Fluorinated silicon polymers

• US 5,057,377 A
• Filed: 07/23/1990
• Issued: 10/15/1991
• Est. Priority Date: 05/16/1990
• Status: Expired due to Term

• Current Assignee: Huntsman International LLC (Huntsman Corporation)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Karydas, Athanasios, Rodgers, Juliana
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): MOORE, MARGARET G
• Application Number:
  US07/556,936
• Time in Patent Office: 449 Days
• Field of Search: 528/28, 525/440, 525/453, 525/460, 525/474, 428/447
• US Class Current: 428/447
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/38 having heteroatoms other than oxygen C08G18/32 takes precedence
• CPC Class Codes: C08G 18/3812 having fluorine atoms
• CPC Class Codes: C08G 18/3861 containing sulfonamide and/or sulfonylhydrazide groups
• CPC Class Codes: C08G 18/387 in addition to a perfluoroalkyl group
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/8041 with compounds of C08G18/3271
• CPC Class Codes: C08G 18/8054 with compounds of C08G18/38
• CPC Class Codes: C08G 18/8077 Oximes
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

This invention relates to polymeric compositions derived by the polycondensation of heteroatom containing perfluoroalkyl terminated neopentyl glycols, and diamino, dihydroxy, or dimercapto-polysiloxanes and optionally other diols, dimercaptans or diamines with organic diisocyanates; and blends of polycondensation polymers with oxime-blocked organic polyisocyanates. These compositions and blends are useful as coatings on glass, wood, paper, leather and especially textiles.

Claims

1. A urethane containing polymer comprising about 5% to about 70% by weight of perfluoroalkyl containing segments of bis-R_f containing neopentyleneoxy units and about 20-95% by weight of siloxane segments, wherein the perfluoroalkyl containing segment is selected from those of the structure:

##STR19## and the siloxane-containing segment is selected from those of the structure;

##STR20## wherein R_f is a straight or branched chain perfluoroalkyl up to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, or mixtures thereof;

E is straight or branched chain alkylene of 1 to 10 carbon atoms or said alkylene interrupted by one to three groups independently selected from the group consisting of --NR--, --O--, --S--, --COO--, --OOC--, --CONR--, --NRCO--, --SO₂ NR-- and NRSO₂ --, or attached at the R_f end with --CONR-- or --SO₂ NR-- where such R_f is attached to the respective carbonyl carbon or sulfur atom thereof and X is --S--, --O--, SO₂ -- or --NR--;

or E is a direct bond and X is --CONR-- or --SO₂ NR where R_f is attached to the respective carbonyl carbon or sulfur atom thereof; and

R is independently hydrogen, alkyl of 1 to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbon atoms;

m is 1-3 and x is 1 to 20;

Z is --)--, --S-- or --NR₄ -- where R₄ is hydrogen or lower alkyl;

R₁ is straight or branched chain alkylene of up to 6 carbon atoms which may be interrupted by --N(R)-- where R is as defined hereinabove or is a polyoxyalkylene group of the formula

space="preserve" listing-type="equation">--(alk--O).sub.f --alk--

where alk is straight or branched chain alkylene of 2 to 4 carbon atoms and f is an integer of 1 to about 50. R₂, R_a, R_b, R_c, R_d and R_e are straight or branched chain alkyl of up to 18 carbon atoms, alkoxy of up to 5 carbon atoms, phenyl or aralkylene of 7 to 19 carbon atoms;

X₁ and X₂ are integers from 1 to 500 with the proviso that X₁ +X₂ is 5 to 1300; and

z is 1 to 20;

and D is the residue of an aromatic, aliphatic, cycloaliphatic or araliphatic diisocyanate.

2. A polymer according to claim 1 wherein R_f is a mixture of perfluoroalkyl of 4 to 18 carbon atoms.

3. A polymer according to claim 2 wherein R_f contains 4 to 12 carbon atoms, E is alkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂ CH₂ --, --CH₂ CH₂ SO₂ NHCH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or -13 SO₂ NHCH₂ CH₂ --, X is --S--, --SO₂ -- or --O--, and m is 1 or 2.

4. A polymer according to claim 2 wherein R_f is perfluoroalkyl of 6 to 12 carbon atoms, E is ethylene, m=1, and X is S.

5. A polymer according to claim 2 wherein R_f is perfluoroalkyl of 6 to 12 carbon atoms, E is ethylene, m=2, and X is S.

6. A polymer according to claim 1 wherein D is the residue of an aliphatic or cycloaliphatic isocyanate of up to 16 carbon atoms.

7. A polymer according to claim 2 wherein D is the residue of an aliphatic or cycloaliphatic isocyanate of up to 16 carbon atoms.

8. A polymer according to claim 3 wherein D is the residue of an aliphatic or cycloaliphatic isocyanate of up to 16 carbon atoms.

9. A polymer according to claim 1 wherein, R₂, R_a, R_b, R_c, R_d and R_e are alkyl of 1 to 4 carbon atoms or alkoxy of up to 5 carbon atoms, R₁ is alkylene of up to 6 carbon atoms which may be interrupted by --N(R)--and X₁ +X₂ is 5 to 100.

10. A polymer according to claim 2 wherein, R₂, R_a, R_b, R_c, R_d and R_e are alkyl of 1 to 4 carbon atoms or alkoxy of up to 5 carbon atoms, R₁ is alkylene of up to 6 carbon atoms which may be interrupted by --N(R)-- and X₁ +X₂ is 5 to 100.

11. A polymer according to claim 3 wherein, R₂, R_a, R_b, R_c, R_d and R_e are alkyl of 1 to 4 carbon atoms or alkoxy of up to 5 carbon atoms, R₁ is alkylene of up to 6 carbon atoms which may be interrupted by --N(R)-- and X₁ +X₂ is 5 to 100.

12. A polymer according to claim 6 wherein, R₂, R_a, R_b, R_c, R_d and R_e are alkyl of 1 to 4 carbon atoms or alkoxy of up to 5 carbon atoms, R₁ is alkylene of up to 6 carbon atoms which may be interrupted by --N(R)-- and X₁ +X₂ is 5 to 100.

13. A polymer according to claim 7 wherein, R₂, R_a, R_b, R_c, R_d and R_e are alkyl of 1 to 4 carbon atoms or alkoxy of up to 5 carbon atoms, R₁ is alkylene of up to 6 carbon atoms which may be interrupted by --N(R)-- and X₁ +X₂ is 5 to 100.

14. A polymer according to claim 8 wherein, R₂, R_a, R_b, R_c, R_d and R_e are alkyl of 1 to 4 carbon atoms or alkoxy of up to 5 carbon atoms, R₁ is alkylene of up to 6 carbon atoms which may be interrupted by --N(R)-- and X₁ +X₂ is 5 to 100.

15. A blend of the urethane containing polymer according to claim 1 and an effective crosslinking amount of a blocked organic polyisocyanate crosslinking agent.

16. A blend of the urethane containing polymer according to claim 14 and an effective crosslinking amount of a blocked organic polyisocyanate crosslinking agent.

17. A polyamide or cellulosic textile fabric treated with an oleophobic and hydrophobic amount of a cured blend of the composition according to claim 15.

18. A polyamide or cellulosic textile fabric treated with an oleophobic and hydrophobic amount of a cured blend of the composition according to claim 16.