Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From fluorine-containing reactant
Reexamination Certificate
1999-12-28
2002-06-11
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From fluorine-containing reactant
C528S070000, C528S076000, C528S080000, C528S085000, C525S410000, C525S453000, C525S460000, C526S242000, C549S511000
Reexamination Certificate
active
06403760
ABSTRACT:
FIELD OF INVENTION
The present invention relates to monohydroxyl polyfluorooxetane oligomers and polymers. The present invention further relates to radiation curable coatings made from functionalized polyfluorooxetane oligomers or polymers.
BACKGROUND OF THE INVENTION
Traditionally radiation curable coatings utilized combinations of silicone oils, wetting agents and polyethylene waxes to provide smoothness, abrasion resistance, low friction and scratch resistance. However these materials can be largely fugitive in nature and thus migratory leading to handling problems, lowering durability, and possibly working at cross-purposes leading to decreases in other coating properties such as gloss.
U.S. Pat. No. 5,411,996 disclosed the use of fluoroalcohol in U.V. epoxy-silicone coating formulations. The fluorinated alcohols were used to solubilize the U.V. initiator (sulfonium salt) to allow the polymerization reaction to occur.
U.S. Pat. No. 5,081,165 related to an anti-fouling coating composition comprising a photopolymerization initiator or thermal polymerization initiator and fluorine containing (meth)acrylate.
U.S. Pat. No. 4,833,207 relates to a curable composition for forming a cladding for an optical fiber having a refractive index of about 1.43 to 1.60.
U.S. Pat. No. 5,674,951 discloses isocyanate functionalized polyoxetane polymers with pendant fluorinated side chains that can optionally be chain extended with polyoxetanes or other polyethers, have the isocyanate group blocked, and be crosslinked into a network. These coatings were effective for glass run channels.
SUMMARY OF THE INVENTION
Monoalcohols are reacted with fluorooxetane monomers to produce monohydroxyl polyfluorooxetane oligomers and polymers utilizing cationic catalysts. The polyfluorooxetane oligomers and polymers can be reacted with cyclic ethers, or they can be functionalized with various end groups and thereafter used in a radiation curable coating composition. Generally, the oligomer or polymer can contain various functional groups such as acrylate, methacrylate, or a less reactive allylic, or other functional groups such as melamine, amine, epoxide, silyl, isocyanate, aceteyl acetate, and the like. These polyfluorooxetanes can be called fluorinated polyoxetanes or polyoxetanes with partially fluorinated pendant side groups (chains). These fluorinated oxetane repeating units have a single pendant fluorinated side group per repeating unit or they can have two pendant fluorinated side groups per repeating unit. The coating composition comprises the functionalized oligomer or polymer, a comonomer, optional UV initiator, crosslinking agents, and optionally other additives like pigments, plasticizers, rheology modifiers etc.
The functionalized polyfluorooxetane can be produced by several methods, but due to the reactivity of the hydroxyl groups of the polyfluorooxetane it is desirable to sequentially add the reactants so nearly complete functionalization of the polyfluorooxetane can be achieved. Typically, an isocyanate or epoxy functionalize polyfluorooxetane is first formed and that is reacted with a compound which will yield a functionalized polyfluorooxetane with intervening urethane linkages or linkages derived from the epoxy compound. Alternatively the functionalizing compound can be reacted with epoxy or isocyanate and the resulting compound then reacted with the polyfluorooxetane. Alternatively the fluorinated polyol may be made through tranesterification or an unsaturated alcohol may be used in the initiation step for the formation of the mono-functional fluorinated material.
DETAILED DESCRIPTION OF THE INVENTION
Generally, any type of monoalcohol can be utilized to produce the monohydroxyl polyfluorooxetane (MOX) oligomers or polymers of the present invention. The monoalcohol generally has from 1 to about 40 and preferably from about 1 to about 18 carbon atoms. Examples of specific types of monohydric alcohols include the various aliphatic alcohols such as the paraffinic alcohols, for example methyl alcohol, ethyl alcohol, propyl alcohol, etc., or the olefinic alcohols, for example vinyl alcohol, allyl alcohol, and the like. Various alicyclic alcohols such as cyclohexanol and the like can be utilized, as well as various aromatic alcohols such as benzyl alcohol, phenol, and the like. Various heterocyclic alcohols can also be utilized such as furfuryl alcohol, and the like. Moreover, halogenated alcohols and especially fluoroalcohols are desired such as trifluoroethanol, heptafluorobutanol, and the like. Especially preferred monohydric alcohols include benzyl alcohol, trifluoroethanol, heptafluorobutanol, and allyl alcohol.
The oxetane monomer used to form the polyfluorooxetane has the structure
and the repeating unit derived from the oxetane monomer has the formula
where each n is the same or different and independently, is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and individually is an oxaperfluorinated polyether having from 4 to 60 carbon atoms. The amount of the fluorooxetane monomers utilized is sufficient to yield a degree of polymerization (DP) of from about 2 to about 150, desirably from about 3 to about 50, and preferably from about 12 to about 25.
Generally any suitable cationic catalyst can be utilized to polymerize the fluorooxetane monomers such as various Lewis acids and complexes thereof. Examples of such cationic catalysts include Sn(IV)Cl
4
, antimony pentafluoride, phosphorous pentafluoride, and the like, with a complex of borontrifluoride and tetrahydrofuran being preferred. Optionally, various co-catalysts can be utilized such as water, butanediol, cyclohexanedimethanol, and the like.
The homopolymerization is generally carried out in the presence of a catalyst as well as in a solvent for the monoalcohol and the fluorooxetane monomer. Examples of suitable solvents include trifluorotoluene, dichloroethane, dimethylformamide, as well as dichloromethane. The amount of the alcohol and catalyst will generally vary inversely with the desired molecular weight of the polymer. That is, the polymerization is initiated by each alcohol and catalyst molecule generally on a quantitative basis for a given amount of fluorooxetane monomer, hence, the molecular weight of the polyfluorooxetane oligomer or polymer will be determined by the amount of alcohol utilized.
The reaction rate will vary with temperature. Accordingly, the reaction time is generally from 2 hours to 40 hours, and desirably is from about 4 to about 24 hours. The polymerization temperatures are generally from about 0° C. up to about 100° C., and desirably from about 18° C. to about 50° C. Lower reaction temperatures result in very slow reaction rates, whereas higher reaction temperatures can enhance the formation of cyclic structures containing from 3 to 4 oxetane units. As noted, monomer conversion to polymer is essentially quantitative. The monohydroxyl polyfluorooxetane oligomers or polymers produced are washed with water to obtain a neutral pH and the water removed as by decanting. Subsequently, any suitable desiccant can be utilized such as calcium chloride, phosphorous pentoxide, calcium carbonate, magnesium sulfate, molecular sieves, to dry the oligomers or polymers.
The monofunctional polyfluorooxetane oligomers or polymers generally have the formula
where “n” R, Rf and DP are as described hereinabove and R
1
is the organic group of the reactive monoalcohol. That is, R
1
can be an aliphatic group such as a paraffinic group or an olefinic group, or an alicyclic group, or an aromatic group, or a heterocyclic group, or a halogenated organic group, and the like, having from 1 to about 40 and preferably from 1 to about 18 carbon atoms. If more than one type of mono
Carlson Roland
Garcia Guillermina C.
Malik Aslam
Medsker Robert E.
Weinert Raymond J.
Hudak Daniel J.
OMNOVA Solutions Inc.
Rywalski Robert F.
Wu David W.
Zalukaeva Tanya
LandOfFree
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