Perfluoropolyvinyl modified aryl intermediates/monomers

The present invention comprises aryl compounds having partially fluorinated pendent groups and (meth)acrylate dependent groups, useful for free radical polymerization. The resulting polymers are useful for producing various water and oil repellents, soil resists, and surfactants.

Water and oil repellents, soil resists, and surfactants compounds generally are prepared from linear perfluorinated 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 perfluorinated alcohols, which are in short supply.

U.S. Pat. No. 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 uninterruputed 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.

A compound of formula (I)

wherein

R f is —CF 3 , —C 2 F 5 , —CF 2 CFXCF 3 ;

X to —F, or —OC 3 F 7 ;

Y is —H, —Cl, or —Br;

R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 ; —(CH 2 ) n (OCH 2 CH 2 ) m O—R 1 ;

n is 1 to 10;

m is 1 to 10;

R 1 is —C(R 3 )═CH 2 ;

R 3 is H or CH 3 ;

a is 1 to 5; and

b is 1 to 5.

Herein trademarks are shown in upper case.

The term “(meth)acrylate” is used herein defined to mean both “acrylate” and “methacrylate”.

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

wherein

R f is —CF 3 , —C 2 F 5 , —CF 2 CFXCF 3 ;

X to —F, or —OC 3 F 7 ;

Y is —H, —Cl, or —Br;

R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 ; —(CH 2 ) n (OCH 2 CH 2 ) m O—R 1 ;

n is 1 to 10;

m is 1 to 10;

R 1 is —C(R 3 )═CH 2 ;

R 3 is H or CH 3 ;

a is 1 to 5; and

b is 1 to 5.

Compounds of the present invention include pendent groups (R f —O—CFY—CF 2 O—) 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 R f —O—CFY—CF 2 O—, 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 R f —O—CFY—CF 2 O— and —R groups may be ortho, para, or meta on the benzene ring or combinations thereof.

Preferred compounds of Formula (I) include those wherein R f is —CF 3 , or —C 2 F 5 ; Y is H; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) 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 6.

Also preferred are compounds of Formula (I) wherein R f is —CF 3 , or —C 2 F 5 ; Y is H; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 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 R f is —CF 3 , or —C 2 F 5 ; Y is H; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) m O—R 1 ; R 1 , 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 R f is —CF 3 , or —C 2 F 5 ; Y is H; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) m O—R 1 ; R 1 , 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 those wherein R f is —CF 3 , or —C 2 F 5 ; Y is Cl or Br; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) 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 6. Also preferred are compounds of Formula (I) wherein R f is —CF 3 , or —C 2 F 5 ; Y is Cl or Br; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 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.

Preferred compounds of Formula (I) also include those wherein R f is —CF 2 CFXCF 3 ; X is F; Y is H, Cl or Br; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) 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 6. Also preferred are compounds of Formula (I) wherein R f is —CF 2 CFXCF 3 ; X is F; Y is H, Cl or Br; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 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 R f is —CF 2 CFXCF 3 ; X is —OC 3 F 7 ; Y is H, Cl or Br; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) m O—R 1 ; R 1 , R 3 , a, and b are defined as above; m is 1, 2, 3, 4 , 5, or 6; and n is 1, 2, 3, 4, 5, or 6. Also preferred are compounds of Formula (I) wherein R f is —CF 2 CFXCF 3 ; X is —OC 3 F 7 ; Y is H, Cl or Br; R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 , or —(CH 2 ) n (OCH 2 CH 2 ) m O—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 (I) include, but are not limited to,

In the present invention, (meth)acrylate containing compounds of Formula (I) wherein R f is —CF 3 , —C 2 F 5 , —CF 2 CFXCF 3 ; X is —F, or —OC 3 F 7 ; and Y is —H, —Cl, or —Br; and R is —O—C(O)—R 1 , —(CH 2 ) n O—C(O)—R 1 , —(OCH 2 CH 2 ) m OC(O)—R 1 ; —(CH 2 ) n (OCH 2 CH 2 ) m O—R 1 ; n is 1 to 10; m is 1 to 10; R 1 is —C(R 3 )═CH 2 ; R 3 is H or CH 3 ; a is 1 to 5; and b is 1 to 5 can be prepared by contacting compounds of Formula (I) wherein R f is —CF 3 , —C 2 F 5 , —CF 2 CFXCF 3 ; X is —F, or —OC 3 F 7 ; and Y is —H, —Cl, or —Br and R is —(CH 2 ) n OH, —(OCH 2 CH 2 ) m OH, —(CH 2 ) n (OCH 2 CH 2 ) m OH with methyl (meth)acrylate and a catalyst, such as titanium(IV) butoxide.

Compounds of Formula (I) wherein R f is —CF 3 , —CF 3 , —C 2 F 5 , —CF 2 CFXCF 3 ; X is —F, or —OC 3 F 7 ; and Y is —H, —Cl, or —Br and R is —(CH 2 ) n OH, —(OCH 2 CH 2 ) m OH, —(CH 2 ) n (OCH 2 CH 2 ) m OH can be prepared by can be prepared by contacting functionalized aryl rings of Formula (V)

wherein a is 1 to 5 and b is 1 to 5;

with one or more perfluorovinyl ethers of formula (VI)

wherein R f is —CF 3 , —C 2 F 5 , —CF 2 CFXCF 3 ; X is —F, or —OC 3 F 7 ; and Y is —H, —Cl, or —Br.

For compounds of Formula (VI), when R f is —CF 3 , the compound is perfluoromethylvinyl ether of Formula (VII)

when R f is —C 2 F 5 , the compound is a perfluorovinyl ethyl ether of Formula (VIII)

when R f is —CF 2 CFXCF 3 and X is —F, the compound is a perfluoropropylvinyl ether of Formula (IX)

and when R f is —CF 2 CFXCF 3 and X is —OC 3 F 7 , the compound is a perfluoropropylvinyl ether of Formula (X)

The reaction of the aryl compounds of Formula (XIII) with perfluorovinyl 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, tetrahydrofuran, carbon tetrachloride, and carbon tetrabromide. In Formula (I), when tetrahydrofuran is the solvent, then Y is H. In Formula (I), when carbon tetrachloride is the solvent, then Y is Cl. 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 is and water repellency as well as stain resistance to fibrous substrates.

Materials

Perfluorovinyl ethers 1,1,1,2,2,3,3-heptafluoro-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, Del. All other reactants, unless otherwise specified, are available from Sigma-Aldrich, St. Louis, Mo.

4-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)benzyl methacrylate

In a dry box, tetrahydrofuan (50 mL) and 4-(hydroxymethyl)phenol (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. 1,1,2,2,3,3-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-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)phenyl)methanol.

In the dry box, the (4-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)phenyl)methanol (36.5 g, 0.656 mol) and methyl methacrylate (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 methacrylate. The content was analyzed by proton NMR and shown to be 4-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)benzyl methacrylate.

2-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)phenoxy)ethyl methacrylate

In a dry box, tetrahydrofuan (50 mL) and 2-(hydroxyethoxy)phenol (0.77 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 overnight. The content was analyzed by proton NMR and shown to be 2-(2-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)phenoxy)ethanol.

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 mol) and methyl methacrylate (64.0 g, 0.640 mol) were added to around 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,-hexafluoro-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 107-110 at 0.85 torr.