Reactive polyoxazolines having a perfluorinated group

Abstract

A compound of the formula: (I) wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2)X—; R.sup.3 is a reactive group; R.sup.f is a perfluorinated alkyl group; Y is selected from a bond, S(O).sub.2—N(CH.sub.3)—, —S(O).sub.2—N(CH.sub.2CH.sub.3)—, —S(O).sub.2—O— —S(O).sub.2— —C(O)—, —C(O)—S— —C(O)—O— —C(O)—NH—, —C(O)—N(CH.sub.3)—, —C(O)—N(CH.sub.2CH.sub.3)—, —(CH.sub.2CH.sub.2O)y-, —O—, and —O—C(O)—CH═CH—C(O)—O—; n is greater than 10; x is 2 to 20; and y is at least 1. ##STR00001##

Claims

1. A compound of the formula: ##STR00030## wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—; R.sup.3 is a reactive group selected from (i) a polymerizable group, (ii) an organic group containing a hydrolyzable group, or (iii) a polymerizable group and an organic group containing a hydrolyzable group; R.sup.f is a perfluorinated alkyl group comprising 1 to 5 carbon atoms; Y is selected from —S(O).sub.2—N(CH.sub.3)—, —S(O).sub.2—N(CH.sub.2CH.sub.3)—, —C(O)—NH—, —C(O)—N(CH.sub.3)—, and —C(O)—N(CH.sub.2CH.sub.3)—; n is an integer from 20 to 100; x is an integer from 2 to 20; and y is an integer of at least 1.

2. The compound of claim 1 wherein R.sup.1 is selected from H, methyl, and ethyl.

3. The compound of claim 1 wherein R.sup.3 is selected from a vinyl group, a vinylether group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group.

4. The compound of claim 1 wherein Y is selected from —S(O).sub.2—N(CH.sub.3)—, and —C(O)—NH—.

5. The compound of claim 1 wherein n is an integer no greater than 500.

6. The compound of claim 1 wherein x is an integer from 2 to 10.

7. The compound of claim 1 wherein y is an integer no greater than 20.

8. The compound of claim 3, wherein R.sup.3 is of the formula —W—Si(R.sup.9).sub.3 wherein: W is an organic group; each R.sup.9 group is independently selected from an alkyl group, an aryl group, a combination thereof, and a hydrolyzable group; and at least one R.sup.9 is a hydrolyzable group.

9. The compound of claim 3, wherein R.sup.3 comprises an ethylenically unsaturated group.

10. The compound of claim 3, wherein R.sup.3 is selected from a vinyl group, a vinylether group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group.

11. The compound of claim 10, wherein the trialkoxysilylalkylamino group is of the formula —N(R)—R.sup.7—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein R is H, methyl, or ethyl, and each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, and R.sup.7 is an alkylene group.

12. The compound of claim 10, wherein the trialkoxysilylalkylthio group is of the formula —S—R.sup.8—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, and R.sup.8 is an alkylene group.

13. The compound of claim 11, wherein R.sup.3 is a polymerizable group selected from a (meth)acryloyloxy and a (meth)acryloylamino.

14. The compound of claim 3, wherein Y is selected from —S(O).sub.2—N(CH.sub.3)—, and —C(O)—NH—.

Description

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

(1) The present disclosure provides reactive polyoxazolines (POx) having a perfluorinated alkyl group.

(2) In recent years, the use of polyoxazolines (POx) in biomedical applications has gained interest due to their high biocompatibility and stealth behavior that resembles polyethylene glycol (PEG). POx's can be obtained through living cationic ring opening polymerization, which provides an easy access to a wide variety of well-defined polymers. Furthermore, the functionality and the resulting physical properties of POx's can be tuned simply by changing the initiator, monomer, and the end-group used in the polymerization. Poly(methyl-oxazoline)s and poly(ethyl-oxazoline)s have been shown to have faster in-vivo clearance and in the case of poly(methyl-oxazoline) more hydrophilic character than PEG, which brings a great advantage for antifouling applications. Polyoxazolines also have improved chemical stability, allowing for the production of more durable coatings than those including PEG.

(3) The present disclosure provides reactive polyoxazolines (POx) having a perfluorinated alkyl group. The polyoxazolines are employed as the hydrophilic component, and a perfluorinated alkyl group is employed as the hydrophobic component. Such amphiphilic polymerizable polymers are suitable for making polymers that can be used in making antifouling coatings.

(4) In one embodiment, the present disclosure provides a compound (i.e., polymerizable or substrate-reactive polyoxazoline) of the formula:

(5) ##STR00005##

(6) In certain embodiments, R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof. In certain embodiments, R.sup.1 is H, a (C1-C20)alkyl group, a (C6-C12)aryl group, a (C6-C12)ar(C1-C20)alkyl group, or a (C1-C20)alk(C6-C12)aryl group. In certain embodiments, R.sup.1 is selected from H, methyl, and ethyl.

(7) In certain embodiments, R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—.

(8) In certain embodiments, R.sup.3 is a reactive group (e.g., a polymerizable group and/or a substrate-reactive group).

(9) In certain embodiments, R.sup.3 is a polymerizable group, in particular an ethylenically unsaturated group selected from a vinyl group, a vinylether group, a (meth)acryloyloxy group, and a (meth)acryloylamino group (including embodiments wherein the nitrogen is optionally substituted with methyl or ethyl).

(10) In certain embodiments, R.sup.3 is a substrate-reactive group (e.g., an organic group containing a hydrolyzable silyl group) that provides functionality for bonding to a substrate surface.

(11) In certain embodiments R.sup.3 is of the formula —W—Si(R.sup.9).sub.3 wherein W is an organic group and each R.sup.9 group is independently selected from an alkyl group, an aryl group, or a combination thereof (an alkaryl group or an aralkyl group) and a hydrolyzable group; and at least one R.sup.9 is a hydrolyzable group. In certain embodiments, the hydrolyzable group is selected from a halo, an alkoxy group, and an acyloxy group. In certain embodiments, the hydrolyzable group is selected from a halo, a (C1-C4)alkoxy group, and a (C1-C4)acyloxy group. In certain embodiments, all three R.sup.9 groups are hydrolyzable groups. In certain embodiments, all three R.sup.9 groups are the same.

(12) In certain embodiments, W is selected from an alkylene group, an arylene group, and a combination thereof (i.e., an alkarylene group or an aralkylene group), optionally including —O—, —C(O)—, —NR—, —S—, or a combination thereof, wherein R is H, methyl, or ethyl. Such optional group is typically not directly bonded to the silyl group. In certain embodiments, W is selected from a (C1-C20)alkylene group, a (C6-C12)arylene group, and combination thereof, optionally including —O—, —C(O)—, —NR—, —S—, or a combination thereof. For example, W can be of the divalent group of formula —N(R)—R.sup.7 or —S—R.sup.8— where R.sup.7 and R.sup.8 are each an alkylene group and R is H, methyl, or ethyl.

(13) Examples substrate-reactive groups include trialkoxysilylalkylamino (including embodiments wherein the nitrogen is optionally substituted with methyl or ethyl) and trialkoxysilylalkylthio. Such groups are not only substrate-reactive but may also be polymerizable and form a network.

(14) In certain embodiments, R.sup.3 is selected from a (meth)acryloyloxy group, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, and a trialkyoxysilylalkylamino group.

(15) In certain embodiments, R.sup.3 is selected from a (meth)acryloyloxy group, and a (meth)acryloylamino group.

(16) In certain embodiments, the trialkoxysilylalkylamino group is of the formula —N(R)—R.sup.7—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein R is H, methyl, or ethyl, and each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, and R.sup.7 is an alkylene group. In certain embodiments, the trialkoxysilylalkylamino group is of the formula —N(R)—CH.sub.2CH.sub.2CH.sub.2—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein R is H, methyl, or ethyl, and each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, preferably methyl or ethyl.

(17) In certain embodiments, the trialkoxysilylalkylthio group is of the formula —S—R—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, and R.sup.8 is an alkylene group. In certain embodiments, the trialkoxysilylalkylthio is of the formula —S—CH.sub.2CH.sub.2CH.sub.2—Si(OR.sup.4)(OR)(OR.sup.6), wherein R is H, methyl, or ethyl, and each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, preferably methyl or ethyl.

(18) In certain embodiments, R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—. Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —S(O).sub.2—N(CH.sub.2CH.sub.3)—, —S(O).sub.2—O—, —S(O).sub.2—, —C(O)—, —C(O)—S—, —C(O)—O—, —C(O)—NH—, —C(O)—N(CH.sub.3)—, —C(O)—N(CH.sub.2CH.sub.3)—, —(CH.sub.2CH.sub.2O).sub.y—, —O—, and —O—C(O)—CH═CH—C(O)—O—. In certain embodiments, Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —C(O)—NH—, and —(CH.sub.2CH.sub.2O).sub.y—.

(19) In certain embodiments, R.sup.f is a perfluorinated alkyl group. In certain embodiments, R.sup.f is a perfluorinated (C1-C5)alkyl group. In certain embodiments, R.sup.f is a perfluorinated C4 alkyl group.

(20) In certain embodiments, n is an integer of greater than 10. In certain embodiments, n is no greater than 500. In certain embodiments, n is 20 to 100.

(21) In certain embodiments, x is an integer from 2 to 20. In certain embodiments, x is 2 to 10. In certain embodiments, x is 2 to 6.

(22) In certain embodiments, y is an integer equal to at least 1. In certain embodiments, y is no greater than 20. In certain embodiments, y is 1 to 5.

(23) In one embodiment, the present disclosure provides a compound (i.e., a polymerizable or substrate-reactive polyoxazoline) of the formula:

(24) ##STR00006##
wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—; R.sup.3 is a reactive group; R.sup.f is a perfluorinated alkyl group; Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —S(O).sub.2—N(CH.sub.2CH.sub.3)—, —S(O).sub.2—O—, —S(O).sub.2—, —C(O)—, —C(O)—S—, —C(O)—O—, —C(O)—NH—, —C(O)—N(CH.sub.3)—, —C(O)—N(CH.sub.2CH.sub.3)—, —(CH.sub.2CH.sub.2O).sub.y—, —O—, and —O—C(O)—CH═CH—C(O)—O—; n is greater than 10; x is 2 to 20; and y is at least 1.

(25) In one embodiment, the present disclosure provides a compound of the formula:

(26) ##STR00007##
wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—; R.sup.3 is a reactive group selected from a polymerizable group and a group of formula —W—Si(R.sup.9).sub.3; R.sup.f is a perfluorinated alkyl group; Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —S(O).sub.2—N(CH.sub.2CH.sub.3)—, —S(O).sub.2—O—, —S(O).sub.2—, —C(O)—, —C(O)—S—, —C(O)—O—, —C(O)—NH—, —C(O)—N(CH.sub.3)—, —C(O)—N(CH.sub.2CH.sub.3)—, —(CH.sub.2CH.sub.2O).sub.y—, —O—, and —O—C(O)—CH═CH—C(O)—O—; n is an integer of greater than 10; x is an integer from 2 to 20; y is an integer of at least 1; W is an organic group; and each R.sup.9 is independently an alkyl group, aryl group, or a combination thereof, or a hydrolyzable group, wherein at least one R.sup.9 is a hydrolyzable group.

(27) In one embodiment, the present disclosure provides a compound (i.e., a polymerizable or substrate-reactive polyoxazoline) of the formula:

(28) ##STR00008##
wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—; R.sup.3 is a reactive group selected from a vinyl group, a vinylether group, a (meth)acryloyloxy group (i.e., an acryloyloxy or methacryloyloxy), a (meth)acryloylamino group (i.e., an acryloylamino or methacryloylamino), a trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group; R.sup.f is a perfluorinated (C1-C5)alkyl group; Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —C(O)—NH—, and —(CH.sub.2CH.sub.2O).sub.y—; n is 20 to 100; x is 2 to 20; and y is 1 to 20.

(29) Such compounds are reactive polyoxazolines that can be made using conventional techniques. An exemplary reaction scheme is shown in the Examples Section (Scheme I). Typically, an oxazoline, particularly a 2-oxazoline that includes an R.sup.1 group at the 2-position, is subjected to a ring opening reaction in a suitable solvent (e.g., acetonitrile) in the presence of an initiator (e.g., methyl trifluoromethansulfonate (i.e., methyl triflate), perfluorobutyl ethylene triflate, perfluorobutyl sulfonamide triflate, methyl toluene sulfonate (i.e., methyl tosylate), and methyl iodide) with heating (e.g., at a temperature of 80° C.), and subsequently modified to include a polymerizable group (e.g., upon reaction with (meth)acrylic acid) or a substrate reactive group (e.g., upon reaction with a compound of formula H—W—Si(R.sup.9).sub.3) in the presence of a base (e.g., triethylamine).

(30) The resultant compounds of the present disclosure are useful in making polymers suitable for use in making anti-fog, anti-fouling, and/or easy clean coatings. They can be homopolymerized or copolymerized with other monomers to make suitable coatings. If desired, they can be combined with components, such as metal silicates (e.g., lithium silicate), to form hard coatings as is known in the art.

(31) A coating composition can include a solvent. Useful solvents for the coating compositions include those in which the compound is soluble to at least 1% by weight. Typically, water is used, although other solvents such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone, methyl acetate, ethyl acetate, heptane, toluene, xylene, and ethylene glycol alkyl ether can be used. Those solvents can be used alone or as mixtures thereof. The coating composition is typically a homogeneous mixture that has a viscosity appropriate to the application conditions and method. For example, a material to be brush or roller coated would likely be preferred to have a higher viscosity than a dip coating composition. The coating composition is typically relatively dilute, often containing at least 0.1 wt-%, or at least 1 wt-%, of the compound. Typically, a coating composition includes no greater than 50 wt-%, or no greater than 25 wt-%, of the compound.

(32) A wide variety of coating methods can be used to apply a composition of the present disclosure, such as brushing, spraying, dipping, rolling, spreading, and the like. The obtained coating on the substrate may be cured at room temperature or at an elevated temperature (e.g., 40° C. to 300° C.). In some embodiments the curing may be effected by a catalyst (such as an organic or inorganic acid or base, chelate of titanium (e.g., titanium isopropoxide), and tin based compounds (e.g., dibutyldiacetoxytin), at room temperature or elevated temperatures.

(33) The substrate on which the coating can be disposed can be any of a wide variety of materials. Useful substrates include ceramics, siliceous substrates including glass, metal, natural and man-made stone, and polymeric materials, including thermoplastics and thermosets. Suitable materials include, for example, poly(meth)acrylates, polycarbonates, polystyrenes, styrene copolymers such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate, silicones such as that used in medical tubing, paints such as those based on acrylic resins, powder coatings such as polyurethane or hybrid powder coatings, and wood. The substrates can be in the form of wovens, nonwovens, or films, for example.

(34) In some embodiments, the substrate is selected to have a group that can react with the polyoxazoline. For example, the substrate can have a glass or ceramic-containing surface that has silanol groups that can undergo a condensation reaction with group R.sup.3 selected from a trialkoxysilylalkylthio or a trialkoxysilylamino group. The product of this reaction results in the formation of a —Si—O—Si— bond between the polyoxazoline and the substrate.

(35) The following is a list of illustrative embodiments of the present disclosure.

(36) Embodiment 1 is a compound of the formula:

(37) ##STR00009##

(38) wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—; R.sup.3 is a reactive group; R.sup.f is a perfluorinated alkyl group; Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —S(O).sub.2—N(CH.sub.2CH.sub.3)—, —S(O).sub.2—O—, —S(O).sub.2—, —C(O)—, —C(O)—S—, —C(O)—O—, —C(O)—NH—, —C(O)—N(CH.sub.3)—, —C(O)—N(CH.sub.2CH.sub.3)—, —(CH.sub.2CH.sub.2O).sub.y—, —O—, and —O—C(O)—CH═CH—C(O)—O—; n is an integer of greater than 10; x is an integer from 2 to 20; and y is an integer of at least 1.

(39) Embodiment 2 is the compound of embodiment 1 wherein R.sup.1 is H, a (C1-C20)alkyl group, a (C6-C12)aryl group, a (C6-C12)ar(C1-C20)alkyl group, or a (C1-C20)alk(C6-C12)aryl group.

(40) Embodiment 3 is the compound of embodiment 1 wherein R.sup.1 is selected from H, methyl, and ethyl.

(41) Embodiment 4 is the compound of any one of embodiments 1 through 3 wherein the reactive R.sup.3 group is a polymerizable group or a substrate-reactive group.

(42) Embodiment 5 is the compound of embodiment 4 wherein R.sup.3 is of the formula —W—Si(R.sup.9).sub.3

(43) wherein: W is an organic group; each R.sup.9 group is independently selected from an alkyl group, an aryl group, a combination thereof, and a hydrolyzable group; and at least one R.sup.9 is a hydrolyzable group.

(44) Embodiment 6 is the compound of embodiment 4 wherein R.sup.3 comprises an ethylenically unsaturated group.

(45) Embodiment 7 is the compound of embodiment 4 wherein R.sup.3 is selected from a vinyl group, a vinylether group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group.

(46) Embodiment 8 is the compound of embodiment 7 wherein R.sup.3 is selected from a (meth)acryloyloxy group, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group.

(47) Embodiment 9 is the compound of embodiment 8 wherein R.sup.3 is selected from a (meth)acryloyloxy group and a (meth)acryloylamino group.

(48) Embodiment 10 is the compound of any one of embodiments 7 through 9 wherein the amide nitrogen of the (meth)acryloylamino group is optionally substituted with a methyl or ethyl group.

(49) Embodiment 11 is the compound of any one of embodiments 7 through 9 wherein the trialkoxysilylalkylamino group is of the formula —N(R)—R.sup.7—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein R is H, methyl, or ethyl, and each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, and R.sup.7 is an alkylene group.

(50) Embodiment 12 is the compound of any one of embodiments 7 through 9 wherein the trialkoxysilylalkylthio group is of the formula —S—R.sup.8—Si(OR.sup.4)(OR.sup.5)(OR.sup.6), wherein each R.sup.4, R.sup.5, and R.sup.6 is an alkyl group, and R.sup.8 is an alkylene group.

(51) Embodiment 13 is the compound of any one of embodiments 1 through 12 wherein Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —C(O)—NH—, and —(CH.sub.2CH.sub.2O).sub.y—.

(52) Embodiment 14 is the compound of any one of embodiments 1 through 13 wherein R.sup.f is a perfluorinated (C1-C5)alkyl group.

(53) Embodiment 15 is the compound of embodiment 14 wherein R.sup.f is a perfluorinated C4 alkyl group.

(54) Embodiment 16 is the compound of any one of embodiments 1 through 15 wherein n is an integer no greater than 500.

(55) Embodiment 17 is the compound of embodiment 16 wherein n is an integer from 20 to 100.

(56) Embodiment 18 is the compound of any one of embodiments 1 through 17 wherein x is from 2 to 10.

(57) Embodiment 19 is the compound of embodiment 16 wherein x is an integer from 2 to 6.

(58) Embodiment 20 is the compound of any one of embodiments 1 through 19 wherein y is an integer no greater than 20.

(59) Embodiment 21 is the compound of embodiment 18 wherein y is an integer from 1 to 5.

(60) Embodiment 22 is a compound of the formula:

(61) ##STR00010##

(62) wherein: R.sup.1 is selected from H, an alkyl group, an aryl group, and combinations thereof; R.sup.2 is R.sup.f—Y—(CH.sub.2).sub.x—; R.sup.3 is selected from a vinyl group, a vinylether group, a (meth)acryloyloxy group, and a (meth)acryloylamino group, a trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group; R.sup.f is a perfluorinated (C1-C5)alkyl group; Y is selected from a bond, —S(O).sub.2—N(CH.sub.3)—, —C(O)—NH—, and —(CH.sub.2CH.sub.2O).sub.y—; n is an integer from 20 to 100; x is an integer from 2 to 20; and y is an integer from 1 to 20.

(63) Embodiment 23 is the compound of embodiment 22 wherein R.sup.3 is a polymerizable group selected from a (meth)acryloyloxy and a (meth)acryloylamino.

EXAMPLES

(64) Objects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.

(65) General Procedures for Polymer Synthesis:

(66) Glassware was dried overnight in an oven at 150° C. prior to use. Reagents were purchased from Fisher Scientific or Sigma Aldrich. Acetonitrile was anhydrous grade. Methyl iodide, methyl tosylate, and oxazoline monomers were distilled over CaH.sub.2 and stored over 3 Å molecular sieves. Other reagents for oxazoline polymerization were stored over 3 Å molecular sieves prior to use. Solvents were removed at reduced pressure using a rotary evaporator.

(67) TABLE-US-00001 Scheme I: General scheme for the synthesis of poly(oxazoline) polymers (wherein “LG” = leaving group, and the * represents the point of attachment of the group) R.sup.1 R.sup.2 LG R.sup.3 *—H R.sup.f—Y—(CH.sub.2).sub.x—* *—I *—CH.sub.3 *—CH.sub.2CH.sub.3 0 *—S—(CH.sub.2CH.sub.2CH.sub.2)—Si(OR.sup.4)(OR.sup.5)(OR.sup.6) *—NR—(CH.sub.2CH.sub.2CH.sub.2)—Si(OR.sup.4)(OR.sup.5)(OR.sup.6) (R = H, Me = Et) R.sup.f—Y:

Preparatory Example 1: Synthesis of R2-LG

(68) ##STR00025##

(69) A round bottom flask, equipped with a stopcock, was purged with nitrogen, then charged with anhydrous dichloromethane (20 milliliters (mL)), 1,4-dioxane (20 mL), pyridine (2.0 grams (g), 24.6 millimoles (mmol)) and 1H, 1H, 2H, 2H-perfluorohexanol (5.0 g, 18.9 mmol). The solution was cooled to 0° C., then trifluoromethanesulfonic anhydride (7.0 g, 24.6 mmol) was added drop-wise by syringe to the vigorously stirring solution. After stirring for 2 hours at 0° C., the solution was slowly warmed to room temperature and then stirred for additional 10 hours. The resulting suspension was filtered to remove the precipitated salts. The solution was then washed successively with 1 Normal (N) HCl, saturated NaHCO.sub.3, 10% copper sulfide solution, and brine. The organic phase was dried over anhydrous Na.sub.2SO.sub.4 and excess solvent was removed under vacuum. The resulting brown oil was distilled under reduced pressure to yield 3.0 g of the product as colorless liquid.

Preparatory Example 2: Synthesis of R2-LG

(70) ##STR00026##

(71) A round bottom flask, equipped with a stopcock, was purged with nitrogen, then charged with anhydrous dichloromethane (50 mL), 1,4-dioxane (50 mL), pyridine (3.6 g, 45.4 mmol) and N-methyl-1,1,2,2,3,3,4,4-nonafluoro-N-(2-hydroxyethyl)butane-1-sulphonamide (12.5 g, 34.9 mmol). The solution was cooled to 0° C., then trifluoromethanesulfonic anhydride (12.8 g, 45.4 mmol) was added drop-wise by syringe to the vigorously stirring solution. After stirring for 2 hours at 0° C., the solution was slowly warmed to room temperature and then stirred for additional 10 hours. The resulting suspension was filtered to remove the precipitated salts. The solution was then washed successively with 1N HCl, saturated NaHCO.sub.3, 10% copper sulfide solution, and brine. The organic phase was dried over anhydrous Na.sub.2SO.sub.4 and excess solvent was removed under vacuum. Recrystallization of the resulting solid from cold toluene yielded 7.5 g of the product as white solid.

Example 1: Synthesis of Polymerizable Polyoxazoline

(72) ##STR00027##

(73) A 3-necked flask with attached condenser and stopcock was purged with nitrogen, then charged with acetonitrile (20 mL) and perfluorobutyl ethylene triflate (R.sup.2-LG) initiator of Preparatory Example 1 (0.4 g, 1.0 mmol). The solution was cooled to 0° C., then 2-methyl-2-oxazoline (2.6 g, 30 mmol) was added by syringe. After stirring for 2 hours while slowly warming to room temperature, the solution was heated to 80° C. in an oil bath, then stirred for 20 hours. After cooling to room temperature, acrylic acid (0.36 g, 5.0 mmol) and triethylamine (0.61 g, 6.0 mmol) were added by syringe in that order. The solution was heated back up to 80° C., and stirred for another 24 hours. After cooling, the solution was filtered, then added dropwise with vigorous stirring to 200 mL of diethyl ether to precipitate the polymer. The resulting suspension was stirred for 15 minutes (min). The precipitate was isolated by filtration, washed with diethyl ether, and dried under vacuum at 80° C. overnight, yielding 2.6 g of white solid. End-group analysis by .sup.1H-NMR spectroscopy showed that polymer with n=30 was obtained.

Example 2: Synthesis of Polymerizable Polyoxazoline

(74) ##STR00028##

(75) A 3-necked flask with attached condenser and stopcock was purged with nitrogen, then charged with acetonitrile (15 mL) and perfluorobutyl sulfonamide triflate (R.sup.2-LG) initiator of Preparatory Example 2 (0.74 g, 1.5 mmol). The solution was cooled to 0° C., then 2-methyl-2-oxazoline (3.9 g, 46 mmol) was added by syringe. After stirring for 15 minutes, the solution was warmed to 80° C., then stirred for 16 hours. After cooling to room temperature, acrylic acid (0.16 g, 2.3 mmol) and triethylamine (0.31 g, 3.0 mmol) were added by syringe in that order. The solution was heated back up to 80° C., and stirred for another 4 hours. After cooling, the acetonitrile was evaporated with a stream of nitrogen, and the remainder was dissolved in 50 mL of chloroform. This solution was filtered, then concentrated to about 20 mL. The solution was then added dropwise, with vigorous stirring, to 200 mL of diethyl ether to precipitate the polymer. The resulting suspension was left in the freezer overnight. The precipitate was isolated by filtration, washed with diethyl ether, and dried under vacuum at 80° C. overnight, yielding 4.7 g of white solid. Accounting for the presence of triethylammonium triflate impurities, the yield was 96%. End-group analysis by .sup.1H-NMR spectroscopy showed that polymer with n=30 was obtained.

Example 3: Synthesis of Alkoxysilane-Functional Polymer

(76) ##STR00029##

(77) A 3-necked flask with attached condenser and stopcock was purged with nitrogen, then charged with acetonitrile (5 mL) and perfluorobutyl sulfonamide triflate initiator (R.sup.2-LG) initiator of Preparatory Example 2 (0.63 g, 1.3 mmol). The solution was heated to 40° C., then 2-methyl-2-oxazoline (3.3 g, 39 mmol) was added by syringe. After stirring for 15 minutes, the solution was warmed to 80° C., then stirred for 17 hours. After cooling to 0° C., (3-mercaptopropyl)trimethoxysilane (0.30 g, 1.6 mmol) and triethylamine (0.26 g, 2.6 mmol) were added by syringe in that order. The solution was heated back up to 80° C., and stirred for another 2 hours. After cooling, the acetonitrile was evaporated with a stream of nitrogen, and the remainder was dissolved in 50 mL of chloroform with 2.5% methanol. This solution was filtered, then concentrated to about 20 mL. The solution was then added dropwise with vigorous stirring to 200 mL of diethyl ether containing 2.5% methanol. The resulting suspension was left in the freezer overnight. The precipitate was isolated by filtration, washed with diethyl ether, and dried under vacuum at 80° C. overnight, yielding 4.0 g of white solid. Accounting for the presence of triethylammonium triflate impurities, the yield was close to quantitative. End-group analysis by .sup.1H-NMR spectroscopy showed that polymer with n=30 was obtained.

Example 4: Preparation and Characterization of Coatings

(78) The polymer of Example 3 was dissolved in water at a concentration of 10% by weight. This solution was mixed in varying ratios with an aqueous solution of lithium silicate (Nissan Chemical Industries) diluted to a concentration of 10% by weight. These solutions were then coated on 2 mil polyethylene terephthalate (PET) film with a number 12 wire-wound rod (BYK instruments). The films were dried and cured in an oven at 80° C. for 1 hour.

(79) Coatings were characterized by dynamic contact angle and by measuring transmission and haze. Dynamic contact angle measurements were observed using a DSA 100 video contact angle goniometer (Kruss Inc.) equipped with a Hamilton syringe having a flat-tipped needle. Deionized water and n-hexadecane were used as the probe fluids. Advancing contact angle and receding contact angle were measured as water was supplied via the syringe into or out of sessile droplets (drop volume approximately 5 microliters (μL)). All reported values are averages of six contact angle measurements of drops on three different areas of each sample (left and right angles measured for each drop). Reported errors are one standard deviation. Percent (%) Transmission and % Haze were measured for coated films using a Haze-gard plus (BYK Instruments Inc.). Measurements were collected on three different areas of each sample and reported errors are one standard deviation. The results are summarized in Table 1 below.

(80) TABLE-US-00002 TABLE 1 Optical and Surface Properties of Coated PET Film Ratio of Optical Properties Contact Angles Polymer to % Trans- Water Water Hexadecane Hexadecane Lithium Silicate mission % Haze Advancing Receding Advancing Receding 1:4 84.7 ± 1.3 32.4 ± 1.2  wets wets wets Wets 1:2 91.9 ± 0.1 12.80 ± 0.78  23.0 ± 1.8 12.6 ± 0.8 wets Wets 1:1 91.6 ± 0.2 1.73 ± 0.14 27.5 ± 1.1 13.2 46.7 ± 0.6 27.2 ± 0.5 2:1 91.4 ± 0.3 2.25 ± 0.87 34.3 ± 4.4 20.6 ± 0.9 46.8 ± 0.7 20.2 ± 0.8 4:1 91.2 ± 0.1 1.80 ± 0.01 46.6 ± 0.7 14.2 ± 0.7 45.8 ± 0.9 32.2 ± 0.4

Example 5: Anti-Fog Properties

(81) The anti-fog properties of the coatings prepared in Example 4 were assessed via the following test. In a 1000 mL covered beaker, 400 mL of water was heated to 80° C. The lid contained a circular cut opening of 4 cm diameter, which was covered with a metal plate. The plate was removed, and the film sample was immediately placed over the opening with the coated side down. The degree of fogging observed on the film was recorded initially (within moments of applying the film), after 30 seconds (sec), and after 60 sec. The degree of fogging was graded by assigning one of the following ratings: P=pass (the film remains completely transparent), SF=slight fail (water droplights reduce visibility through the film slightly), F=fail (significant loss of visibility through the film), or BF=big fail (the film is rendered opaque with fog). The results are shown in Table 2.

(82) TABLE-US-00003 TABLE 2 Fogging Properties of Coated PET Films Ratio of Polymer Fogging Fogging to Lithium Initial After After Silicate in Coating Fogging 30 Sec 60 Sec 1:4 F P P 1:2 SF P P 1:1 F SF SF 2:1 SF P P 4:1 P P P No Coating BF BF BF

(83) The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows.