 0 0 PCTrus94lo4274 temperatures. More preferably a temperature of from 1 0~C to 350C, most preferably from 1 05C to 250C, is used to produce the perfluorocyclobutane rings at a convenient rate. Within that range, a temperature of from 130 to 230 is generally most preferred for cyclization of perfluorovinyl aromatic or aliphatic 5 ethers or sulfides, while a temperature of from 50C to 80C is needed to formperfluorocyclobutane groups when the perfluorovinyl group is attached directly to an aromatic ring. In the case of perfluoroalkyl perfluorovinyl ether groups, however, temperature of at least 300C, preferably at least 350C, is generally required.

Preferably, especially when the perfluorovinyl compounds are capable of radical initiated addition polymerization, conditions conducive to free radical polymerization, for example presence of oxygen, ozone, peroxygen compounds and other free radical generating compounds are avoided so that the perfluorovinyl groups will dimerize into perfluorocyclobutane groups rather thanundergoing addition polymerization. Compounds known in the art for stabilizationagainst free radical polymerization are alternatively used. Similarly, especially when the perfluorovinyl groups are capable of addition polymerization in the presence of anions or cations, compounds which supply such anions or cations 20 are avoided. For instance, fluoride ions (for example from carbonyl fluorides or metal fluorides) chloride, hydroxide, phenoxide are preferably avoided. To avoidsuch compounds as carbonyl fluorides, oxidative conditions such as presence of oxygen, hypochlorite, dichromate, permanganate are preferably avoided because perfluorovinyl groups are known to oxidize to form carbonyl fluorides.
2s Perfluorovinyl ethers, thioethers, sulfones, sulfoxides are relatively stable with regard to addition polymerization and oxidation; and, therefore, such precautions are generally unnecessary when such perfluorovinyl compounds are used.

Monomers or admixtures thereof are suitably neat or, optionally, in 30 admixture with other materials such as in solution, in emulsion, in dispersions or in any other form in which monomer molecules can be contacted with one another to form a polymer. Liquid admixtures are advantageous for maintaining contact between monomer molecules such that higher molecular weight polymers are formed. This is particularly useful when linear thermoplastic polymers are the WO 94125547 PCT/US~4/04274 216Q70~

products. Neat polymerizations or oligomerizations are also generally preferred to foml relatively low molecular weight fluid products. Alternatively, in the case of monomers containing three or more dimerizable perfluorovinyl groups, the polymerization or oligomerization may be carried out in the presence of a large excess of the end-capping agent, which compound contains only one dimerizable perfluorovinyl group. This synthetic method creates an excess of the fluid product containing one perfluorocyclobutane ring, which then acts as a solvent for the production of the branched lubricant prepared from the end-capped monomer containing three or more dimerizable perfluorovinyl groups. This method also o advantageously maintains a low molecular weight in the branched lubricant fluid.
By carrying out the polymerization in an excess of end-capping agent, a polyfunctional monomer is less likely to react with other polyfunctional monomers to create sufficient networking in the molecular structure to form gels or other insoluble products.
Suitable solvents are those which are inert to the conditions encountered in the polymerization reaction and include perfluorotetradecahydrophenanthrene (MULTIFLUORTM APF 215 commercially available from Air Products Corp.). At atmospheric pressure, preferred solvents are those which attain temperatures of 170-2~0C such as dichlorobenzene, trichlorobenzene, diphenyl oxide, perfluorotetradecahydrophenanthrene, and mesitylene. Although solvents such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene give less satisfactory resultssuch as discoloration of the finished polymer, they are suitably used when theirdisadvantages are tolerable in a final product. When a solvent is used the concentration of monomers in solvent is advantageously from 0.1 to 99.9 weight percent preferably, from 10 to 90 percent by weight monomer.

Polymerization or dimerization suitably takes place at any pressure.
Pressures are generally chosen such that the monomers and any solvents and/or dispersing media remain liquid at the temperatures used for polymerization.
When the monomers or other materials evaporate at temperatures used, then it is generally preferable to maintain a pressure at least sufficient to maintain the materials liquid.

WO 94/25547 2 ~ 6 0 7 ~ O PCT/USg4/04274 While the compounds of the present invention are described as single molecules having specified substituents present in a stated ratio, it will be realized by one skilled in the art that the compounds will exist as statistical mixtures of molecules. Some of these molecules will have the specified ratio of substituentss while others will have higher or lower ratios. However, the perfluorocyclobutane ring containing fluids will, within these statistical mixtures, have substituents present at the specified ratios.

The product is then recovered using conventional techniques, such as by 0 evaporation of the polymerization solvent or light components of the polymerization under reduced pressure, including the end-capping compound which contained one dimerizable perfluorovinyl group, as well as the dimer of the end-capping compound which contained one dimerizable perfluorovinyl group.

The compounds of this invention are useful as lubricants over extended temperature ranges. They may be used alone and also may be used in conjunction with various additives to improve their performance. Additionally, they may themselves be used as additives with other base stocks. Advantageously, the polymers are used at temperatures of from 50C to 350C, preferably from 20C to 200C.

When used as an additive to a base stock, the poly(perfluorocyclobutane aryl ether) of the present invention must be compatible with the base stock. By compatible, it is meant that the poly(perfluorocyclobutane aryl ether) of the 25 present invention is readily dispersible or soluble in the base stock, either with or without the addition of an appropriate surfactant. Examples of known lubricant base stocks useful in the compositions of this invention include organic oils and greases within the skill in the art. When the poly(perfluorocyclobutane aryl ethers) of the present invention are used as additives to conventional, compatible 30 base stocks, it is preferred that the base stocks are poly alpha olefins, polyglycols, polyphenyl ethers and polyol esters. It is more preferred that the base stocks are polyphenyl ethers such as 5P4E (a polyphenyl ether having 5 phenyl rings with 4 ether linkages, such as that commercially available from Monsanto Corp. under WO 94/25547 21 6 ~ 7 0 ~ PCT/US94/04274 the trade designation OS-124). Other preferred base stocks include polyol esterssuch as pentaerythritol tetra Cs-Cg esters (PET), and poly alpha olefins.

The lubricant compositions of this invention comprise from 0.1 to 100 s weight percent of the poly(perfluorocyclobutane aryl ether) of the invention. That is, the poly(perfluorocyclobutane aryl ether) of this invention may be used as alubricant base stock [i.e., lubricant composition is up to 100 weight percent poly(perfluorocyclobutane aryl ether)] or they may be used as additives with other lubricants [i.e., lubricant composition contains at least 0.1 weight percent 10 poly(perfluorocyclobutane aryl ether)].

When the poly(perfluorocyclobutane aryl ethers) of this invention are used as lubricant additives, it is preferred that they are used in amounts of at least 0.5 weight percent, more preferably at least ~ weight percent. It is also preferred that lS the poly(perfluorocyclobutane aryl ethers) of the present invention, when used as additives, are used in amounts of no greater than 50 weight percent, preferably no greater than 20 weight percent.

As discussed above, the poly(perfluorocyclobutane aryl ethers) of the 20 present invention may be used as lubricants themselves, either alone or with the addition of additives or other lubricants known in the art. When used as the lubricant base stock, additives useful in high temperature lubricants may be added. In this context, it is preferred that the poly(perfluorocyclobutane aryl ethers) of this invention comprise at least ~0 weight percent, more preferably at 2s least 95 weight percent of the composition with one or more additives making up the remainder of the lubricant composition. Additionally, the poly(perfluorocyclobutane aryl ethers) of this invention may be blended with other base stocks to prepare lubricants.

A preferred embodiment of the present invention is a magnetic recording media comprising a substrate having a magnetic recording lamina thereon, the lamina comprising magnetic particles with a binder in the case of particulate media or without a binder in the case of thin film media, for instance nickel-cobalt.

The lamina includes a lubricating amount of at least one poly(perfluorocyclo-butane aryl ether) which may be used as either an internal or topical lubricant.Effective poly(perfluorocyclobutane aryl ethers) for this purpose are preferablysubstituted with fluorine, trifluoromethyl, trifluoromethoxy, tetrafluoroethoxy,5 perfluoroalkyoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, pentafluorosulfanyl, alkylphosphonates, piperanyl, amino and alcohol groups. In each case an alkyl or alkoxy group preferably has from 1 to 12 carbon atoms, and an aryl group preferably has from 6 to 20 carbon atoms.

The lubricant polymers described herein are particularly useful as topical lubricants for thin film magnetic recording media. Thin film magnetic recording media generally include a substrate which may be a non-magnetic metal or a plastic such as a polyester (for example polyethylene terephthalate). A magnetic5 film such as a metal or a metal alloy such as cobalt-nickel is applied to the substrate. The thickness of the magnetic layer is on the order of 0.20 micrometers. The lubricant is preferably on the surface of the magnetic layer preferably 10 to 1000 Angstrons (10-9 to 10~7m), more preferably from 2.0 nanometers to 0.20 micrometers (2x10-9 to 2x1 0~7m).

Similarly, the lubricant polymers are useful in particulate magnetic recording media. Particulate magnetic recording media generally include a substrate which may be a non- magnetic metal or a plastic such as polyester.
Magnetic particle containing pigments such as cobalt gamma Fe2O3, barium 25 ferrite or iron metal, with a binder are applied to the substrate. The amount of pigment can vary from 17.0 to 21.0 weight percent based on total formulation weight. The preferred range is from 17.0 to 19.0 weight percent. The binder is advantageously a thermosetting resin such as urethane, vinyl or a combination thereof, present in an amount between 2.5 and 6.0 weight percent, based on total30 formulation weight. The preferred range is between 3.0 and 6.0 weight percent.

When used as a topical lubricant for either particulate or thin film media, the poly(perfluorocyclobutyl aryl ether) lubricant is conveniently applied to the surface either neat or in solution with a volatile solvent. Suitable solvents for the 2l6~70a lubricant include aromatic hydrocarbons (for example toluene), ethers (for example diethyl ether, dimethoxyethane, dioxane, tetrahydrofuran, diethoxyethane), halogenated hydrocarbons (for example dichloromethane), alcohols (for example methanol or ethanol), ketones, (for example acetone), s esters (for example ethyl acetate), alicyclic hydrocarbons (for example cyclohexane), dimethylformamide, dimethylsulfoxide, and silicone fluids.

Alternatively, when used as an internal lubricant in particulate magnetic media, the poly(perfluorocyclobutane aryl ether) lubricant is included in the o composition of the mixture applied to the substrate to form the recording lamina.
This mixture includes binder, pigment containing magnetic particles and a volatile solvent together with the lubricant polymer. Suitable solvents for the lubricantinclude those listed for topical uses.

Magnetic media containing polymer lubricants of the invention are advantageously prepared in the following way: a dispersion comprising a urethane-vinyl binder and a magnetic particle containing pigment is prepared, for example in tetrahydrofuran solvent. Preferred pigments include iron metal, barium ferrite and cobalt gamma Fe2O3. Pigment to binder ratios are preferably 20 between 3:1 and 8:1. Pigment is preferably present in an amount from 2.5 to 6.0 weight percent based on total formulation weight. Lubricant is added to the dispersion in an amount preferably between 0 and 5 weight percent, more preferably from 0.1 to 2 weight percent of total formulation weight. A surfactant is added to the composition in an amount preferably between 0.50 and 1.0 weight 25 percent of total formulation weight. The magnetic particles are advantageously oriented by application of a magnetic field. Conveniently, the solvent is evaporated and the polymer binder is cured by a thermal process.

Alternatively, the lubricant described herein is used topically in thin film, or30 non-porous hard and flexible magnetic media.

Coatings of polymeric lubricants are alternatively applied as described in U.S. Patent 5,246,782.

WO 94/25547 21 ~ q 7 0 0 PCTIUS94/04274 Surface treated thin film media containing the lubricant of the present invention compare favorably with media surfaces treated with a hexafluoropropylene epoxide polymer available from E.l. DuPont de Nemours Co.
under the trade designation KrytoxTM 143 AC and tetrafluoroethylene epoxide s polymers commercially available from Ausimont, U.S.A., Inc., under the trade designation FomblinTM AM 2001. Physical properties including sliding friction and scratch resistance were evaluated to assess surface durability. The results of these comparisons are set forth in Example 8.

O The magnetic recording media containing the lubricant polymer of the present invention demonstrate improved surface durability. This is shown in the laboratory sample test results set forth in Examples 8 and 9. The cobalt-nickel thin film magnetic media (tape) coated with poly(perfluorocyclobutane aryl ether) lubricants demonstrate equivalent or improved friction and scratch resistance, when compared to cobalt-nickel thin film magnetic media (tape) coated with KrytoxTM 143AC, FomblinTM AM 2001, or no lubricant. Furthermore, the poly(perfluorocyclobutane aryl ether) lubricants do not require the use of FreonTU
or other halogenated solvents in the coating process, whereas FreonTM or other halogenated solvents are needed in the coating process with such lubricants as KrytoxTM 143AC and FomblinTM AM 2001.

Magnetic media containing poly(perfluorocyclobutane aryl ether) lubricants are advantageous in comparison to other commercially available products in that the lubricants of the invention provide optimal physical and magnetic performance 25 such as low static and dynamic coefficients of friction and high coercivitey of underlying or surrounding magnetic media and are economical to produce. A
dynamic coefficient of friction obtained is preferably less than 2, more preferably - less than 0.5, even more preferably less than 0.25, most preferably less than 0.16. A static coefficient of friction less than 0.25.
Furthermore, the poly(perfluorocyclobutane aryl ether)polymers exhibit advantageous enhanced lubricant stability in bases and water.

The following examples are provided for illustrative purposes only and should not be construed as limiting the invention in any way. Unless stated otherwise, all parts, ratios and percentages are by weight. Examples (Ex) of theinvention are designated numerically while comparative samples (C.S.) are not s examples of the invention and are designated alphabetically.

FXAMPLE 1: PREPARATION OF A FLUID POLYMER OF 1.3-~IS(TRIFLUOROVINYLOXY)BENZENE AND 3-TRIFLUQROVINYLOXY-1'.1'.1'-TRIFLUOROTOLUENE

To synthesize m-trifluorovinyloxy-1',1',1'-trifluorotoluene, DMSO (1000 ml), toluene (250 ml), and 3-trifluoromethylphenol (200g, 1.23 mole) were placed in a2 liter ~-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a thermocouple attached to a temperature controller. The stirred solution was purged of oxygen by placing a dip tube below the surface of the solution and allowing nitrogen to be blown into the solution for 15 minutes. Potassium hydroxide (45 percent solution, 1 53.3g, 1.23 mole) was added to the flask all at once, and a line to supply nitrogen was attached to a reflux condenser which wasplaced on top of the Dean-Stark trap. The mixture was then heated to 85C and water was removed azeotropically under a mild vacuum of 100 mm Hg (13.33 kPa) absolute pressure. When water ceased to collect in the Dean-Stark trap, thetemperature of the reaction was increased to 125C at 100 mm Hg (13.33 kPa) absolute pressùre and 100 ml of toluene was removed by distillation, leaving a reaction mixture in the flask.
2s The reaction mixture was cooled to room temperature, and 1,2-dibromotetrafluoroethane (132.09, 0.51 mole) was added slowly using a dropping addition funnel. The mixture was heated to 65C overnight, then allowed to cool to room temperature. A liquid suspension of potassium bromide (KBr) a by-product of the reaction of 1,2-dibromotetrafluoroethane and potassium 3-trifluoromethyl phenoxide and DMSO (dimethylsulfoxide) was added to a 1.5 times voiumetric excess of water in a separatory funnel and shaken vigorously.
The product formed a separate, lower layer at the bottom of the funnel and was removed. This crude product (lower layer) was washed again with an equal wo 94/25547 2 ~ 6 D 7 0 0 PCT~S94/04274 volume of water. A small amount of toluene was removed from the crude product by evaporation on a rotary evaporator at 30C and 20 mm Hg (2.62 kPa) absolute pressure, and the product was thereafter distilled from the crude reaction mixture at 85C and 15 mm Hg (2.0 kPa) absolute pressure to provide the product, m-(2-s bromotetrafluoroethoxy)-1',1',1'-trifluorotoluene (248 9, 0.73 mole, 59 percent yield) as a water white oil. This product gives the following mass spectral data:
m/e: 342 (20.1 percent); 340 (19.8 percent); 323 (7.9 percent); 321 (7.2 percent);
21 1 (25.6 percent); 145 (100.0 percent).

o The product of the above reaction (248 g, 0.73 mole) was combined with granular zinc (59.09, 0.90 mole) in dry acetonitrile (600 ml) and stirred at 83C for 4 hours to form a reaction mixture. The mixture was cooled to room temperature and filtered on a 15 micrometer sintered glass filter funnel to remove the zinc salts from the acetonitrile solution of the product. The acetonitrile was distilled out of the crude reaction mixture under reduced pressure (28C, 150 mm Hg (20 kPa) absolute pressure) after which the product was recovered by distillation at 80Cand 100 mm Hg (13.33 kPa) absolute pressure to give 158 9 (889.7 percent yield) of the product, m-trifluorovinyloxy-1',1',1'-trifluorotoluene, which was 97.8 percent pure by GC (gas chromatographic) analysis, with the remainder of the product being the by-product m-(1, 1 ,2,2,-tetrafluoroethoxy)-1', 1',1 '-trifluorotoluene.

The product gave the following mass spectral data: m/e: 242 (52.3 percent); 223 (12.3 percent); 195 (14.2 percent); 145 (100 percent); 125 (18.3 percent); 95 (30.6 percent).

A mixture was prepared from 1.25 ml of 1,3-bis(trifluorovinyloxy)benzene (as prepared in U.S. Patent 5,023,380) and 8.75 ml of 3-trifluorovinyloxy-1',1',1'-trifluorotoluene to make a total of 10 ml. This mixture was placed in a 50 ml round bottom flask fmed with a nitrogen padded reflux condenser and was 30 refluxed under nitrogen for 20 hours.

The resulting product was analyzed by GC/MS (gas chromatographic mass spectroscopy) and found to be a mixture of hexafluorocyclobutane products whose major components were 1,2-bis(3'-trifluoromethylphenoxy) WO 94/25547 216 0 7 0 ~) PCT/IJS94/04274 ~

hexafluorocyclobutane and 1,3-bis(2'-[3"-trifluoromethylphenoxy]
hexafluorocyclobutyl)phenyl ether (having two perfluorocyclobutane rings), with a trace amount of 1~2-bis(3~-[2~-{3U~-trifluoromethylphenoxy}hexafluorocyclobutyloxy]phenyl)hexafluorocyclobutyl ethers (having three perfluorocyclobutane rings). By vacuum distillation two fractions were collected.

The first fraction contained primarily mono-perfluorocyclobutane material consisting of two isomers (cis and trans 1,2-substituted hexafluorocyclobutane) lO with similar mass spectra (given for one isomer only): m/e: 484 (20.2 percent);
465 (12.9 percent); 273 (29.2 percent); 242 (30.1 percent); 207 (11.2 percent);
195 (13.0 percent); 145 (100.0 percent);

The second fraction contained predominantly di-perfluorocyclobutane S material, consisting mainly of three isomers (cis-cis, cis-trans, and trans-trans) of 1,2-substituted hexafluorocyclobutanes, and small amounts of four isomers of a product containing one 1,2-substituted hexafluorocyclobutane ring and one 1,3-substituted hexafluorocyclobutane ring (cis-1,2 cis-1,3; cis-1,2 trans-1,3; trans-1,2 cis-1,3; and trans-1,2 trans-1,3). All seven products gave roughly the same 20 peaks in their mass spectra in differing intensities. The following mass spectral data was for the first product isomer to elute from the gas chromatography (GC) column, and corresponded to one of the three main isomers of two perfluorocyclobutane rings: m/e: 754 (36.4 percent); 593 (12.5 percent); 492 (14.1 percent); 415 (21.9 percent); 273 (27.7 percent); 242 (39.1 percent); 195 (21.5 25 percent); 173 (23.4 percent); 145 (100.0 percent); 126 (28.5 percent); 95 (23.1 percent); 92 (34.7 percent); 76 (57.6 percent); 64 (27.3 percent).

The second fraction also contained a small amount of material containing three perfluorocyclobutane rings, consisting of six isomers (cis-cis-cis, cis-cis-30 trans, cis-trans-cis, cis-trans-trans, trans-cis-trans, and trans-trans-trans) of 1,2-substituted hexafluorocyclobutanes. Because of the small amount of this product present in the mixture, the corresponding products containing one or more 1,3-substituted hexafluorocyclobutane rings were not detected. The mass spectra of the six isomers showed roughly the same peaks in slightly differing intensities.

~1607~Q

The following mass spectral data was from the first product isomer of tri-perfluorocyclobutane material to elute from the GC column: m/e: 1024 (21.6 percent); 593 (16.3 percent); 492 (35.5 percent); 415 (17.6 percent); 281 (16.2 percent); 273 (16.4 percent); 242 (26.0 percent); 208 (15.9 percent); 207 (71.9 s percent); 145 (100.0 percent); 92 (19.7 percent); 76 (26.8 percent).

In all cases, the primary products of cyclization were 1,2-substituted hexafluorocyclobutanes, with small amounts (1-2 percent) of 1,3-substituted hexafluorocyclobutanes observable by GC/MS, (except for the tri-l0 perfluorocyclobutane material, of which only trace amounts were seen) the twobeing distinguished by a small peak at m/e = 100, corresponding to a fragment of CF2=CF2 present in the mass spectra of the 1,2-substituted hexafluorocyclobutanes which was absent in the 1,3-substituted products.
Absolute configurations of the different isomers were not assigned.
This example shows that a compound containing one trifluorovinyl group can be combined with a compound containing two trifluorovinyl groups (the mixture then heated to cause cyclization of the trifluorovinyl groups) to provide a fluid containing perfluorocyclobutane groups. Such fluids are of the type useful as 20 IOW dielectric hydraulic fluids or lubricants.

FXAMPLE 2: PREPARATION OF A FLUID POLYMER OF 1.3-BIS(TRIFLUOROVINYLOXY)BENZENE (1'.1',2',2' TETRAFLUOROETHOXY)-TRIFLUOROVINYLOXYBENZENE AND 1.3-BIS(1 ',1 '.2'.2'-25 TETRAFLUOROETHOXY)BENZENE

A mixture (25 ml) consisting of 1,3-bis(trifluorovinyloxy)benzene taS
prepared in US Patent 5,023,380) (26 percent), 3-(1',1',2',2', tetrafluoroethoxy)trifluorovinyloxybenzene (54 percent), 1,3-bis(1 ',1 ',2',2'-30 tetrafluoroethoxy)benzene (15 percent), and tetraglyme (5 percent) was placed ina 100 ml round bottom flask and heated at reflux under nitrogen for 5 hours. The resulting viscous oil was checked by GC and was found to contain unreacted 1,3-bis(1',1',2',2',-tetrafluoroethoxy)benzene and tetraglyme, as well as mixtures of isomers of heavy components. After removal of the light, unreacted components, 21607~ ~
WO 94/25~47 PCT/US94/04274 two fractions were cleanly separated by fractional distiilation and each was analyzed by GC/MS.

The first fraction was found to contain primarily 1,2-bis(3~-[1~ ,2U,2u-tetrafluoroethoxy]phenoxy)hexafluorocyclobutane as two isomers (cis and trans substituted hexafluorocyclobutane) followed by small amounts (1-2 percent each) of two 1,3-substituted hexafluorocyclobutane products (cis and trans), all having roughly similar mass spectra. The following was the mass spectral data for the first isomer to elute from the chromatography column, and corresponded to one ofo the 1,2-substituted isomers: m/e: 580 (25.8 percent); 371 (11.3 percent); 321 (12.5 percent); 290 (23.4 percent); 270 (36.4 percent); 243 (69.9 percent); 193 (100.0 percent); 95 (96.4 percent); 92 (5~.9 percent); 76 (26.7 percent); 64 (29.9 percent); 51 (21.9 percent).

lS The second fraction contained 1 ,3-bis(2'-~3"-~ 1 u~, 1"',2"',2"'-tetrafluoroethoxy}phenoxy]hexa- fluorocyclobutyl)phenyl ether, primarily as three isomers of 1,2-substituted hexafluorocyclobutanes with a small amount of four isomers of the product with one 1,2-substituted and one 1,3-substituted hexafluorocyclobutane ring. The seven isomers all gave roughly the same peaks 2~ in their mass spectra in differing intensities. The following mass spectral data was for the first isomer to elute from the GC column, and corresponded to one of thethree main isomers of the product: m/e: 850 (24.7 percent); 540 (24.2 percent);
371 (41.5 percent); 321 (12.9 percent); 301 (16.4 percent); 290 (33.9 percent);
270 (74.4 percent); 243 (63.9 percent); 207 (24.1 percent); 193 (86.7 percent);
2s 173 (14.8 percent); 95 (100.0 percent); 92 (63.2 percent), 76 (71.8 percent)64 (32.6 percent); 51 (15.5 percent).

This example shows that a compound containing one trifluorovinyl group is combined with a compound containing two trifluorovinyl groups in a solvent and the resulting mixture heated to cause cyclization of the trifluorovinyl groups. Such fluids are of the type useful as low dielectric hydraulic fluids or lubricants.

EXAMPLE 3: PREPARATION OF FLUIDS OF 1. 1. 1 -TRIS(4-- TRIFLUOROETHENYLOXYPHENYL)ETHANE AND 3-TRIFI UOROETHENYLOXY-1'1'-1'-TRIFLUOROTOLUENE

L~ ~ O ~L
F F ~ F F F

F~ ~\ F

1 ~ F

n Formula 5 wherein n is from 0 to 20, preferably 0 or from 1 to 20; each L is independently0 trifluoromethyl, fluorine, trifluoromethoxy, tetrafluoroethoxy, perfluoroalkoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester,alkyl or aryl sulfones, amide, pentafluorosulfanyl, alkyl phosphonate, piperaryl, amino or alcohol groups, preferably, and in this example, trifluoromethyl. Whereeach alkyl group is preferably from 1 to 12 carbon atoms and each aryl group is 15 preferably from 6 to 20 carbon atoms.

Samples of 1, 1, 1-tris(4-trifluoroethenyloxyphenyl)ethane (as prepared in U.S. Patent 5,023,380) (60.3g, 0. 1 1 0 mole) and 3-trifluoroethenyloxy- 1'-1'-1'-trifluorotoluene (as prepared in Example 1) (213.99, 0.884 mole) were combined 20 in a 250 ml round bottomed flask containing a magnetic stirring bar. A
thermocouple was inserted through one neck of the flask into the solution to monitor the temperature. The thermocouple was attached to a temperature WO 94125~;47 216 0 7 0 ~ PCTIUS94/04274 ~

controller which controlled the power output to a heating mantle on the flask through a Variac rheostat power source. A gas dispersion tube was inserted into the flask below the liquid level, and the liquid was deoxygenated by bubbling nitrogen into the flask with stirring for 15 minutes. The solution was stirred and s heated according to the following schedule: 125C for 3 hours; 130C for 1 hour;
137C for 1 hour; 140C for 15 hours; 145C for 1.5 hours; 150C for 3 hours;
160C for 5 hours; 175C for 14 hours; 180C for 3 hours. The solution was cooled to room temperature, transf~rred to a 2~0 ml single necked round bottom flask, and evaporated on a rotary evaporator at 2.0 mm Hg (0.266 kPa) and o 160C to remove the product 1,2-bis(3-trifluoromethylphenoxy) hexafluorocyclobutane as a 1:1 mixture of cis and trans isomers (168 g, 0.347 mole). This compound was designated Lubricant 1 in Examples 6 and 8.

Mass Spectrometric Analysis, m/e (percent): 7~ (12.8 percent); 125 (15.3 S percent); 145 (100 percent); 146 (21 percent); 195 (17.4 percent); 242 (15.6 percent); 273 (30.8 percent); 323 (11.4 percent); 465 (55.9 percent); 466 (10.9 percent); 484 (29.2 percent).

The residue from the evaporation was analyzed by gel permeation chromatography (GPC, as standardized against polystyrene) and was found to contain a number of low molecular weight fractions. The lowest molecular weight fraction comprised 42.1 area percent of the GPC curve, analyzed at weight average molecular weight 1337, corresponding to the compound of Formula 5 with n = 1 (calculated molecular weight = 1272). The next higher molecular 2s weight fraction comprised 24.8 area percent of the GPC curve, and analyzed at a weight average molecular weight of 2124, corresponding to the compound of Formula 5 with n =2 (calculated molecular weight = 2060). The third fraction comprised 14.7 area percent of the GPC curve, and analyzed at a weight average molecular weight of 2921, corresponding to the compound of Formula 5 with n= 3 (calculated molecular weight = 2848). The remainder of the content of the fluid comprised 18.4 area percent of the GPC curve, and was composed of a mixture of higher molecular weight compounds of Formula 5, with the two components combined in ratios according to the formula [X]n[Y]n+2 where X = 1,1,1-tris(4-~ 21~07~0 trifluoroethenyloxyphenyl)-ethane and Y = 3-trifluoroethenyloxy-1'-1'-1'-trifluorotoluene, and n was greater than or equal to 4, and less than or equal to 18. This mixture was designated Lubricant 2 in Examples 7 and 9.

These examples demonstrate the preparation of novel molecular compositions which have a high fluorine content by weight, but which possess alkyl hydrocarbon and aromatic hydrocarbon substituents to increase their compatibility with hydrocarbon organic chemical systems. This increased o compatibility with hydrocarbon organic systems allows the application of coatings of these fluids to a substrate surface from a wide variety of hydrocarbon organic solvents, eliminating the need for application from FreonTM solvents which are in disfavor. Such fluid coatings are useful as lubricants to reduce friction and wear.

FXAMpLE 4: FRICTION AND WEAR TEST

The anti-wear and extreme-pressure characteristics of the poly(perfluorocyclobutane aryl ether) lubricant polymers of this invention were measured by pin-on-disk testing. In this example a silicon nitride (SiN) pin with 20 hemispherical tip geometry was slided against a disk made of a film of biphenyl perfluorocyclobutyl ether polymer as prepared in U.S. Patent 5,023,380. Test load range was 2-1~ Newtons (0.44 to 3.3 pounds). The sliding speed was 50 cm/sec and each test was run for 120 seconds at 25C. During each test, the torque as a fraction of the wear cycles was monitored on a real time data 25 acquisition basis for data analysis to yield the coefficient of friction.

The average dynamic coefficient of friction of the biphenyl perfluorocyclobutyl ether polymer was 1.23+0.20. As a comparison the average dynamic coefficient of friction of a 2 mil film of KaptonTM polyimide (commercially 30 available from E.l. Du Pont de Nemours Co.) was 0.90+0.15.

The data in the above example shows that the perfluorocyclobutane ring containing thermoplastic polymer performs favorably when compared to a leading polymeric lubricant film.

21607~ --FXAMPLE 5: FRICTION AND WEAR TESTS

The procedure of Example 4 was followed with thermoset polymer 5 prepared from 1,1,1,-tris(4-trifluorovinyloxyphenyl) ethane as prepared in U.S.
Patent 5,023,380 as the disk composition.

The average dynamic coefficient of friction of the thermoset polymer prepared from 1,1,1-tris(4-trifluorovinyloxyphenyl)ethane was 0.97+0.20. As a l0 comparison the average dynamic coefficient of friction of a 2 mil film of KaptonTM
polyimide (commercially available from E.l. Du Pont de Nemours Co.) was 0.90+0.15.

The data in the example above demonstrates the perfluorocyclobutane ring lS containing thermoset polymer performs favorably when compared to a leading polymeric lubricant film.

FXAMPLE 6 AND COMPARATIVE SAMPLE A: ADDITIVE FRICTION AND
WF~R TESTS

The anti-wear and extreme pressure characteristics of the compounds and compositions of this invention were measured using the four-ball test using a Falex friction and wear tester according to the manufacturer's directions. In this Example, 1, 2-bis(3-trifluoromethylphenyloxy) hexafluorocyclobutane as prepared 25 in Example 3 (with various amounts of a polyphenyl ether, ~P4E (commercially available from Monsanto, Corp. under the trade designation OS-124), the amounts indicated in Table 1 was tested. The four-ball bearing balls used in this test were made of M-~0 steel. The test load was 13~ Newtons (30 pounds). The test speed was 1200 rpm and each test was run for 1 hour unless noted 30 otherwise. A sample of 60 cubic centimeters (60 x 10~6m3) of fluid were used for each test. Each test was conducted at 200C. During each test, the torque was monitored on a real time data acquisition basis for data analysis to yield the coefficient of friction. Optical microscope pictures of the bearing balls were taken ,~ 21~Q7G~

at the test completion, and scar diameter was measured from these pictures. The data obtained was shown in Table 1.

T- ble 1 Test# Concentration of Scar Coefficient Lubricant 1 Diameter of in OS-124 (mm) Friction (weight percent) C.S. A 0 1.06 0.28 Ex.6 10 0.88 0.16 The data shown in Table 1 demonstrates the effectiveness of a compound of the invention as an additive to improve the tribological properties of known lubricants.

10 FXAMPLE 7 AND COMPARATIVE SAMPLE B: ADDITIVE FRICTION AND
WEAR TEST

The procedure of Example 6 was followed with the exception that the poly(perfluorocyclobutane aryl ether) Lubricant 2 as prepared in Example 3 was S used in place of 1,2-bis(3-trifluoromethylphenyloxy)hexafluorocyclobutane (Lubricant 1 ) used in Example 6. The results obtained were reported in Table 2.
Table 2 Test # Concentration of Scar Coefficient Lubricant 2 Diameter of in OS-124 (mm) Friction (weight percent) C.S. B 0 1.06 0.28 Ex.7 10 0.~6 0.14 - 20 The data shown in Table 2 above demonstrates the effectiveness of the compound of this invention as an additive to improve the tribological properties of known lubricants.

~1~0~ ~

FXAMPI FS 8 AND 9 AND COMPARATIVE SAMPLES ~. D AND E:
EVALUATIONS AS TOPICAL LUBRICANTS ON COBALT-NICKEL MAGNFTIC
TAP~

s Experimental samples of topically-iubricated 8 mm cobalt-nickel magnetic tape were prepared by submerging unlubricated tape into a 0.1 or 1.0 weight percent (as indicated in Table 3) lubricant solution in Freon~ 113 (commerciallyavailable from E.l. DuPont de Nemours Co.) or methyl ethyl ketone (MEK).
Separate tape samples were prepared with I ubricant 1 (as Example 8) and Lubricant 2 (as Example 9) of the present invention, as well as comparison examples including a hexa-fluoropropylene epoxide polymer commercially available from E.l. DuPont de Nemours Co. under the trade designation KrytoxTM
143AC (as C.S. D); tetrafluoroethylene epoxide polymer commercially available from Ausimont U.S.A., Inc. under the trade designation FomblinTM AM 2001 (as lS C.S. E); and tape without lubricant (as C.S. C).

Coefficient of friction was measured by the procedure of ASTM D-3028 using a frictionometer commercially available from Custom Scientific Instruments, Inc.
Scratch appearance force and scratch depth were measured by a scratch test performed according to the procedure of ASTM D-2197 except that it was miniaturized by a factor of 10-3 to measure micrometer rather than millimeter scratches. In this test, a loaded stylus was dragged across a sample surface, and 2s the sample was inspected under 30X magnification to determine whether there was a visible scratch. Stylus load was varied from 0 to 40 mg in 10 mg steps. A
commercial profilometer with a stylus radius of 2.5~m was used for the test and was used to measure the depth of a scratch when one was observed. Depth was measured by retracing the scratch at 90 degrees to the observed scratch with a stylus load 10 mg less than the load used to make the scratch so that the measuring stylus does not increase the scratch depth.

The test results were shown below in Table 3.

WO 94/25547 2 i 6 0 70 a PCT/US94/04274 Table 3 Example Solvent Concentration CoefficientScratch Scratch (weightpercent) of AppearanceDepth (nm) FrictionForce (mg)(40 mg load) C. S. C Freon 113 0 0.35 30 15.0 C. S. D Freon 113 1 0.34 ,40 0 C. S. E Freon 113 1 0.07 >4~ 0 Ex. 8 MEK 1 0.08 40 5.0 Ex. 9 MEK 0.1 0.22 20 20.0 Test results show test Lubricant 1 and Lubricant 2 which were described in s EXAMPLE 3 were effective as topical lubricants for thin film magnetic media and were effectively applied from methyl ethyl ketone rather than a chlorofluorocarbon.

Claims

Claims:

1. A lubricant comprising compounds having a formula represented by Formula 2:

[R-X-Q-X-]v-[R'-X-Q-X]m-[R"-X-Q-X]n[R''']p-wherein each of R, and R''' are the same or different aromatic groups; R' is a branching group; R'' is an unbranched chain extending group derived from compounds having 2 dimerizable perfluorovinyl groups; X is oxygen or sulfur and Q is a perfluorocyclobutane group; subscripts v, m, n, and p are integers representing the number of groups in the brackets preceeding them such that v + p = am + 2 where (a + 2) is the number of dimerizable perfluorovinyl groups on R', and is 3 or 4.

2. The lubricant of Claim 1 wherein R is selected from perchlorophenylene, phenylene, biphenylene, naphthylene, dichlorophenylene, benzophenone, nitrophenylene, p,p'(2,2-diphenylene propane) [-C6H4-C(CH3)2-C6H4]; p,p'-(2,2-diphenylene-1,1,1,3,3,3 hexafluoropropane), [-C6H4-C(CF3)2-C6H4-], 1,4-bis(hexafluoroisopropyl)benzene [-C(CF3)2-C6H4-C(CF3)2-], 1,3-bis(hexafluoroisopropyl)benzene [-C(CF3)2-C6H4-C(CF3)2-], biphenylene;
phenylene; 9,9'-diphenylfluorene, oxydiphenylene; thiodiphenylene;
2,2-diphenylene propane; 2,2'-diphenylene, 1,1,1,3,3,3-hexafluoropropane;
1,1-diphenylene-1-phenylethane; naphthalene, anthracene and mixtures thereof .

3. The lubricant of Claim 2 wherein R has at least one fluorine or fluorine-containing substituent in addition to the perfluorocyclobutane rings.

4. A lubricant comprising at least one compound having a structure represented by at least one of Formulas 4 or 5:

Formula 4 wherein J is H, or an inert or reactive substituent; and K is an unsubstituted or inertly substituted hydrocarbyl group; or Formula 5 wherein n is an integer of from 0 to 20 and L is independently trifluoromethyl, fluorine, trifluoromethoxy, tetrafluoroethoxy, perfluoroalkoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, pentafluorosulfanyl, alkylphosphonate, piperaryl, amino or alcohol groups.

5. The lubricant of Claim 4 which is of Formula 5 wherein n is 0;
and L is a trifluoromethyl group.

6. The use of a composition comprising a lubricant base stock and at least 0.1 weight percent of a least one poly(perfluorocyclobutane aryl ether) as a lubricant.

7. The use of Claim 6 in which the poly(perfluorocyclobutane aryl ether) has aryl groups substituted with at least one fluorine, trifluoromethyl, tetrafluoroethoxy, trifluoromethoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfone, amide, pentafluorosulfanyl, alkyl phosphonate, piperanyl, amine group, alcohol or combination thereof.

8. The use of Claim 6 wherein the lubricant is prepared from a mixture of monomers having two dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group in a ratio of monomers having two dimerizable perfluorovinyl groups to end-capping agents of from 1:10 to 10:1.

9. The use of Claim 6 wherein the lubricant is a mixture of linear and branched structures, prepared from a mixture of monomers having two or more dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group, wherein the ratio of monomers having two dimerizable perfluorovinyl groups to monomers having more than two dimerizable perfluorovinyl groups to end-capping agents is from 1:0.1:1.5 to 1:200:2000.

10. A magnetic recording media comprising a substrate; a magnetic recording media thereon and a lubricating amount of a poly(perfluorocyclobutane aryl ether) lubricant as described in any of Claims 1 , 2, 3, 4, 5, 6, 7, 8, or 9.

11. A method of preparing magnetic media by forming a dispersion comprising a binder, a magnetic particle containing pigment, a lubricating amount of a poly(perfluorocyclobutane aryl ether), and a surfactant;
orienting the magnetic particles by application of a magnetic field;
evaporating the solvent; and curing the polymer binder.

12. A method of lubricating an engine using a lubricant comprising at least one poly(perfluorocyclobutane aryl ether) compound as described in any of Claims 1, 2, 3, 4, 5, 6, 7, 8, or 9.

13. A method of lubricating magnetic recording media using a lubricant comprising at least one poly(perfluorocyclobutane aryl ether) compound as described in any of Claims 1, 2, 3, 4, 5, 6, 7, 8, or 9.