THERMALLY STABLE BIURET AND ISOCYANURATE BASED SURFACE MODIFYING MACROMOLECULES AND USES THEREOF

• US 20110207893A1
• Filed: 08/28/2009
• Published: 08/25/2011
• Est. Priority Date: 08/28/2008
• Status: Abandoned Application

• Current Assignee: Interface Biologics, Inc.
• Original Assignee: Interface Biologics, Inc.
• Inventors: Ho, Jeannette, Piotrowicz, Alexandra, Witmeyer, Richard, Mullick, Sanjoy, Chang, Weilun
• Application Number:
  US13/060,542
• Publication Number:
  US 20110207893A1
• Time in Patent Office: Days
• US Class Current: 525/381
• CPC Class Codes: C08G 18/227 of antimony, bismuth or arsenic
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/6208 Hydrogenated polymers of conjugated dienes
• CPC Class Codes: C08G 18/714 containing nitrogen in addition to isocyanate or isothiocyanate nitrogen
• 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 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/791 containing isocyanurate groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8087 containing halogen atoms
• CPC Class Codes: C08L 2205/025 containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• CPC Class Codes: C08L 27/06 Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 81/06 Polysulfones; Polyethersulfones
• CPC Class Codes: C08L 83/04 Polysiloxanes
• 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):

2. The surface modifier of claim 1, wherein

said surface modifier has a thermal degradation temperature of between 200°

C. and 450°

C.;

or

said soft segment has a number average molecular weight (Mn), of 500 to 3,500 Daltons;

or

soft segment comprises hydrogenated polybutadiene (HLBH), poly (2,2 dimethyl-1-3-propylcarbonate) (PCN), polybutadiene (LBHP), polytetramethylene oxide (PTMO), diethyleneglycol-orthophthalicanhydride polyester (PDP), poly (hexamethyhlenecarbonate)diol, hydroxyl terminated polydimethylsiloxanes (PrO-PDMS-PrO) block copolymer, poly(tetramethyleneoxide)diol, hydrogenated-hydroxyl terminated polyisoprene, poly(ethyleneglycol)-block-poly(propyleneglycol))-block-poly(ethylene glycol), 1,12-dodecanediol, hydrogenated polyisoprene (HHTPI), poly(hexamethylene carbonate), poly(2-butyl-2-ethyl-1,3-propyl carbonate), or hydroxylterminated polydimethylsiloxanes block copolymer (C22);

or

said hard segment is formed by reacting a triisocyanate with a diol comprising said soft segment, wherein said triisocyanate is selected from hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer;

or

each surface active group has a molecular weight of between 100-1,500 Da;

or

said surface active group comprises polydimethylsiloxanes hydrocarbons, polyfluoroalkyl, fluorinated polyethers, and combinations thereof;

or

n is 0 or 1;

or

said surface modifier has a theoretical molecular weight of less than 10,000 Daltons;

or

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 25 to 55% (w/w) of said surface active group.

10. The surface modifier of claim 1, wherein said surface active group is selected from the group consisting of radicals of the general formula CH_mF_(3-m)(CF₂)_rCH₂CH₂—

and CH_mF_(3-m)(CF₂)_s(CH₂CH₂O)_χ

—

, wherein

m is 0, 1, 2, or 3;

χ

is an integer between 1-10;

r is an integer between 2-20; and

s is an integer between 1-20.

11. The surface modifier of claim 10, wherein

m is 0 or 1;

or

each surface active group is selected, independently, from (CF₃)(CF₂)₅CH₂CH₂O—

, (CF₃)(CF₂)₇CH₂CH₂O—

, (CF₃)(CF₂)₅CH₂CH₂O—

, CHF₂(CF₂)₃CH₂O—

, and (CF₃)(CF₂)₂CH₂O—

.

18. The surface modifier of any of claim 1, wherein said surface modifier is formed by a process that comprises the steps of

a) combining a solution comprising a biuret or urethane trimer with a solution comprising the surface active group;

and

b) combining the product of (a) with a solution comprising the soft segment; and

wherein

step (a) or step (b) is performed in the presence of a bismuth catalyst;

or

both step (a) and step (b) are performed in the presence of a bismuth catalyst.

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

25. An article formed from the admixture of claim 21.

32. A method for making an article, said method comprising the steps of:

(i) combining a base polymer with the surface modifier of claim 1 to form a mixture; and

(ii) heating said mixture to at least 200°

C.

3-9. -9. (canceled)

12-17. -17. (canceled)

19-20. -20. (canceled)

22-24. -24. (canceled)

26-31. -31. (canceled)

33. (canceled)

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

35. The method of claim 34, wherein

said diol soft segment comprises hydrogenated hydroxyl terminated polybutadiene (HLBH), poly(2,2 dimethyl-1-3-propylcarbonate)diol (PCN), hydroxyl terminated polybutadiene polyol (LBHP), polytetramethylene oxide (PTMO), diethyleneglycol-orthophthalicanhydride polyester polyol (PDP), hydrogenated hydroxyl terminated polyisoprene (HHTPI), poly(hexamethylene carbonate)diol, poly(2-butyl-2-ethyl-1,3-propyl carbonate) diol, or hydroxylterminated polydimethylsiloxanes block copolymer (C22);

or

step (a) comprises reacting a monohydroxylic surface active group with HLBH or PCN;

or

said triisocyanate comprises hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer;

or

said monohydroxylic surface active group is selected from compounds of the general formula CH_mF_(3-m)(CF₂)_rCH₂CH₂—

OH and CH_mF_(3-m)(CF₂)_s(CH₂CH₂O)_χ

—

CH₂CH₂OH, wherein m is 0, 1, 2, or 3;

χ

is an integer between 0-10;

r is an integer between 2-20; and

s is an integer between 1-20.

36-38. -38. (canceled)

39. A surface modifier of formula (II):

40. The surface modifier of claim 39, wherein said surface modifier is formed by a process that comprises the steps of

a) combining a solution comprising a biuret or urethane trimer with a solution comprising the surface active group;

and

b) combining the product of (a) with a solution comprising the soft segment;

wherein step (a) or step (b) is performed in the presence of a bismuth catalyst, or both step (a) and step (b) are performed in the presence of a bismuth catalyst.

43. An admixture comprising a surface modifier of any of claim 39 admixed with a base polymer.

47. An article formed from the admixture of claim 43.

54. A method for making an article, said method comprising the steps of:

(i) combining a base polymer with the surface modifier of claim 39 to form a mixture; and

(ii) heating said mixture to at least 200°

C.

55. The method of claim 54 wherein step (ii) comprises heating said mixture to a temperature of between 220°

C. and 345°

C.

41-42. -42. (canceled)

44-46. -46. (canceled)

48-53. -53. (canceled)

56. A method of increasing repellency by annealing a surface modifier with a base polymer wherein the annealing temperature is between 50°

C. and 75°

C. and the annealing time is between 1-24 hours, wherein said surface modifier has a structure selected from

57-60. -60. (canceled)