Fluoroacrylate-mercaptofunctional copolymers

• US 20060142518A1
• Filed: 12/28/2004
• Published: 06/29/2006
• Est. Priority Date: 12/28/2004
• Status: Active Grant

• 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.
• Granted Patent: US 7,291,688 B2
• Time in Patent Office: Days
• US Class Current: 526/319
• 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;

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.

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 reaction product of (a), (b), and (c) is represented by the formula:

C₄F₉—

X—

OC(O)NH-A-HNC(O)O—

(C_pH_2p)(O)COC(R′

)═

CH₂

wherein;

R═

H 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,

q=1 to 8,

A=an unbranched symmetric alkylene group, arylene group, or aralkylene group,

p=2 to 30, and

R′

═

H, CH₃, or F.

7. The copolymer of claim 6 wherein reaction product of (a), (b), and (c) is C₄F₉SO₂N(CH₃)C₂H₄OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═

CH₂.

8. 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

—

(CH₂)_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;

Q=—

(CH₂)_b—

, —

C(O)(CH₂)_a—

, or —

OC(O)(CH₂)_a—

;

a=1 to 10;

n=1 or greater; and

k=2 or greater.

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

HS(Q′

-(B′

)_n-Q′

S)_bH

wherein;

B′

=a multivalent segment selected from the group consisting of —

(CH₂)_b—

, —

(CH₂CH₂O)_b—

, —

(CHCH₃CH₂O)_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—

.

10. 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.

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

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

13. The copolymer of claim 12 wherein the comonomer is a (meth)acrylate or fluoro(meth)acrylate.

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

15. The composition of claim 14 wherein the composition is a release coating composition.

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

17. The article of claim 16 wherein the substrate comprises a material selected from the group consisting of polyethylene terephthalate, polyolefins, and polyolefin coated paper.

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

19. The article of claim 16 wherein the substrate is a non-woven substrate.

20. An article comprising a substrate having one or more surfaces coated with the composition of claim 15.

21. The article of claim 20 wherein the article is a release liner.