WO2005010074A1

WO2005010074A1 - Radiation polymerization of fluorooxetanes

Info

Publication number: WO2005010074A1
Application number: PCT/US2004/023697
Authority: WO
Inventors: Charles Kausch; Raymond Weinert; Guillermina Garcia
Original assignee: Omnova Solutions Inc
Current assignee: Omnova Solutions Inc
Priority date: 2003-07-23
Filing date: 2004-07-23
Publication date: 2005-02-03
Anticipated expiration: 2006-01-23

Abstract

Exposure to radiation, such as ultraviolet light, can result in (co)polymerization of mixtures that include fluorooxetane monomers, an initiator containing at least one hydroxyl group, and a radiation sensitive (cationic and optionally a free-radical) catalyst. The polymerization process can be carried out in the absence of a solvent.

Description

HADIATIOM FO-LYMEMZATIOM OF FLUOROOXETAMES [01] This application gains benefit from U.S. Provisional Serial No.

60/489,342, -filed on July 23, 2003.

BACKGROUND OF THE INVENTION

[02] The present invention relates generally to the polymerization of fluorooxetane (FOX) monomers, more specifically to polymerizations conducted in the presence of a hydroxyl-containing initiator and a radiation induced or activatable catalyst to produce a polyoxetane having a high number average molecular weight.

[03] Heretofore, oxetane monomers containing pendant fluorinated ether groups, often in combination with other cationically polymerizable monomers and prepolymers, have been polymerized in the presence of a Lewis acid catalyst (e.g., BF3 • etherate and BF3 • THF) and a mono- or poly-hydroxy aliphatic initiator (e.g., a diol such as ethylene glycol or 1,4-butanediol). The catalyst and initiator usually are mixed in a solvent prior to addition of the FOX monomers.

SUMMARY OF THE INVENTION [04] In general the present invention provides a process for making a polymer that comprises side chains that are at least partially fluorinated, the process comprising the steps of combining ingredients including a fluorooxetane monomer, a hydroxyl-containing initiator, and a radiation catalyst, providing radiation to form a radiation-polymerized fluorinated polyoxetane polymer, where said fluorooxetane monomer can be represented by the formulas

wherein each n is the same or different and independently is an integer of from 1 to about 6, R is hydrogen or an alkyl of from 1 to about 6 carbon atoms, and each Rf is the same or different and independently is a fluorinated alkyl of from 1 to about 20 carbon atoms, and wherein a minimum of 25% of the non-carbon atoms of said fluorinated alkyl are fluorine atoms and the remaining non-carbon atoms are hydrogen, iodine, chlorine, or bromine.

[05] The present invention also includes an polymeric network formed by a process comprising the steps of combining ingredients including a fluorooxetane monomer, a hydroxyl-containing initiator, and a radiation catalyst to form a film, applying radiation to the film to form polymeric network, where said fluorooxetane monomer can be represented by the formula

wherein each n is the same or different and independently is an integer of from 1 to about 6, R is hydrogen or an alkyl of from 1 to about 6 carbon atoms, and each Rf is the same or different and independently is a fluorinated alkyl of from 1 to about 20 carbon atoms, and wherein a minimum of 25% of the non-carbon atoms of said fluorinated alkyl are fluorine atoms and the remaining non-carbon atoms are hydrogen, iodine, chlorine, or bromine. [06] The present invention further a radiation-polymerizable composition comprising ingredients including a hydroxyl-containing initiator, and a radiation catalyst, and fluorooxetane monomer that can be represented by the formulas

wherein each n is the same or different and independently is an integer of from 1 to about 6, R is hydrogen or an alkyl of from 1 to about 6 carbon atoms, and each Rf is the same or different and independently is a fluorinated alkyl of from 1 to about 20 carbon atoms, and wherein a minimum of 25% of the non-carbon atoms of said fluorinated alkyl are fluorine atoms and the remaining non-carbon atoms are hydrogen, iodine, chlorine, or bromine. DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[07] Exemplary FOX monomers useful in the present process include those that include at least one pendent fluorinated group, preferably a pendent fluoroalkoxyalkyl group such as -CH2OCH2 where Rf is a (per) fluorinated group, preferably a perfluorinated alkyl group. Such monomers, with or without other type(s) of monomers, are polymerized by exposure to radiation. Conventional Lewis acid catalysts generally are not utilized but, instead, cationic radiation activated catalysts are utilized with one or more of a variety of hydroxyl group- containing initiators such as, e.g., mono- or poly-hydroxy alcohols, polyester- or polyether-containing polyols, and epoxy esters or epoxy carboxylates. [08] The FOX monomers can be polymerized alone or with unsaturated monomers which typically contain a functional group (e.g., an epoxy (meth)acrylate or (meth)acrylated urethane). Alternatively, FOX monomers can be polymerized by radiation and, subsequently the other type(s) of monomers polymerized as by radiation or other technique. [09] Preferred FOX monomers have the general formula

wherein each n independently is an integer of from 1 to about 6, preferably 1 or 2;

R is H or a C1 -C6 alkyl group, preferably a C1-C2 alkyl group; and each Rf independently is a linear or branched fluorinated Cj-C20 alkyl group, preferably a

C1-C15 group, more preferably a C^-Cs alkyl group, and most preferably a C1-C6 alkyl group. Of the non-carbon atoms in each Rf, a minimum of 25%, preferably at least about 50%, more preferably at least about 75%, even more preferably at least about 85%, and most preferably at least about 95% are F and, optionally, the remainder can be H, I, Cl, or Br.

[10] Examples of FOX monomers include 3-(2,2,2-Trifluoroethoxymethyl)-3-

Methyloxetane (3-FOX), 3-(2,2,3,3,4,4,4-Heptafluorobutoxymethyl)-3-

Methyloxetane (7-FOX), 3-methyl-3-{ [3,3,4, 4,5,5,6, 6,6- nonafluorohexyl)oxy] methyl} oxetane (9-FOX), and 3,3-bis-(2,2,2- trifluoroethoxymethyl) oxetane (3B-FOX).

[11] Preparation of FOX monomers is known; exemplary methods can be found in, e.g., U.S. Pat Nos. 5,650,483; 5,668,250; 5,668,251; 5,663,289; and 6,479,623, those teachings being fully incorporated herein by reference. [12] Polymerization of the FOX monomers generally is carried out in the absence of an inert or non-reactive solvent with respect to the FOX monomers. If solvents are utilized, they generally are halogenated hydrocarbons such as, e.g., CH2CI2, CCI4, CHCL3 CHCl=CCl2, chlorobenzene, CH3CH₂Br, dichloroethane, fluorinated solvents, etc. with a preferred solvent being CH2CI2 alone or mixed with one of a variety of chlorofluorocarbons. Other solvents such as SO2, hexane, petroleum ether, toluene, dioxane and xylene as well as other common solvents can also be used. Desirably, the amount of any solvent utilized is generally less than about 25 or 15 pbw, desirably less than about 10 or 5 pbw, preferably less than about 3 pbw, and most preferably 0 pbw, based upon 100 pbw of the FOX monomer (s).

[13] The polymerization of the present invention does not require Lewis acid catalysts such as complexes of BF3, PF5, SbFs, ZnCl2, AlBrs, and the like. The amount of any such catalyst, if utilized, is very low, for example less than about 1 pbw, preferably less than about 0.5 pbw, more preferably less than 0.1 pbw based upon 100 pbw of the total amount of the FOX monomers. [14] Useful initiators generally contain at least one hydroxyl group and include water (which can be derived from atmospheric humidity, if desired), alcohols, polyols containing typically a polyether or polyester intermediate, and epoxy esters or carboxylates. The alcohols can have anywhere from 1 to about 4 hydroxyl groups and thus include mono- and polyols. The number of carbon atoms can vary generally from about 1 to about 40, with from about 1 to about 5 or 10 being preferred. Examples of monoalcohols include monools such as monohydroxyl aliphatic alcohols including alkyl, olefinic, cyclic, and aromatic alcohols such as methanol, ethanol, propanol, allyl alcohol, cyclohexanol, furyl alcohol, benzyl alcohol and the like; polymeric alcohols which generally are made from one or more C2-C6 alkylene oxides such as, e.g., ethylene oxide, propylene oxide, or THF, with the number of repeat units generally ranging from about 2 to about 50, desirably from about 3 to about 30, preferably from about 5 to 20; telomer fluoroalcohols which have the general formula CF3CF2(CF2CF2)_X CH2CH2OH where x typically is an integer of from 1 to about 19, usually from about 8 to about 12; and fluorinated alcohols which generally have from 2 to about 18 carbon atoms such as trifluoroethanol, heptafluorobutanol, heptadecylfluorooctanol, and the like. Preferred monohydroxyl alcohols include benzyl alcohol, trifluoroethanol, heptafluorobutanol, pentafluoropropanol, pentafluorobutanol, nonafluorohexanol, various perfluoroalkyl monoalcohols and allylic alcohol. [15] Preferred initiators include diols or glycols that contain up to about 10 carbon atoms such as, e.g., ethylene glycol, propylene glycol, butane- 1,4-diol, isobutene-l,3-diol, pentane- 1,5 -diol, and l-cyclohexyl-l,3-butane diol. [16] Polyether and polyester polyol initiators generally include polyerhers such as those derived from C2-C alkylene oxides. Suitable polyether polyols include polyoxypropylene or polyoxylene ethylene di- and triols, copolymers such as poly(oxyethylene-oxypropylene) di- and triols, and the like. The polyether polyol initiators generally have a degree of polymerization, Dp, of from about 2 to about 40 and, desirably, from 2 to about 20.

[17] Polyester polyols typically are formed from the condensation of monomers such as one or more C^-C^g polyhydric alcohols with one or more C2-

C14 polycarboxylic acids or their anhydrides. Examples of suitable polyhydric alcohols include ethylene glycol; propylene glycol such as 1,2- and 1,3-propylene glycol; glycerol; pentaerythritol; trimethylolpropane; 1,4,6-octanetriol; butanediol; pentanediol; hexanediol; dodecanediol; octanediol; chloropentanediol, glycerol monoallyl ether; glycerol monoethyl ether, diethylene glycol; 2-ethylhexanediol- 1,4; cyclohexanediol-1,4; 1,2,6-hexanetriol; neopentyl glycol; 1,3,5-hexanetriol; l,3-bis-(2-hydroxyethoxy)propane; and the like; C2-C18 cyclic ethers also may be used. Examples of polycarboxylic acids include phthalic acid; isophthalic acid; terephthalic acid; tetrachlorophthalic acid; maleic acid; dodecylmaleic acid; octadecenylmaleic acid; fumaric acid; aconitic acid; trimellitic acid; tricarballylic acid; 3,3'-thiodipropionic acid; succinic acid; adipic acid; malonic acid, glutaric acid, pimelic acid, sebacic acid, cyclohexane-l,2-dicarboxylic acid; 1,4- cyclohexadiene- 1 , 2-dicarboxylic acid; 3-methyl-3, 5-cyclohexadiene- 1,2- dicarboxylic acid; and the corresponding acid anhydrides, acid chlorides and acid esters such as phthalic anhydride, phthaloyl chloride and the dimethyl ester of phthalic acid. Polyesters from lactones (for example caprolactone) also can be used. Polyester polyol initiators generally have a Dp of from about 2 to about 25 and, desirably, from about 2 to about 20.

[18] Preferred polyester polyol initiators can prepared by reacting adipic and/or phthalic acid (or derivatives thereof) with one or more glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, hexamethylene glycol, trimethylolpropane, or trimethylolethane. Other polyester polyol initiators include poly (ethylene adipate) glycol, poly (diethylene adipate) glycol, poly(ethylene/propylene adipate) glycol, poly (propylene adipate) glycol, poly(butylenes adipate) glycol, poly(neopentyl adipate) glycol, poly (hexamethylene adipate) glycol, poly(hexamethylene/neopentyl adipate) glycol, and the like.

[19] Epoxy carboxylates and epoxy esters are suitable initiators which give rise to polymerization, generally in the presence of a cation such as that generated by a catalyst. These initiators and include generally cycloaliphatic epoxy compounds such as Cyracure™ UVR-6110 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate and Cyracure™ UVR-6128 bis-(3,4-epoxycyclohexyl) adipate, both which are commercially available from Dow Chemical Co. (Midland, Michigan). Cyracure™ UVR-6105 epoxide (Dow) also can also be utilized.

[20] The amount of the initiator(s) used is generally from about 0.01 to about 20 pbw, preferably about 0.1 to about 10 pbw, more preferably from about 0.3 to about 5 pbw, and most preferably from about 0.5 to about 2 pbw for every 100 pbw of the FOX monomers. [21] The radiation-polymerizable composition may optionally contain one or more co-reactants. In some embodiments, the co-reactant is believed to increase the reaction rate of the polymerization of the one or more FOX monomers. Useful co-reactants include radiation-polymerizable monomers. Examples of suitable co- reactants include vinyl ethers, vinyl esters, and epoxies, generally in an amount of from about 0.1 to about 10 pbw, and preferably from about 0.5 to about 8 pbw per 100 pbw of FOX monomers.

[22] The vinyl ethers include a C1-C20 hydrocarbon group such as a C1-C20 aliphatic group, a C3-C10 cycloaliphatic group, a Cβ-Cis aromatic group, or combinations thereof. The vinyl ether can also contain a C2-C4 alkylene oxide group. Examples of specific vinyl ethers include divinyl ether, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl cetyl ether, vinyl cyclohexane ether, and the like.

[23] The vinyl esters are structurally similar to the vinyl ethers with respect to the types and sizes of useful hydrocarbon groups. Examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl cyclohexate, and various acrylates with a C^-C^o ester portion (e.g., ethyl acrylate). [24] The epoxy co-reactants generally have a total number of carbon atoms of from about 2 to about 20, preferably from about 3 to about 15, and include epichlorohydrin, various C/j-Cβ alkylene oxides such as ethylene and propylene oxide; phenyloxirane, epoxy cyclopentane, dimethyloxirane, diglycidyl ether, and epoxy compounds of the formula

O / \ Ax H₂C-CH-CH₂-O-R-O-CH₂-CH-CH₂

where R is a Ci -Cβ alkyl group. Glycidal methacrylate and bis-phenol A and its derivatives also can be used.

[25] Useful radiation catalysts include those affected by specific wavelengths of the electromagnetic spectrum such as visible light, UV light having a wavelength of from about 10 to about 400 nm and preferably from about 200 to about 390 nm, at a dose of about 10 to about 3,000 mJ/cm2, or particles such as that generated by an electron beam apparatus at a level of from about 1 to about 4 MRad.

[26] Preferred catalysts are radiation- or photo-induced cationic catalysts which generally generate a cation upon irradiation and initiate acid-catalyzed ring- opening polymerization of the FOX monomers and any co-reactants. For example, a catalyst used in the cationic UV polymerization relies on the production of compounds such as HPF6 or HSbFό to provide the cationic polymerizing species.

Classes of such catalysts include the hexafluoroantimonates (salts), pentafluorohydroxyantimonates (salts), hexafluorophosphates (salts), hexa- fluoroarsenates (salts) and other photo-induced cationic polymerization initiators represented by the following formulas (I) to (XV):

Ar₂I⁺ - (I)

wherein Ar is an aryl group, for example, a phenyl group; and XT is PF6^~, SbF ^~ or

Ar₃S⁺ XT (II) wherein Ar and X^~ are defined as above;

wherein R^ is a C1-C12 alkyl or alkoxy group, n is an integer of from 0 to 3, and X^~ is defined above;

(IV)

wherein Y^" is PF6^~, SbF ^", AsF6^~ or SbFs(OH) ^~;

CV)

wherein X^" is defined as above;

wherein XT is defined as above;

wherein X^~ is defined as above;

R⁴ R³— S⁺X~ I , ^R (VIII) wherein R^ is a C -C15 aralkyl group or a C3-C9 alkenyl group, R4 is a Cι~C7 hydrocarbon group or a hydroxyphenyl group, R^ is a C1-C5 alkyl group which may contain O and/or S atom(s), and X^" is defined as above;

wherein each of R^ and R^ independently is a C1-C12 alkyl or alkoxy group;

wherein R^ and R? are defined as above; and

[27] Such catalysts include Cyracure™ UVI-6974 mixed triphenylsulfonium hexafluoroantimonate salts, Cyracure™ UVI-6990 mixed triphenylsufonium hexafluorophosphate salts, and Cyracure UVI-6970, all commercially available from Dow Chemical; Ciba™ Irgacure™ 264 photoinitiator (Ciba Specialty Chemicals; Tarrytown, New York), and CIT-1682 photoinitiator (Nippon Soda Co., Ltd.). Compounds which contain the hexafluorophosphate anion (PFβ-) are preferred. These and other suitable cationic polymerization catalysts are set forth in U.S. Pat. Nos. 5,721,020, 5,882,842, and 6,555,595, which are hereby incorporated by reference.

[28] Various iodinium catalysts include compounds such as set forth in

Formulas XII and XIII above.

[29] The amount of catalyst employed in the compositions of this invention is generally from about 0.01 to about 10 pbw, preferably from about 0.1 to about 5 pbw, and more preferably from about 0.5 to about 3 pbw per 100 pbw of FOX monomer(s) .

[30] The FOX monomer(s) in the presence of the initiator(s) and the radiation catalyst(s), preferably free of any solvent or Lewis acid catalyst, are polymerized to form oligomers or desirably polymers. The radiation is typically UV light but other radiation can be utilized. The hydroxyl-terminated polyfluorooxetane can also be used as the initiating species of the cationic initiator. [31] In some embodiments, an induction period is observed, where polymerization does not begin upon exposure of the radiation-polymerizable composition to radiation, but instead begins after some period of time has elapsed after exposure to the radiation. Advantageously, the induction period can be reduced by addition of a co-reactant. In a preferred embodiment, the co-reactant is a monomer that is radiation-polymerizable. [32] The FOX monomer(s) can optionally be copolymerized with a variety of comonomers having epoxy (oxirane) functionality such as epichlorohydrin, propylene oxide as well as C -Ci5, preferably C7-C12, alkyl-substituted oxiranes or mixtures thereof; monomers having a 4-membered cyclic ether group such as trimethylene oxide, 3,3-bromomethyl(methyl)oxetane; monomers having a 5- membered cyclic ether group such as THF, tetrahydropyran, and 2-methyltetra- hydrofuran; and the like. Still other suitable monomers include 1,4-dioxane, 1,3- dioxane and 1,3-dioxalane as well as trioxane and caprolactone. Copolymerization is carried out generally under the same conditions as is the polymerization of the FOX monomers set forth hereinbelow. The amount of comonomer(s) when utilized, desirably ranges from about 1 to about 20%, preferably up to about 10%, by weight based upon the total weight of monomers.

[33] The radiation polymerization of the FOX monomers and the optional comonomer(s) can be carried out at ambient temperatures or at elevated temperatures such as about 30° up to about 50°C, about 75°C, about 100°C, about 150°C, or even about 200°C.

[34] The resulting oligomers or (co) polymers generally contain repeat units of the formula

CH₂-0-(CH₂)_nRf CH O-(CH₂)_nRf -(0-CH₂-C-CH₂)-_Dp or -(O-C^-C-C^)-^ R CH₂-0-(CH₂)_nRf I IB

where each n, R, and Rf is as noted above and Dp is from about 6 to about 500, preferably from about 10 about 40, such that the number average molecular weight (M_n) is from about 1000 to about 75,000, desirably from about 2000 to about 50,000, preferably from about 3000 to about 25,000, more preferably from about 4000 about 20,000, and most preferably from about 5000 to about 15,000. [35] Inasmuch as the initiator often is incorporated into the resultant polymer but the catalyst is not, the polymer typically has an initiator residue located at an end thereof. Whenever the initiator is a polyol, for example two OH end groups, the polymer can be represented by the following formulas

CH₂-0-(CH₂)_nRf CH₂-0-(CH₂)_nRf H-(0-CH₂-C-CH₂)- OR'-OH or H-(0-CH₂-C-CH₂)- OR'-OH I Dp Dp R CH₂-0-(CH₂)_nRf IA IB

where R' is the hydrocarbyl or organic, e.g., alcohol or polyester or polyether, residue of the initiator. When the initiator contains only one hydroxyl group, for example a monool, the terminal end group is generally hydrocarbyl and the polymer can thus be represented by the following formulas:

CH₂-0-(CH₂)_nRf CH₂-0-(CH₂)_nRf H-(0-CH₂-C-CH₂)- OR' or H-(0-CH₂-C-CH₂)- OR' I Dp Dp R CH₂-0-(CH₂)_nRf I IB

[36] Such hydrocarbyl-terminated polymers result in compositions which have a low amount of cyclic ethers such as less than about 10 or about 5 and desirably less than about 3 pbw per 100 pbw of the FOX monomer (s). [37] When co-reactants and/or comonomers are utilized, the above noted repeat groups can contain such comonomers therein. For example when a co- reactant such as an epoxy, a vinyl ether, or a vinyl ester monomer is utilized, or a comonomer such as THF, the same will be incorporated in the backbone in a random manner. [38] The following example serves to illustrate but not to limit the invention with regard to UV light polymerization of FOX monomers in the absence of solvent: To a reaction vessel, 20 g of 9-Fox monomer was added, followed by 0.20 g heloxy 61 (butyl glycidyl ether), and 0.20 g Cyracure™ UVT-6974 photoinitiator in the presence of atmospheric moisture. The mixture was stirred, added to a small crystallizing dish, and conveyed through a Linde™ UV unit at 20 cm/sec (40 feet/min), 6 passes. NMR spectroscopy revealed that the polyfluorooxetane polymer had a degree of polymerization (Dp) of about 23.

[39] The FOX monomer(s) can be reacted or polymerized by radiation either alone or in the presence of other monomers capable of being polymerized as by a free radical mechanism. In one embodiment, the second type or class of monomers can generally be described as functional containing unsaturated monomers and thus can be any type of compound containing the same such as unsaturated acids, unsaturated esters, unsaturated epoxy compounds, and the like. Acrylic acid, the acrylates, and the acrylated urethanes form preferred monomers. [40] Various scenarios exist with regard to the polymerization of the two different classes of monomers. One scenario is that the various FOX monomers can first be polymerized by UV light followed by radiation polymerization and optional cure of various one or more second class of monomers in the presence of the formed polyfluorooxetanes. Another scenario is that the FOX monomers can be polymerized generally simultaneously with the second class monomers utilizing two polymerizing mechanisms, that is a radiation polymerization of the FOX monomers in a manner noted hereinabove utilizing polyol initiators and UV light catalysts with polymerization of the second class monomers, such as an acrylate, via a different mechanism, e.g., radiation via a free radical mechanism. In either situation the result is a blend or mixture of the two polymers, or an interpenetrating network of the two different types or classes of polymers, or combinations thereof. With respect to the second polymerization or that of the second class of monomers, the type, wavelength, and intensity of radiation utilized can be the same as set forth hereinabove with regard to the FOX monomers. [41] Examples of the second class of monomers include (meth) acrylate or hydroxy(meth)acrylate monomers, (meth) acrylate- or hydroxy (meth) acrylate- terminated urethane oligomers or polymers, epoxy acrylates, and the like.

[42] Examples of suitable acrylates include 2-phenoxyethyl acrylate, ethoxylated phenol monoacrylate, lauryl acrylate, hexadecyl acrylate, stearyl acrylate, tripropy ene glycol, methylether monoacrylate, neopentylglycol propoxylate(2)methylether monoacrylate, propoxylated(2-20)nonylphenol mono acrylate, and the like. Suitable alkyl (meth) acrylates are those with C1-C20 alkyl groups and include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2- ethyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl (meth) acrylate, isobornyl acrylate, and cyclohexyl (meth) acrylate, and the like. Examples of suitable (meth) acrylates having ether groups include 2- methoxyethylmethacrylate, 2-ethoxyethylmethacrylate, 3- methoxypropylmethacrylate, and the like. Examples of suitable hydroxyalkyl (meth) acrylates include 2-hydroxethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, 4-hydroxybutylacrylate, 6-hydroxyhexylacrylate, p- hydroxycyclohexyl (meth) acrylate, hydroxypolyethylene glycol (meth) acrylates, hydroxypolypropylene glycol (meth) acrylates and alkoxy derivatives thereof, and the like.

[43] A (meth) acrylate terminated polyurethane can be made by reacting one or more polyisocyanates with one or more polyols, that is a polyol intermediate, and then providing a (meth) acrylate end group. The polyol intermediate is generally a polyether polyol, preferably a polythioether polyol, a polyacetal polyol, a polyolefin polyol, an organic polyol, preferably a polycarbonate polyol, or preferably a polyester polyol, or combinations thereof, desirably having primary or secondary hydroxy groups. Such polyols and the preparation thereof are well known to the art and to the literature. The (meth) acrylate terminated polyurethane generally has a weight average molecular weight (M_w) of from about 400 to about 15,000 (preferably about 5000 or about 10,000) and desirably from about 800 to about 2000 (preferably 1500). [44] Polyether polyols generally are derived from C2-C10 monomers. Such polyols include polyoxypropylene or polyoxyethylene di- and triols, poly(oxyethylene-oxypropylene) di- and triols, and the like. Polythioether polyols which can be used include products obtained by condensing thiodiglycol either alone or with other glycols, dicarboxylic acids, formaldehyde, aminoalcohols or aminocarboxylic acids. Useful polyacetal polyols include those prepared by reacting, for example, glycols such as diethylene glycol, triethylene glycol and hexanediol with formaldehyde. Suitable pol acetals also may be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols include hydros-terminated butadiene homo- and copolymers. Organic polyols having molecular weights below 400 can also be used in the preparation of the prepolymers particularly include those made from monomers such as di- and triols and mixtures thereof, but higher functionality polyols can be used. Examples of such lower molecular weight monomers include ethylene glycol, diethylene glycol, tetraethylene glycol bis(hydroxyethyl) terephthalate, cyclohexane dimethanol, furan dimethanol, glycerol, neopentyl glycol and the reaction products, up to molecular weight 399 of such polyols with propylene oxide and/or ethylene oxide.

[45] The polycarbonate polyols which can be used include products obtained by reacting monomers such as C2-C10 diols such as 1,3-propanediol, 1,4- butanediol, 1,6-hexanediol, diethyene glycol or tetraethylene glycol with C13-C20 diaryl carbonates, for example diphenyl carbonate, or with phosgene.

[46] Useful polyester polyols are the same as those described previously.

Preferred polyol intermediates include polyesters as prepared from the reaction between adipic acid or phthalic acid or isomers thereof with glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, hexamethylene glycol, trimethylolpropane, or trimethylolethane. Specific polyester intermediates include poly (ethylene adipate) glycol, poly (diethylene adipate) glycol, poly(ethylene/propylene adipate) glycol, poly (propylene adipate) glycol, poly(butylenes adipate) glycol, poly (neopentyl adipate) glycol, poly (hexamethylene adipate) glycol, poly(hexamethylene/neopentyl adipate) lycol, and the like.

[47] The polyisocyanate(s) that are reacted with the polyol intermediate to form a polyurethane generally have the formula R(NCO)_n where n is from about 2 to about 4, with approximately 2 being preferred (because combinations of various polyisocyanates can be utilized, the equivalent amount of isocyanate can vary and often n is not an integer) and R is a C2-C20 preferably C6-C15 aliphatic group; a C.2-C.20- preferably C6-C12 (alkyl-substituted) aromatic group; or combinations thereof. Examples of suitable polyisocyanates include hexamethylene diisocyanate (HMDI), 2,2,4-and/or 2,4,4-trimethyl hexamethylene diisocyanate, p- or m- tetramethyl -i-ylene diisocyanate, methylene bis(4-cyclohexyl isocyanate) (hydrogenated MDI), 4,4-methylene diphenyl isocyanate (MDI) mixtures of MDI with polymeric MDI having an average isocyanate functionality of from about 2 to about 3.2, p- and m-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate (TDI) and adducts thereof, and isophorone diisocyanate (IPDI). Also useful are diisocyanates prepared by capping low molecular weight compounds, that is less than 300, such as epsilon-caprolactam, butanone oxime, phenol, etc., with diisocyanates. Any combination of polyisocyanates can be employed. Preferred polyisocyanates include aliphatic diisocyanates such as IPDI, MDI, HMDI, and the like.

[48] The equivalent number ratio of the one or more diisocyanates to the total of the one or more polyol intermediates can be from about 0.8 to about 1.2, and desirably from about 0.9 to about 1.1. [49] To render the above-noted polyurethanes reactive to radiation, they can be reacted with a hydroxyl (meth) acrylate to yield a terminal (meth) acrylate end group. Such compounds can be the same as set forth hereinabove with regard to the acrylate-type monomers. [50] The epoxy acrylates can be any epoxy compounds terminated by an acrylate group wherein the epoxy can be any of the epoxy co-reactants set forth above.

[51] The second class of monomers (i.e., the acrylates or urethane acrylates) are polymerized by a free radical mechanism in the presence of various known initiators. One such class of initiators include benzophenone and substituted benzophenones, benzoin and its derivatives such as benzoin butyl ether and benzoin ethyl ether, benzil ketals such as benzil dimethyl ketal acetophenone derivatives such as ,α-diethoxyacetophenone and α,α-dimethyl-α- hydroxyacetophenone, benzoates such as methyl-o-benzoyl benzoate, thioxanthones, Michler's ketone, and acylphosphine oxides or bis-acylphosphine oxides. Examples of other photoinitiators include hydroxylcyclohexyl phenyl ketone (HCPK), 2-benzyl-2-N, N-dimethylamino-l-(4-morpholino phenyl)-l- butanone (DBMP), 1 -hydroxyl cyclohexyl phenyl ketone, benzophenone, 2-methyl- l-(4-methylthio)phenyl-2-morpholino propan-1-one (MMP), and the like. Ciba™ Irgacure™ 500 benzophenone and 1-hy -ro-cycycloheχyl acetophenone (Ciba Specialty Chemicals) is a preferred liquid free-radical photoinitiator. [52] The amount of the one or more UV initiators with respect to the free radical-initiated acrylic monomer, urethane-acrylate polymer, or epoxy acrylate is generally from about 0.5 to about 10, desirably from about 1 to about 5 pbw, preferably from about 2 to about 4, per 100 pbw of the one or more second class of monomers such as the acrylates or urethane-acrylates. [53] The one or more above noted acrylate-type polymers (second type of polymers) often are crosslinked to provide improved properties. Such crosslinking agents include various (meth)acrylate-terminated polyols containing two or more hydroxyl end groups. Examples of such polyols include 1,6-hexanediol diacrylate, bisphenol A ethoxylated diacrylate, polyethylene glycol diacrylate (200-600), tripropylene glycol diacrylate, neopentylglycol propoxylate diacrylate, ethoxylated neopentyl glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane ethoxylated methylether diacrylate, and the like.

[54] Examples of trifunctional compounds include various acrylates such as trimethylolpropane triacrylate, trimethylolpropane propoxylate triacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated pentaerythritol triacrylate, and the like.

[55] Examples of other polyfunctional compounds include various acrylates such as ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, and the like. [56] Whether the two types of monomers, i.e., FOX and the second class such as the acrylate type, are polymerized together, or an existing radiation polymerized polyfluorooxetane polymer is polymerized with acrylate monomers and/or urethane-acrylate, etc., type polymers, the amount of the FOX monomer or polymer can vary from about 0.1% to about 15%, desirably from about 0.5% to about 10%, preferably from about 1% to about 5% by weight based upon the total weight of FOX monomers or polymers and the total weight of the one or more second class of monomers or polymers. The polymerization is carried out by blending various components together and then applying the radiation such as in the form of UV light.

[57] In one embodiment, a radiation-polymerizable coating composition including a fluorooxetane monomer, a hydroxyl-containing initiator, and a radiation catalyst is formed into a film, and the film is exposed to radiation to polymerize the monomer and form an infinite polymeric network. In a preferred embodiment, the film is formed on a surface or substrate and exposed to radiation in a controlled environment. The thickness of the coating prior to cure or exposure to the radiation can vary; although in certain embodiments, the thickness of the film can vary from about 1 micrometer to about 1 centimeter, preferably from about 10 micrometers to about 5 millimeters, and more preferably from about 50 micrometers to about 1 millimeter.

[58] Utilization of FOX monomers or polymers have been found to impart improved properties to the acrylic type polymers and thus the compositions are often used as additives with regard to yielding improved contact angle and improved stain resistance, mar resistance, scratch resistance, improved flow, wetting, and leveling properties, and the like. Moreover, the blends, interpenetrating polymer networks, etc. of the two different types of compositions can be utilized in coating formulations such as for paints, laminates, and the like. Other uses include electronic components such as computer chips, etc. as a photoresist composition, for halographic images and gratings and the like. [59] In order to demonstrate the practice of the present invention, the following examples have been prepared and tested. The examples should not, however, be viewed as limiting the scope of the invention. The claims will serve to define the invention.

EXAMPLES [60] Various recipes were made utilizing the ingredients set forth in Table 1. Table 1: Comparative experiment with Poly-3-FOX acrylate, polyol, and monomer

[61] Cyracure UVI-6974: Triphenylsulfonium hexafluoroantimonate salt, cationic UV catalysts made by Union Carbide/Dow. [62] Cyracure UVR-6110: A cycloaliphatic epoxide cationic, UV curable monomer initiator made by Union Carbide/Dow. [63] Irgacure 500: A liquid free radical photo initiator composed of 1- hydroxycyclohexyl acetophenone and benzophenone in a 1:1 mixture made by Ciba Geigy. [64] Ebercryl 4833: An aliphatic urethane diacrylate diluted 10% with n- vinyl pyrrolidone made by UCB-Radcure. [65] Ebecryl 8301: Hexafunctional aliphatic urethane acrylate containing an acrylated polyol diluent made by UCB-Radcure. [66] The polymers of Table 1 made by photoinitiation were prepared by adding the ingredients to a reaction vessel, as in any order, and polymerizing with UV light as before. As apparent from the data, Example B yielded slightly better contact angles than Control A which utilized a polyFOX acrylate, and Example C contained improved Hoffman scratch results as well as contact angle compared with Control D which utilized no FOX monomer or polymer. These results were obtained wherein the FOX polymer or monomer were utilized in small amounts, i.e. as an additive.

[67] Various modifications and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.

Claims

(CLAIMS What is claimed is:

1. A process for making a polymer that comprises side chains that are at least partially fluorinated, the process comprising the steps of: combining ingredients including a fluorooxetane monomer, a hydroxyl- containing initiator, and a radiation catalyst; providing radiation to form a radiation-polymerized fluorinated polyoxetane polymer; where said fluorooxetane monomer can be represented by the formulas

2. An polymeric network formed by a process comprising the steps of: combining ingredients including a fluorooxetane monomer, a hydroxyl- containing initiator, and a radiation catalyst to form a film; applying radiation to the film to form polymeric network, where said fluorooxetane monomer can be represented by the formula

A radiation-polymerizable composition comprising: ingredients including a hydroxyl-containing initiator, and a radiation catalyst, and fluorooxetane monomer that can be represented by the formulas

4. The process of claim 1, polymeric network of claim 2, or composition of claim 3, wherein the ingredients further comprise a vinyl ether, a vinyl ester, an epoxy, a C1-C15 alkyl-substituted oxirane, a cyclic ether having a 4-membered or 5- membered ring, a dioxane, a dioxalane, a trioxane, a caprolactone, or mixture thereof.

5. The process of claim 1, polymeric network of claim 2, or composition of claim 3, wherein the ingredients further comprise a free radical initiator and an unsaturated acid, unsaturated ester, unsaturated epoxy, or mixture thereof.

6. The process of claim 1, polymeric network of claim 2, wherein the process further comprises the steps of combining the radiation-polymerized fluorinated polyoxetane with one or more radiation-polymerizable monomers; and polymerizing the one or more radiation-polymerizable monomers.

7. The process of claim 1, polymeric network of claim 2, wherein the polyoxetane polymer has a number average molecular weight of from about 1000 to about 75,000.

8. The process of claim 1, polymeric network of claim 2, or composition of claim 3, wherein the ingredients comprise less than about 1 pbw Lewis acid catalyst, based upon 100 pbw of the total amount of the fluorooxetane monomer.

9. The process of claim 1, polymeric network of claim 2, or composition of claim 3, wherein the catalyst comprises hexafluoroantimonate, pentafluorohydroxyantimonate, hexafluorophosphate, hexafluoroarsenate or a catalyst that can be represented by the following formulas (I) to (XV) :

Ar₂I⁺ XT (I)

wherein Ar is an aryl group, and X^~is PF6^~, SbF ^" or AsF6^~ Ar,S (ID

wherein Ar and X^~ are defined as above;

(IV)

wherein Y^" is PFe^", SbFe^", AsF6^~ or SbFs(OH) ;

(V)

wherein XT is defined as above;

wherein X is defined as above;

wherein XT is defined as above;

R⁴ R³— S⁺X- (NIII)

wherein R^ is a C7-C15 aralkyl group or a C3-C9 alkenyl group, R4 is a C1-C7 hydrocarbon group or a hydroxyphenyl group, R^ is a C1-C5 alkyl group that optionally comprises O, S, or O and S atoms, and X^~ is defined as above;

wherein each of R^ and R? independently is a C1-C12 alkyl or alkoxy group;

wherein R^ and R? are defined as above; or

10. The composition of claim 3, further comprising a second monomer, wherein the amount of fluorooxetane monomer is from about 1 to about 15 weight percent, based upon the total weight of monomers.