Surface modifying macromolecules with high degradation temperatures and uses thereof

• US 8,338,537 B2
• Filed: 05/07/2012
• Issued: 12/25/2012
• Est. Priority Date: 12/14/2006
• Status: Active Grant

• Current Assignee: Evonik Canada Inc. (Rag-Stiftung)
• Original Assignee: Interface Biologics, Inc.
• Inventors: Mullick, Sanjoy, Witmeyer, Richard, Santerre, Paul, Chang, Weilun
• Primary Examiner(s): Gulakowski, Randy
• Assistant Examiner(s): BOYLE, KARA BRADY
• Application Number:
  US13/465,406
• Publication Number:
  US 20120220724A1
• Time in Patent Office: 232 Days
• Field of Search: 525/55, 525/123, 526/89, 526/301, 623/1.1
• US Class Current: 525/123
• 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 18/227 of antimony, bismuth or arsenic
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/4211 derived from aromatic dicarboxylic acids and dialcohols
• CPC Class Codes: C08G 18/4238 derived from dicarboxylic acids and dialcohols
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/69 Polymers of conjugated dienes hydrogenated polymers of conjugated dienes C08G18/6208
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/755 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/765 alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: H01L 2224/48091 Arched
• CPC Class Codes: H01L 2224/48137 the bodies being arranged next to each other, e.g. on a common substrate
• CPC Class Codes: H01L 27/156 two-dimensional arrays
• CPC Class Codes: H01L 2924/00014 the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
• CPC Class Codes: H01L 2933/0083 Periodic patterns for optical field-shaping in or on the semiconductor body or semiconductor body package, e.g. photonic bandgap structures
• CPC Class Codes: H01L 33/502 Wavelength conversion materials
• CPC Class Codes: H01L 33/58 : Optical field-shaping elements
• CPC Class Codes: Y10T 428/139 : Open-ended, self-supporting conduit, cylinder, or tube-type article

Abstract

The invention relates to surface modifying macromolecules (SMMs) having high degradation temperatures and their use in the manufacture of articles made from base polymers which require high temperature processing. The surface modifier is admixed with the base polymer to impart alcohol and water repellency properties.

Claims

1. A surface modifier of formula (I):

G-[B-A]_n-B-G 

 

(I)

wherein

(i) A is a soft segment comprising poly(hexamethylene carbonate)diol (PHCN);

poly(ethylene-co-butylene)diol (PEB);

1,6-hexanediol-orthophthalic anhydride polyester polyol (SPH);

or neopentyl glycol-ortho phthalic anhydride polyester polyol (SPN);

(ii) B is a hard segment comprising a urethane formed from a diisocyanate selected from 4,4′

-methylene bis(cyclohexyl isocyanate)(HMDI);

isophorone diisocyanate (IPDI);

or m-tetramethylxylene diisocyanate (TMXDI); and

(iii) G is a polyfluoroalkyl group;

wherein n is an integer from 1 to 10,

and wherein said surface modifier has a theoretical molecular weight of less than 10,000 Daltons.

2. The surface modifier of claim 1, wherein n is 1.

3. The surface modifier of claim 1, wherein said diisocyanate is 4,4′

-methylene bis(cyclohexyl isocyanate) (HMDI).

4. The surface modifier of claim 1, wherein said soft segment has a number average molecular weight, M_n, of 1,000 to 3,500 Daltons.

5. The surface modifier of claim 1, wherein G has a molecular weight of between 100-1,500 Daltons.

6. The surface modifier of claim 1, wherein said polyfluoroalkyl group is

(a) selected from the group consisting of radicals of the general formulas

(i) (CF₃(CF₂)_rCH₂CH₂—

wherein r is 2-20; and

(ii) CF₃(CF₂)_s(CH₂CH₂O)_χ

wherein χ

is 1-10 and s is 1-20;

or

(b) said polyfluoroalkyl group is formed from 1H,1H,2H,2H-perfluoro-1-decanol;

1H,1H,2H,2H-perfluoro-1-octanol;

1H,1H,5H-perfluoro-1-pentanol;

or 1H,1H, perfluoro-1-butanol, or mixtures thereof.

7. The surface modifier of claim 6, wherein said polyfluoroalkyl group is formed from 1H,1H,2H,2H-perfluoro-1-octanol.

8. The surface modifier of claim 1, wherein

(i) A is a soft segment comprising poly(ethylene-co-butylene)diol (PEB);

and

(ii) B is a hard segment formed from 4,4′

-methylene bis(cyclohexyl isocyanate) (HMDI).

9. The surface modifier of claim 8, wherein the polyfluoroalkyl group is formed from 1H,1H,2H,2H-perfluoro-1-octanol.

10. The surface modifier of claim 1, wherein

(i) A is a soft segment comprising neopentyl glycol-ortho phthalic anhydride polyester polyol (SPN);

and

(ii) B is a hard segment formed from 4,4′

-methylene bis(cyclohexyl isocyanate) (HMDI).

11. The surface modifier of claim 10, wherein the polyfluoroalkyl group is formed from 1H,1H,2H,2H-perfluoro-1-octanol.

12. The surface modifier of claim 1, wherein

(i) A is a soft segment comprising 1,6-hexanediol-orthophthalic anhydride polyester polyol (SPH);

and

(ii) B is a hard segment formed from 4,4′

-methylene bis(cyclohexyl isocyanate) (HMDI).

13. The surface modifier of claim 12, wherein the polyfluoroalkyl group is formed from 1H,1H,2H,2H-perfluoro-1-octanol.

14. The surface modifier of claim 1, wherein

(i) A is a soft segment comprising poly(hexamethylene carbonate)diol (PHCN);

and

(ii) B is a hard segment formed from m-tetramethylxylene diisocyanate (TMXDI).

15. The surface modifier of claim 14, wherein the polyfluoroalkyl group is formed from 1H,1H,2H,2H-perfluoro-1-octanol.

16. An admixture comprising the surface modifier of claim 1 admixed with a base polymer.

17. The admixture of claim 16, wherein said base polymer is selected from polypropylenes, polyethylenes, polyesters, polyurethanes, nylons, polysilicones, polystyrenes, poly(methyl methacrylates), polyvinylacetates, polycarbonates, poly(acrylonitrile-butadiene)s, styrene, and polyvinylchlorides, and blends thereof.

18. The admixture of claim 17, wherein said admixture comprises from 0.05% to 10% (w/w) of said surface modifier.

19. An article formed from the admixture of claim 16.

20. The article of claim 19, wherein said article is an implantable medical device.