Polymers having co-continuous architecture

• US 20040236027A1
• Filed: 10/28/2003
• Published: 11/25/2004
• Est. Priority Date: 01/18/2001
• Status: Abandoned Application

• Current Assignee: Bio-Layer Pty Ltd. (AnteoTech Ltd.)
• Original Assignee: Bio-Layer Pty Ltd. (AnteoTech Ltd.)
• Inventors: Shao, Liying, Whittaker, Michael, Maeji, Nobuyoshi Joe, Rasoul, Firas, Kambouris, Peter
• Application Number:
  US10/466,743
• Publication Number:
  US 20040236027A1
• Time in Patent Office: Days
• US Class Current: 525/326.2
• CPC Class Codes: C08F 255/00 Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 255/02 on to polymers of olefins having two or three carbon atoms
• CPC Class Codes: C08F 259/08 on to polymers containing fluorine
• CPC Class Codes: C08J 7/18 using wave energy or particle radiation
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 23/10 Homopolymers or copolymers of propene
• CPC Class Codes: C08L 23/16 Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 51/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• 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

Abstract

The present invention relates generally to a polymer having co-continuous architecture. More particularly, the present invention is directed to a single or plurality of polymer layers in polymeric, co-polymeric, hybrid or blend formation comprising at least one polymer layer having co-continuous architecture. The co-continuous architecture of the one or more polymers permits or otherwise facilitates accessibility of functional groups to an external environment or at least one polymeric layer. The accessible, i.e. co-continuous, nature of the functional groups, in or on the one or more polymers facilitates solid phase chemical processes, chromatography and ion exchange applications. The one or more polymers may also be used as a solid support for a range of diagnostic applications. The present invention further provides a solid support comprising a substrate polymer and one or more further polymers each in pellicular formation with respect to each other and wherein the resulting hybrid polymer comprises a polymer layer which is co-continuous with respect to the substrate polymer and functional groups thereon relative to a solution or solvent phase or other environmental medium surrounding the hybrid polymer. In one form, the co-continuous architecture of a polymer is said to be a polymer having porous-like properties. The present invention further contemplates a method for generating polymers having co-continuous architecture and their use inter alia in solid phase processes including solid phase chemical processes, chromatography and ion exchange as well as their use in a range of diagnostic applications. The present invention further provides a hybrid polymer having two or more polymers in pellicular formation and comprising a polymer layer which is co-continuous with respect to functional groups thereon and the surrounding environment and having a substrate polymer portion with a mouldable shape with a particular mechanical strength and an ability to protect polymeric and/or functional chemical reactivities grafted thereto. In one preferred embodiment, the present invention provides co-continuous architecture formation through use of non-complementary polymers where at least one polymer or co-polymer in a blend of polymers is removable by extraction, salvation or any other chemical or physical means such as but not limited to hydrolysis or degradation. The present invention also provides a polymer having co-continuous architecture in hybrid formation with a rigid basement substrate.

Claims

1. A hybrid polymer comprising a substrate polymer with a surface modified to facilitate co-continuity of functional groups to an external environment and one or a plurality of grafted polymers having a combined thickness of less than 100 microns in pellicular formation, wherein the grafted polymers in the hybrid polymer maintain the co-continuous character of the functional groups to an external environment.

2. The hybrid polymer of claim 1 wherein one of the grafted polymer has a thickness of less than 10 microns.

3. The hybrid polymer of claim 1 wherein one of the grafted polymer has a thickness of less than 5 microns.

4. The hybrid polymer of claim 1 wherein one of the grafted polymer has a thickness of less than 2 microns.

5. The hybrid polymer of claim 1 or 2 or 3, wherein the substrate polymer comprises a polyolefin, a fluoropolymer or a blend of polymers or co-polymers.

6. The hybrid polymer of claim 5, wherein the substrate polymer comprises polypropylene or a polypropylene/EPR co-polymer.

7. The hybrid polymer of claim 5, wherein the substrate polymer comprises a polypropylene/EPDM blend.

8. The hybrid polymer of claim 5, wherein the substrate polymer comprises polyethylene.

9. The hybrid polymer of claim 1 or 2 or 3, wherein the substrate polymer comprises the following characteristics:

a hardness value of from about Hardness Shore “

A”

5 to about Hardness Shore “

D”

100; and

a Flexural Modulus Value of from about 50 to about 2000 Mpa.

10. The hybrid polymer of claim 1 or 2 or 3, wherein the substrate polymer is a polyolefin or fluorinated polymer comprising the following characteristics:

a hardness value of from about Hardness Shore “

A”

10 to about Hardness Shore “

D”

80; and

a Flexural Modulus Value of from about 80 to about 1200 Mpa.

11. The hybrid polymer of claim 1 or 2 or 3, wherein the substrate polymer comprises a solid phase.

12. The hybrid polymer of claim 1 or 2 or 3, wherein the substrate polymer is prepared by a method of macroporous formulation.

13. The hybrid polymer of claim 1 or 2 or 3, wherein the substrate polymer is macroporous.

14. The hybrid polymer of any one of claims 1 to 13, wherein the external environment comprises a liquid, solid or gaseous environment comprising reactive entities.

15. The hybrid polymer of claim 1 or 2 or 3, wherein the one or a plurality of grafted polymers is macroporous.

16. The hybrid polymer of claim 15, wherein the one or a plurality of grafted polymers comprise one or more olefinically-unsaturated monomers.

17. The hybrid polymer of claim 16, wherein the one or more olefinically-unsaturated monomers are selected from the list comprising methyl methacrylate, ethyl methacrylate, propyl methacrylate including all isomers thereof, butyl methacrylate including all isomers thereof, other alkyl methacrylates, corresponding acrylates, functionalized methacrylates and acrylates fluoroalkyl (meth)acrylates, methacrylic acid, acrylic acid, fumaric acid and esters thereof, itaconic acid and esters thereof, nucleic anhydride, styrene, .alpha.-methyl styrene, vinyl halides, acrylonitrile, methacrylonitrile, vinylidene halides of formula CH₂—

C(Hal)₂ wherein each halogen is independently Cl or F, optionally substituted butadiene of the formula CH₂═

C(R₁)C(R₁)═

CH₂ wherein R₁ is independently H, Cl to C₁₀ alkyl, Cl or F, sulphonic acids or derivatives thereof of formula CH₂═

CHSO₂OM wherein M is NaS, K, Li, N(R₂)₄, or —

(CH₂)₂—

D wherein each R₂ is independently H or Cl or C₁₀ alkyl, D is CO₂Z, OH, N(R₂)₂ or SO₂OZ and Z is H. Li, Na, K or N(R₂)₄, acrylamide or derivatives thereof of formula CH₂—

C(CH₃)CON(R₂)₂, and/or mixtures thereof.

18. The hybrid polymer of claim 17, wherein the one or more olefinically-unsaturated monomers are selected from the list comprising functionalized methacrylates and styrene.

19. The hybrid polymer of any one of claims 15 to 18, wherein the one or a plurality of grafted polymers is prepared by a method of macroporous formulation.

20. The hybrid polymer of claim 19, wherein the grafted polymer comprises an inverse opal substrate selected from the list comprising a star polymer, a block polymer and a graft polymer.

21. The hybrid polymer of claim 19, wherein the grafted polymer comprises a polyHIPE-like polymer.

22. The hybrid polymer of claim 19, wherein the grafted polymer is made by a microemulsion polymerization method.

23. The hybrid polymer of claim 1 or 2 or 3, wherein the hybrid polymer has a mouldable shape.

24. The hybrid polymer of claim 23, wherein the shape is a cylinder, film, sheet, bead or disc.

25. The hybrid polymer of claim 24, wherein the hybrid polymer is useful as a substrate for solid phase applications including subsequent grafting.

26. A process for generating a hybrid polymer with a co-continuous character useful as a substrate for solid phase applications, said process comprising grafting a polymer having a thickness of less than 50 microns to a substrate polymer wherein said grafted polymer is sufficiently rigid to permit access of individual functional groups in or within said hybrid polymer to an external environment.

27. The process of claim 26, wherein the substrate polymer comprises a polyolefin, a fluoropolymer or a blend of polymers or co-polymers.

28. The process of claim 26, wherein the substrate polymer comprises polypropylene or a polypropylene/EPR co-polymer.

29. The process of claim 26, wherein the substrate polymer comprises a polypropylene/EPDM blend.

30. The process of claim 26, wherein the substrate polymer comprises polyethylene.

31. The process of claim 26, wherein the substrate polymer comprises the following characteristics:

a hardness value of from about Hardness Shore “

A”

5 to about Hardness Shore “

D”

100; and

a Flexural Modulus Value of from about 50 to about 2000 Mpa.

32. The process of claim 26, wherein the substrate polymer is a polyolefin or fluorinated polymer comprising the following characteristics:

a hardness value of from about Hardness Shore “

A”

10 to about Hardness Shore “

D”

80; and

a Flexural Modulus Value of from about 80 to about 1200 Mpa.

33. The process of claim 26, wherein the substrate polymer comprises a solid phase.

34. The process of claim 26, wherein the substrate polymer is prepared by a method of macroporous formulation.

35. The process of claim 26, wherein the substrate polymer is macroporous.

36. The process of claim 26, wherein one or more polymers or monomeric units thereof are grafted to the substrate polymer in pellicular formation.

37. The process of claim 26, wherein the grafted polymer is macroporous.

38. The process of claim 37, wherein the macroporous grafted polymer comprises one or more olefinically-unsaturated monomers.

39. The process of claim 38, wherein said one or more olefinically-unsaturated monomers are selected from the list comprising methyl methacrylate, ethyl methacrylate, propyl methacrylate including all isomers thereof, butyl methacrylate including all isomers thereof, other alkyl methacrylates, corresponding acrylates, functionalized methacrylates and acrylates fluoroalkyl (meth)acrylates, methacrylic acid, acrylic acid, fumaric acid and esters thereof, itaconic acid and esters thereof, nucleic anhydride, styrene, .alpha.-methyl styrene, vinyl halides, acrylonitrile, methacrylonitrile, vinylidene halides of formula CH₂—

C(Hal)₂ wherein each halogen is independently Cl or F, optionally substituted butadiene of the formula CH₂═

C(R₁)C(R₁)═

CH₂ wherein R₁ is independently H, Cl to C₁₀ alkyl, Cl or F, sulphonic acids or derivatives thereof of formula CH₂═

CHSO₂OM wherein M is NaS, K, Li, N(R₂)₄, or —

(CH₂)₂—

D wherein each R₂ is independently H or Cl or C₁₀ alkyl, D is CO₂Z, OH, N(R₂)₂ or SO₂OZ and Z is H. Li, Na, K or N(R₂)₄, acrylamide or derivatives thereof of formula CH₂—

C(CH₃)CON(R₂)₂, and/or mixtures thereof.

40. The process of claim 39, wherein said one or more olefinically-unsaturated monomers are selected from the list comprising functionalized methacrylates and styrene.

41. The process of any one of claims 37 to 40, wherein the grafted polymer is prepared by a method of macroporous formulation.

42. The process of claim 41, wherein the method of macroporous formulation results in a honeycomb-like polymer arrangement selected from the list comprising a star polymer, a block polymer and a graft polymer.

43. The process of claim 41, wherein the macroporous formulation method results in a polyHIPE-type polymer arrangement.

44. The process of claim 41, wherein the macroporous formulation method comprises a microemulsion polymerization method.

45. The process of claim 26, wherein the hybrid polymer has a mouldable shape.

46. The process of claim 45, wherein the shape is a cylinder, film, sheet, bead or disc.

47. The process of claim 26, wherein the hybrid polymer is macroporous.

48. The process of claim 26, wherein the hybrid polymer is used as a substrate for subsequent grafting.

49. The process of claim 48, wherein the subsequent grafting comprises the addition of olefinically-unsaturated monomers.

50. The process of claim 48, wherein the olefinically-unsaturated monomers are selected from the list comprising methyl methacrylate, ethyl methacrylate, propyl methacrylate including all isomers thereof, butyl methacrylate including all isomers thereof, other alkyl methacrylates, corresponding acrylates, functionalized methacrylates and acrylates fluoroalkyl (meth)acrylates, methacrylic acid, acrylic acid, fumaric acid and esters thereof, itaconic acid and esters thereof, nucleic anhydride, styrene, .alpha.-methyl styrene, vinyl halides, acrylonitrile, methacrylonitrile, vinylidene halides of formula CH₂—

C(Hal)₂ wherein each halogen is independently Cl or F, optionally substituted butadiene of the formula CH₂═

C(R₁)C(R₁)═

CH₂ wherein R₁ is independently H, Cl to C₁₀ alkyl, Cl or F, sulphonic acids or derivatives thereof of formula CH₂═

CHSO₂OM wherein M is NaS, K, Li, N(R₂)₄, or —

(CH₂)₂—

D wherein each R₂ is independently H or Cl or C₁₀ alkyl, D is CO₂Z, OH, N(R₂)₂ or SO₂OZ and Z is H. Li, Na, K or N(R₂)₄, acrylamide or derivatives thereof of formula CH₂—

C(CH₃)CON(R₂)₂, and/or mixtures thereof.

51. The process of claim 50, wherein the olefinically-unsaturated monomers are selected from the list comprising functionalized methacrylates and styrene.