PERFLUGRGPOLYVINYL MODIFIED ARYL INTERMEDIATES/MONOMERS

FIELD OF THE INVENTION

The present invention comprises aryi compounds having partially f!uorinated pendent groups and (meth)acry!ate dependent groups, useful for free radical polymerization. The resulting polymers are useful for producing various water and oil repellents, soil resists, and surfactants. BACKGROUND OF THE INVENTION

Water and oil repellents, soil resists, and surfactants compounds generally are prepared from linear perfiuonnated alcohols. These alcohols are expensive and are prepared through several step syntheses. These alcohols are either then reacted to make final products or further synthesized into intermediates prior to making final products. New starting materials are needed that do not utilize linear uninterrupted perfiuonnated alcohols, which are in short supply.

U.S. Patent 7,531 ,700 teaches fluorinated solvents having benzene rings with a) perfluorinated pendent alkyl groups, b) alkyl, alkoxy, or oxyalkyl groups and c) optionally halogen pendent groups useful for the manufacture of organic electronic devices. These solvents are non- reactive.

Patent Application WO 2007/149449 teaches fluoroalkoxystyrenes prepared by contacting a fluorinated olefin with a solution of

hydroxystyrene. These fluoroalkoxystyrenes are useful in resins, elastomers, polymers, or coatings.

Compounds other than linear uninterrupted perfluorinated alcohols are needed which can be used as starting monomers to produce polymers for water and oil repellents and soil resists. The present invention meets this need. SUMMARY OF THE INVENTION

The present invention comprises a compound of formu

wherein

Rf is -CF3, -C ₂ F ₅ , -CF2CFXCF3;

X is -F, or -OCsFy;

Y is -H, -CI, or ~Br;

R is -0~C(0)-R ¹ , -(CH ₂ ) _n O-C(0)-R ¹ , -(OCH ₂ CH ₂ ) _m OC(0)-R ¹ ;

-(CH ₂ )n(OCH ₂ CH2) _m O-Rl ;

n is 1 to 10;

m is 1 to 10;

R is -C(R ³ )=CH ₂ ;

R3 is H or CH3;

a is 1 to 5; and

b is 1 to 5.

DETAILED DESCRIPTION

Herein trademarks are shown in upper case.

The term "(meth)a cry late" is used herein defined to mean both "acrylate" and "methacrylate".

The present invention relates to a compound of formula (I)

wherein

Rf is -CF3, -C2F5, -CF2CFXCF3;

X is -F, or -OC3F7;

Y is -H , -CI , or -Br;

R is -0-C(0)-R ¹ , -(CH2)nO-C(0)-R ¹ , -(OCH2CH ₂ ) _m OC(0)-R ¹ ;

-(CH ₂ ) _n (OCH ₂ CH ₂ ) _m O-R ;

n is 1 to 10;

m is 1 to 10;

R3 is H or CHs;

a is 1 to 5; and

b is 1 to 5.

Compounds of the present invention include pendent groups (Rf-0-CFY-CF20-) _a and (R)b and wherein a is 1 , 2, 3, 4, or 5, and b is 1 , 2, 3, 4 or 5. Compounds of the present invention may 1 , 2, 3, 4, or 5 pendent groups of Rf-0-CFY-CF20-, 1 , 2, 3, 4, or 5 pendent groups of -R, and mixtures thereof, provided that the total number of pendent groups is less than or equal to 6. The Rf-0-CFY~CF20- and -R groups may be ortho, para, or meta on the benzene ring or combinations thereof.

Preferred compounds of Formula (I) include those wherein Rf is -

CF ₃ , or -C ₂ F _5; Y is H; R is -0-C(0)-R ¹ , -(CH ₂ )nO-C(0)-R ,

-{OCH ₂ CH2)mOC(0)-R ¹ , or -(CH ₂ ) _n (OCH ₂ CH2) _m O-R ¹ ; R ¹ , R ³ , a, and b are defined as above; n is 1 , 2, 3, 4, 5, or 6; and m is 1 , 2, 3, 4, 5, or 8. Also preferred are compounds of Formula (I) wherein Rf is -CF3, or -C ₂ F _5; Y is H; R is -0-C(0)-R ¹ , -(CH ₂ ) _n O-C(0)-R ¹ ,

-(OCH ₂ CH2) _m OC(0)-R ¹ , or -(CH2)n(OCH2CH ₂ ) _m O-R ¹ ; R ¹ , R ³ , a, and b are defined as above; n is 1 , 2, or 3; and m is 1 , 2, or 3.

Additional preferred compounds of Formula (I) include those wherein Rf is -CF3, or -C ₂ F5 _; Y is H; R is -OC(Q)-R ¹ ,

-(CH ₂ ) _n O-C(0)-R _! -(OCH ₂ CH ₂ ) _m OC(0)-R _! or

~{CH ₂ ) _n (GCH ₂ CH ₂ ) _m G-R^ ; R^ , R ³ , m, and n are defined as above; a is 1 , 2, or 3; and b is 1 , 2, or 3. Also preferred are compounds of Formula (I) wherein Rf is -CF3, or -C ₂ F5 _; Y is H; R is -0-C(0)-R^ ,

-(CH ₂ ) _n O-C(Q)-R ¹ , -(OCH ₂ CH ₂ ) _m OC(Q)-R ¹ , or

"(^Η ₂ ) _η (ΟΟΗ ₂ ΟΗ ₂ ) _Γ ηΟ-Ρ ¹ ; R^ , R ³ , m, and n are defined as above; a is

1 , or 2; and b is 1 , or 2.

Additional preferred compounds of Formula (I) include ihose wherein Rf is -CF3, or -C ₂ F5 _; Y is CI or Br; R is -0-C(0)-R ,

-(CH ₂ ) _n O-C(0)-Rl _! -(OCH ₂ CH ₂ ) _m OC(0)-Rl _! or

-{CH ₂ ) _n (OCH ₂ CH ₂ ) _m O-R^ ; R^ , R ³ , a, and b are defined as above; n is 1 ,

2, 3, 4, 5, or 6; and m is 1 , 2, 3, 4, 5, or 6. Also preferred are compounds of Formula (I) wherein Rf is -CF3, or -C ₂ F5 _; Y is CI or Br; R is -O-C(O)-

R ¹ . -(CH2) _n O-C(0)-R ¹ , -(OCH ₂ CH ₂ ) _m OC(0)-R ¹ , or

-(CH ₂ ) _n (GCH ₂ CH ₂ ) _m G-R ; R ¹ , R ³ , a, and b are defined as above; n is 1 , 2, or 3; and m is 1 , 2, or 3.

Preferred compounds of Formula (I) also include ihose wherein Rf is -CF ₂ CFXCF3; X is F; Y is H, CI or Br; R is -0-C(0)-R ¹ ,

-(CH ₂ ) _n O-C(0)-R ¹ , -(OCH ₂ CH ₂ ) _m OC(0)-R ¹ _! or

-(CH ₂ ) _n (OCH ₂ CH ₂ ) _m O-R ; R ¹ , R ³ , a, and b are defined as above; n is 1 , 2, 3, 4, 5, or 6; and m is 1 , 2, 3, 4, 5, or 6. Also preferred are compounds of Formula (I) wherein Rf is -CF2CFXCF3; X is F; Y is H, CI or Br; R is -O-

C(0)-R ¹ , -(CH ₂ ) _n O-C(0)-R ¹ , -(OCH ₂ CH2) _m OC(0)-R ¹ _! or

-(CH2)n(OCH2CH2)mO-R^ ; ^a < ^an ^ b are defined as above; n is 1 ,

2, or 3; and m is 1 , 2, or 3.

Additional preferred compounds of Formula (I) include those wherein Rf is -CF2CFXCF3 _; X is -OC3F7; Y is H, Ci or Br; R is -O-C(O)-

R1 , -(CH _2)n O~CtO)-Rl , -(OCH ₂ CH2) _m OC{0)-Rl , or

-(CH ₂ ) _n (OCH2CH2)mO ^~ R^ ^a < ^an d b are defined as above; m is

1 , 2, 3, 4 , 5, or 6; and n is 1 , 2, 3, 4, 5, or 8. Also preferred are

compounds of Formula (\) wherein Rf is -CF2CFXCF3; X is -GC3F7; Y is

H, CI or Br; R is -0-C(0)-R ¹ , -(CH ₂ ) _n O-C(0)-R ¹ ,

-(OCH ₂ CH2)mOC(0)-R ¹ , or -(CH2)n(OCH ₂ CH2)mO-R ¹ ; R ¹ , R ³ , a, and b are defined as above; n is 1 , 2, or 3; and b is 1 , 2, or 3.

Compounds of Formula (I) can be produced in various ways, Examples of compounds of Formula (\) include, but are not limited to,

nd

In the present invention, (meth)acrylate containing compounds of Formula (I) wherein Rf is -CF3, -C2F5, -CF2CFXCF3; X is -F, or -OC3F7; and Y is -H, -CI, or -Br; and R is -0-C(0)-R ¹ , -(CH ₂ ) _n O-C(0)-R ¹ , -(OCH ₂ CH ₂ )mOC(0)-R ¹ ; -(CH2)n(OCH ₂ CH2)mO-R ¹ ; n is 1 to 10; rn is 1 to 10; R ¹ is -C(R ³ )=CH ₂ ; R ³ is H or CH3; a is 1 to 5; and b is 1 to 5 can be prepared by contacting compounds of Formula (!) wherein Rf is -CF3, - C2F5, -CF2CFXCF3; X is -F, or -OC3F7; and Y is -H, -CI, or -Br and R is -(CH ₂ ) _n OH, -(OCH ₂ CH ₂ ) _m OH, -(CH ₂ ) _n (OCH ₂ CH ₂ )mQH with methyl (rneth)acrylate and a catalyst, such as titanium(iV) butoxide.

Compounds of Formula (I) wherein Rf is -CF3, -C2F5, -

CF ₂ CFXCF3; X is -F, or -OC3F7; and Y is -H, -CI, or -Br and R is - (CH ₂ ) _n OH, -(OCH ₂ CH ₂ )mOH, -(CH ₂ ) _n (OCH ₂ CH ₂ )mOH can be prepared by can be prepared by contacting functionaiized aryl rings of Formula (V) wherein a is 1 to 5 and b is 1 to 5;

with one or more perfluoroviny! ethers of formula (V!)

wherein Rf is ~CF3, -C2F5, -CF2CFXCF3; X is -F, or -OC3F7; and Y is -H, -CI, or -Br.

For compounds of Formula (VI), when Rf is -CF3, the compound is perfluoromethylviny! ether of Formula (VII) when Rf is -C2F5, the compound is a perf!uorovinyi ethyl ether of Formula (VIII)

when Rf is -CF2CFXCF3 and X is -F, the compound is a

perfluoropropyivinyl ether of Formula (IX)

and when Rf is -CF2CFXCF3 and X is -OC3F7, the compound is a perfluoropropyivinyl ether of Formula (X)

The reaction of the aryi compounds of Formula (ΧΠ!) with peril uorovinyl ethers of Formula (XIV) can be completed in a solvent and a base. Examples of such bases include, but are not limited to, potassium carbonate, sodium carbonate, and potassium bicarbonate. Examples of suitable solvents include, but are not limited to, tefrahydrofuran, carbon tetrachloride, and carbon tetrabromide. In Formula (I), when

tefrahydrofuran is the solvent, then Y is H. In Formula (I), when carbon tetrachloride is the solvent, then Y is Ci. In Formula (I), when carbon tetrabromide is the solvent, then Y is Br. The reaction temperature can between room temperature and the solvent reflux temperature.

Compounds of the present invention and above defined

embodiments are useful, for example, as starting monomers and intermediates for the preparation of polyacrylate copolymers used for oil and water repeliency as well as stain resistance to fibrous substrates.

EXAMPLES

Materials

Perfluorovinyi ethers 1 ,1 ,1 ,2,2,3, 3~heptafiuoro-3-((1 ,2,2- trifluorovinyl)oxy)propane and 1 ,1 ,1 ,2,2,3,3-heptafluoro-3-(1 ,1 ,1 ,2,3,3- hexafluoro-3-(1 ,2,2trifluorovinyloxy)propan-2-yloxy)propane are commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE. All other reactants, unless otherwise specified, are available from Sigma-Aldrich, St. Louis, MO. Example 1

4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2-

(perfluoropropoxy)propoxy)ethoxy)benzyl methacryiate

In a dry box, tetrahydrofuan (50 mL) and 4-(hydroxymethyl)phenoi

(0.62 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.345 g, 0.0025 mol) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-Heptafluoro-3-(1 ,1 ,1 ,2,3,3-hexafluoro-3- (1 ,2,2trifluorovinyloxy)propan-2-yloxy)propane (3.24 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux over 2 days. The content was analyzed by proton NMR and shown to be (4-(1 ,1 ,2-trifiuoro-2-(1 ,1 ,2,3,3,3- hexafiuoro-2- (perfiuoropropoxy)propoxy)ethoxy)phenyi)methanol.

In the dry box, the (4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafiuoro-2- (perfluoropropoxy)propoxy)ethoxy)phenyl)methanoi (38.5 g, 0.656 mol) and methyl methacryiate (40.0 g, 0.40 mol) were added to a round bottom flask equipped with a stirrer. Titanium(iv) n-butoxide (0.50 mL) was then added to the round bottom flask. The reaction was placed in an oil bath and heated to reflux over about 3 hours. Then the reaction product was distilled to remove excess methyl methacryiate. The content was analyzed by proton NMR and shown to be 4-(1 , 1 ,2~trif!uoro-2~(1 ,1 ,2,3,3,3- hexafluoro-2-(perfiuoropropoxy)propoxy)ethoxy)benzyl methacryiate.

Example 2

2-(2-(1 ,1 ,2-trifiuoro-2-(perfluoropropoxy)ethoxy)phenoxy)ethyl

methacryiate

in a dry box, ieirahydrofuan (50 mL) and 2-(hydroxyethoxy)phenol (0.77 g, 0.005 moi) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.345 g, 0.0025 moi) was then added to the flask. 1 , 1 ,1 , 2,2,3, 3-Heptaf!uoro-3~(1 , 1 ,1 , 2,3, 3-bexafiuoro~3-

(1 ,2,2trifiuorovinyIoxy)propan-2-yIoxy)propane (3.24 g, 0.0075 moi) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux overnight. The content was analyzed by proton NMR and shown to be 2-(2-(1 ,1 ,2-trif!uoro~2-(1 ,1 ,2,3,3,3- hexafluoro-2-(perfiuoropropoxy)propoxy)ethoxy)phenoxy)ethano l.

In the dry box, the 2-(2-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)phenoxy)ethanol (35.0 g, 0.083 moi) and methyl methacrylate (64.0 g, 0.840 moi) were added to a round bottom flask equipped with a stirrer. Titanium(iv) n-butoxide (0.50 mL) was then added to the round bottom flask. The reaction was placed in an oil bath and heated to reflux over about 3 hours. Then the reaction product was distilled to remove excess methyl methacrylate. The content was analyzed by proton NMR to be 2-(2-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3,- hexafiuoro-2-(perfluoropropoxy)ethoxy)phenoxy)ethyl methacrylate. The excess methacrylate was removed under reduced pressure and vacuum distillation of the resulting material gave 9.30 g of the pure material, bp 107-1 10 at 0.85 torr.