Surface modifying macromolecules with high degradation temperatures and uses thereof

• US 20080228253A1
• Filed: 12/14/2007
• Published: 09/18/2008
• Est. Priority Date: 12/14/2006
• Status: Active Grant

• Current Assignee: Evonik Canada Inc. (Rag-Stiftung)
• Original Assignee: Interface Biologics, Inc.
• Inventors: Mullick, Sanjoy, Chang, Weilun, Santerre, Paul, Witmeyer, Richard
• Granted Patent: US 8,071,683 B2
• Time in Patent Office: Days
• US Class Current: 623/1.1
• 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 hydrogenated polybutadiene, poly (2,2 dimethyl-1-3-propylcarbonate), polybutadiene, poly(diethylene glycol)adipate, diethylene glycol-ortho phthalic anhydride polyester, or 1,6-hexanediol-ortho phthalic anhydride polyester;

(ii) B is a hard segment comprising a urethane; and

(iii) G is a surface active group,

wherein n is an integer from 1 to 10 and said surface modifier has a thermal degradation temperature of between 250°

C. and 345°

C.

2. The surface modifier of claim 1, wherein said surface modifier has a thermal degradation temperature of between 300°

C. and 345°

C.

3. The surface modifier of claim 1, wherein said soft segment comprises hydrogenated polybutadiene or poly(2,2 dimethyl-1-3-propylcarbonate).

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

-methylene bis(cyclohexyl urethane) and n is 1 or 2.

6. The surface modifier of claim 1 or 5, wherein said surface modifier is formed by a process that comprises the step of reacting a diisocyanate with a diol comprising said soft segment to form a prepolymer.

7. The surface modifier of claim 6, wherein said diol is selected from poly(2-butyl-2-ethyl-1,3-propyl carbonate) diol;

poly(2,2 dimethyl-1-3-propyl carbonate)diol; and

poly(hexamethylene carbonate)diol.

8. The surface modifier of claim 6, wherein said diisocyanate is selected from 3-isocyanatomethyl, 3,5,5-trimethyl cyclohexylisocyanate;

4,4′

-methylene bis(cyclohexyl isocyanate);

4,4′

-methylene bis(phenyl)isocyanate;

toluene-2,4 diisocyanate);

m-tetramethylxylene diisocyanate; and

hexamethylene diisocyanate.

9. The surface modifier of claim 6, wherein said step of reacting is performed in the presence of a bismuth carboxylate catalyst.

10. The surface modifier of claim 6, wherein said surface modifier is formed by a process that further comprises the step of reacting said prepolymer with a monohydroxylic surface active group.

11. The surface modifier of any of claim 10, wherein said step of reacting said prepolymer with said monohydroxylic surface active group is performed in the presence of a bismuth carboxylate catalyst.

12. The surface modifier of claim 1 or 5, wherein said soft segment has a number average molecular weight, Mn, of 1,000 to 3,500 Daltons.

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

14. The surface modifier of claim 13, wherein said surface active group is selected from polydimethylsiloxanes, hydrocarbons, polyfluoroalkyl, fluorinated polyethers, and combinations thereof.

15. The surface modifier of claim 14, wherein said surface active group is a polyfluoroalkyl.

16. The surface modifier of claim 15, wherein said surface active group is selected from 1H,1H,2H,2H-perfluoro-1-decanol;

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

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

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

17. The surface modifier of claim 15, wherein said surface active group is selected from the group consisting of radicals of the general formula CF₃(CF₂)_rCH₂CH₂—

wherein r is 2-20, and CF₃(CF₂)_s(CH₂CH₂O)_λ

wherein λ

is 1-10 and s is 1-20.

18. The surface modifier of claim 1 or 5, wherein n is 1.

19. The surface modifier of claim 1 or 5, wherein n is 2.

20. The surface modifier of claim 1 or 5, wherein said surface modifier has a theoretical molecular weight of less than 10,000 Daltons.

21. The surface modifier of claim 1 or 5, wherein said surface modifier comprises from 5 to 30% (w/w) of said hard segment, from 40 to 90% (w/w) of said soft segment, and from 5 to 40% (w/w) of said surface active group.

22. An admixture comprising a surface modifier of any of claims 1-20 admixed with a base polymer.

23. The admixture of claim 22, wherein said base polymer is selected from polypropylenes, polyethylenes, polyesters, polyurethanes, nylons, polysilicones, polystyrene, poly(methyl methacrylates), polyvinylacetates, polycarbonates, poly(acrylonitrile-butadiene), styrene, polyvinylchloride, and blends thereof.

24. The admixture of claim 22, formed by (i) combining said base polymer and said surface modifier to form a mixture, and (ii) heating said mixture above 200°

C.

25. The admixture of claim 22, wherein said admixture comprises from 0.05% to 10% (w/w) of said surface modifier.

26. An article formed from an admixture of any of claims 22-25.

27. The article of claim 26, wherein said article is selected from surgical caps, surgical sheets, surgical covering clothes, surgical gowns, masks, gloves, and surgical drapes.

28. The article of claim 26, wherein said article is a filter.

29. The article of claim 28, wherein said filter is part of a respirator, water filter, air filter, or face mask.

30. The article of claim 26, wherein said article is a cable, film, panel, pipe, fiber, or sheet.

31. The article of claim 26, wherein said article is an implantable medical device.

32. The article of claim 31, wherein said article is a cardiac-assist device, a catheter, a stent, a prosthetic implant, an artificial sphincter, or a drug delivery device.

33. A method for making an article, said method comprising the steps of (i) combining a base polymer with a surface modifier of any of claims 1-20 to form a mixture, and (ii) heating said mixture to at least 200°

C.

34. The method of claim 33, wherein step (ii) comprises heating said mixture to a temperature of between 250°

C. and 345°

C.

5. A surface modifier of formula (I):

G-[B-A]_n-B-G 

 

(I)

wherein

(i) A is a soft segment comprising poly(hexamethylene carbonate), poly (ethylene-co-butylene), 1,6-hexanediol-ortho phthalic anhydride polyester, neopentyl glycol-ortho phthalic anhydride polyester, or bisphenol A ethoxylate;

(ii) B is a hard segment comprising a urethane; and

(iii) G is a surface active group,

wherein n is an integer from 1 to 10.

35. A method for increasing the thermal degradation temperature of a surface modifier of formula (I):

G-[B-A]_n-B-G 

 

(I)

wherein

(i) A is a soft segment;

(ii) B is a hard segment comprising a urethane;

(iii) G is a surface active group; and

(iv) n is an integer from 1 to 10,

said method comprising the steps of;

(a) reacting a diisocyanate with a diol soft segment to form a prepolymer; and

(b) reacting said prepolymer with a monohydroxylic surface active group,

wherein step (a) or (b) is performed in the presence of a bismuth carboxylate catalyst.

36. The method of claim 35, wherein said diol soft segment is selected from hydrogenated-hydroxyl terminated polybutadiene, poly(2,2 dimethyl-1-3-propylcarbonate) diol, poly(hexamethylene carbonate)diol, poly(ethylene-co-butylene)diol, hydroxyl terminated polybutadiene polyol, poly(diethylene glycol)adipate, poly(tetramethylene oxide) diol, diethylene glycol-ortho phthalic anhydride polyester polyol, 1,6-hexanediol-ortho phthalic anhydride polyester polyol, neopentyl glycol-ortho phthalic anhydride polyester polyol, and bisphenol A ethoxylate diol.

37. The method of claim 35, wherein step (a) comprises reacting a diisocyanate with hydrogenated-hydroxyl terminated polybutadiene or poly(2,2 dimethyl-1-3-propylcarbonate)diol.

38. The method of claim 35, wherein said diisocyanate is selected from 3-isocyanatomethyl, 3,5,5-trimethyl cyclohexylisocyanate;

4,4′

-methylene bis(cyclohexyl isocyanate);

4,4′

-methylene bis(phenyl)isocyanate;

toluene-2,4 diisocyanate);

m-tetramethylxylene diisocyanate; and

hexamethylene diisocyanate.

39. The method of claim 35, wherein said monohydroxylic surface active group is selected from compounds of the general formula CF₃(CF₂)_rCH₂CH₂OH wherein r is 2-20, and CF₃(CF₂)_s(CH₂CH₂O)_λ

CH₂CH₂OH wherein α

is 1-10 and s is 1-20.