Fluorinated block copolyesters
Disclosed are block copolyesters comprising blocks of fluoroether functionalized aromatic polyester and blocks of unmodified aromatic polyester, the block copolyesters having a blockiness index, B, in the range of 0.25 to 1.0. The block copolymers incorporated into blends with unmodified aromatic polyester impart oil and soil resistance to shaped articles prepared from the blends.
1. A block copolymer having a blockiness index, B, in the range of 0.56 to 0.8, comprising a first block comprising a plurality of non-fluorinated alkylene arylate repeat units adjacent to one another; and a second block comprising a plurality of fluoroether functionalized alkylene arylate repeat units adjacent to one another; said non-fluorinated alkylene arylate repeat units represented by Structure I
wherein each R is independently H or C 1 -C 10 alkyl, and R 3 is C 2 -C 4 alkylene which can be branched or unbranched;
and, said fluoroether functionalized repeat units are represented by Structure II,
wherein Ar represents a benzene or naphthalene radical; each R is independently H, C 1 -C 10 alkyl, C 5 -C 15 aryl, C 6 -C 20 arylalkyl; OH, or a radical represented by the Structure (III)
with the proviso that only one R can be OH or the radical represented by the Structure (III);
R 1 is a C 2 -C 4 alkylene radical which can be branched or unbranched,
X is O or CF 2 ;
Z is H, Cl, or Br;
a=0 or 1;
and, Q represents the Structure (IIa)
wherein q=0-10;
Y is O or CF 2 ;
Rf 1 is (CF 2 ) n , wherein n is 0-10;
and
Rf 2 is (CF 2 ) p , wherein p is 0-10, with the proviso that when p is 0, Y is CF 2 .
2. The block copolymer of claim 1 wherein R 1 is an ethylene radical.
3. The block copolymer of claim 1 wherein R 1 is a trimethylene radical, which can be branched.
4. The block copolymer of claim 1 wherein R 1 is a tetramethylene radical, which can be branched.
5. The block copolymer of claim 1 wherein each R is H.
6. The block copolymer of claim 1 wherein the fluoroether functionalized alkylene arylate repeat unit, Ar is a benzene radical, a=1, each R is H, Z is H, R1 is trimethylene, X is O, Y is O, Rf 1 is CF 2 , and Rf 2 is (CF 2 ) 3 , and q=1.
7. The block copolymer of claim 1 wherein the fluoroether functionalized alkylene arylate repeat unit is represented by the Structure (IVb)
8. The block copolymer of claim 7 wherein a=1, Z is H, R 1 is trimethylene, X is O, Y is O, Rf 1 is CF 2 , and Rf 2 is (CF 2 ) 3 , and q=1.
9. The block copolymer of claim 1 wherein R 3 is trimethylene.
10. The block copolymer of claim 7 wherein R 3 is trimethylene.
11. The block copolymer of claim 1 wherein the non-fluorinated repeat unit represented by Structure I is a trimethylene terephthalate diradical.
12. The block copolymer of claim 1 wherein the block copolymer is a multi-block copolymer.
13. The block copolymer of claim 1 wherein the non-fluorinated alkylene arylate repeat units and the fluoroether functionalized alkylene arylate repeat units are each present at a molar concentration, and wherein further, the mole ratio of non-fluorinated repeat units to fluoroether functionalized repeat units is in the range of 1.5 to 0.67.