Process for producing fluorinated copolymers of (meth)acrylates and (meth)acrylic acid amine complexes

1. A process for producing copolymer having improved stain resistance, oil and water repellency properties comprising (a) contacting 40 to 70 mol % of a (meth)acrylate monomer of Formula (I);

with 30 to 60 mol % of a (meth)acrylic acid and a first amine of Formula (II);

at a ratio of 1 mole of amine per mole of (meth)acrylic acid forming a first mixture; (b) contacting the first mixture with an initiator forming a copolymer;

wherein

Z is Rf(CH2)n-;

Rf is C2 to C10 fluoroalkyl, optionally interrupted by one or more —O—, —CH2-, —CFH—, or combinations thereof;

n is an integer from 1 to 10;

Rh is C2 to C22 linear, branched, cyclic, or aryl alkyl;

R1 and R2 are each independently H or CH3;

R3 is H, CH3, or CH2CH3;

R4 is H, CH3, or CH2CH3;

R5 is Y;

R9 is alkyl, alkyl alcohol, or hydrogen; and

m is 1 to 10.

2. A process of claim 1 , wherein the (meth)acrylate monomer, the (meth)acrylic acid and the first amine are contacted simultaneously.

3. A process of claim 1 , wherein the (meth)acrylic acid and the first amine are contacted prior to contacting with the (meth)acrylate monomer.

4. A process of claim 1 , wherein the initiator is present at a concentration of 0.1 to 6.0 weight percent relative to the total weight of the (meth)acrylate monomer and (meth)acrylic acid.

5. A process of claim 1 , wherein and the polymerization is at a temperature of from about 50 to from about 90° C. for a time at least equal to the half life of the radical initiator.

6. A process of claim 1 , wherein Rf is C4 to C6 fluoroalkyl and n is 2 to 6.

7. A process for producing copolymer having improved stain resistance, oil and water repellency properties comprising (a) contacting 40 to 70 mol % of a (meth)acrylate monomer of Formula (I);

with 30 to 60 mol % of a (meth)acrylic acid and a first amine of Formula (II);

at a ratio of (1-q) mole of amine per mole of (meth)acrylic acid forming a first mixture; (b) contacting the first mixture with an initiator forming a copolymer; (c) contacting the copolymer with q moles of a second amine of Formula (II);

wherein

0<q≦0.9;

Z is Rf(CH2)n-;

Rf is C2 to C10 fluoroalkyl, optionally interrupted by one or more —O—, —CH2-, —CFH—, or combinations thereof;

n is an integer from 1 to 10;

Rh is C2 to C22 linear, branched, cyclic, or aryl alkyl;

R1 and R2 are each independently H or CH3;

R3 is H, CH3, or CH2CH3;

R4 is H, CH3, or CH2CH3;

R5 is Y;

R9 is alkyl, alkyl alcohol, or hydrogen; and

m is 1 to 10.

8. A process of claim 7 , wherein the (meth)acrylate monomer, the (meth)acrylic acid and the first amine are contacted simultaneously.

9. A process of claim 7 , wherein the (meth)acrylic acid and the first amine are contacted prior to contacting with the (meth)acrylate monomer.

10. A process of claim 7 , wherein the initiator is present at a concentration of 0.1 to 6.0 weight percent relative to the total weight of the (meth)acrylate monomer and (meth)acrylic acid.

11. A process of claim 7 , wherein and the polymerization is at a temperature of from about 50 to from about 90° C. for a time at least equal to the half life of the radical initiator.

12. A process of claim 7 , wherein Rf is C4 to C6 fluoroalkyl and n is 2 to 6.