Fluoroacrylate-mercaptofunctional copolymers

• US 7,291,688 B2
• Filed: 12/28/2004
• Issued: 11/06/2007
• Est. Priority Date: 12/28/2004
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Qiu, Zai-Ming, Kumar, Ramesh C., Clark, John C.
• Primary Examiner(s): Wu; David W.
• Assistant Examiner(s): Bernshteyn; M.
• Application Number:
  US11/027,605
• Publication Number:
  US 20060142518A1
• Time in Patent Office: 1,043 Days
• Field of Search: 526/242, 526/286, 526/319, 528/374, 528/70
• US Class Current: 526/242
• CPC Class Codes: C08F 220/38 Esters containing sulfur
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen

Abstract

A copolymer comprises repeating units derived from at least one co-reactant comprising two or more mercapto functional groups, and repeating units derived from a fluoroacrylate comprising the reaction product of:

• • (a) at least one fluorochemical alcohol represented by the formula:
    C₄F₉—X—OH
  • wherein:

• • • R=hydrogen or an alkyl group of 1 to 4 carbon atoms,
    • m=2 to 8,
    • R_f=C_nF_2n+1,
    • n=1 to 5,
    • y=0 to 6, and
    • q=1 to 8;
  • (b) at least one unbranched symmetric diisocyanate; and
  • (c) at least one hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

Claims

1. A copolymer comprising repeating units derived from at least one co-reactant comprising two or more mercapto functional groups, and repeating units derived from a fluoroacrylate comprising the reaction product of:

(a) at least one fluorochemical alcohol represented by the formula;

C₄F₉—

X—

OH

wherein;

2. The copolymer of claim 1 wherein X is

3. The copolymer of claim 1 wherein the fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.

4. The copolymer of claim 1 wherein the unbranched symmetric diisocyanate is 4,4′

-diphenylmethane diisocyanate.

5. The copolymer of claim 1 wherein the hydroxy-terminated alkyl(meth)acrylate or 2-fluoroacrylate monomer is 2-hydroxyethyl acrylate.

6. The copolymer of claim 1 wherein the co-reactant is represented by the formula:

(B)_n(Q-SH)_k

wherein;

B=a multivalent segment selected from the group consisting of

7. The copolymer of claim 1 wherein the co-reactant is represented by the formula:

HS(Q′

-(B′

)<sub>n-Q′

S)b</sub>H

wherein;

B′

=a multivalent segment selected from the group consisting of —

(CH₂)_b—

, —

(CH₂CH₂O)_b—

, —

(CHCH₃CH₂O)_b—

, [—

(CH₂CH₂O)_b—

(CHCH₃CH₂O)_b]—

(CH₂CH₂O)_b—

(CHCH₃CH₂O)_b—

, —

C₄H₈(OC₄H₈)_b—

, —

C₂H₄OC₂H₄OC₂H₄—

, —

C₆H₅CR″

₂C₆H₅—

, and —

(C₂H₄O)_bC₆H₅CR″

₂C₆H₅(OC₂H₄)_b—

;

b=1 to 100;

R″

=CH₃, CF₃, or H;

n=1 or greater; and

Q′

=—

OC(O)CH₂CH₂—

or —

C(O)CH₂CH₂—

.

8. The copolymer of claim 1 wherein the co-reactant is represented by the formula:

(R_f′

)_n(Q″

-SH)_k

wherein;

R_f′

=a multivalent segment comprising a fluorinated alkyl or alkylene group;

Q″

=—

C(O)NH(CH₂)_b—

or —

OC(O)(CH₂)_b—

;

b=2 to 12;

n=1 or greater; and

k=2 or greater.

9. The copolymer of claim 1 wherein the co-reactant is represented by the formula:

10. The copolymer of claim 1 further comprising repeating units derived from at least one comonomer.

11. The copolymer of claim 10 wherein the comonomer is a (meth)acrylate or fluoro(meth)acrylate.

12. A composition comprising a solvent and the copolymer of claim 1.

13. The composition of claim 12 wherein the composition is a release coating composition.

14. An article comprising a substrate having one or more surfaces coated with the composition of claim 12.

15. The article of claim 14 wherein the substrate comprises a material selected from the group consisting of polyethylene terephthalate, polyolefins, and polyolefin coated paper.

16. The article of claim 14 wherein the substrate is a fibrous substrate.

17. The article of claim 14 wherein the substrate is a non-woven substrate.

18. An article comprising a substrate having one or more surfaces coated with the composition of claim 13.

19. The article of claim 18 wherein the article is a release liner.