Control of polymer surface molecular architecture via amphipathic endgroups

• US 7,884,171 B2
• Filed: 12/15/2009
• Issued: 02/08/2011
• Est. Priority Date: 11/12/2002
• Status: Active Grant

• Current Assignee: Polymer Technology Group, Inc. (DSM-Firmenich AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Ward, Robert S., McCrea, Keith R., Parakka, James P., Tian, Yuan
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): LOEWE, ROBERT S
• Application Number:
  US12/638,371
• Publication Number:
  US 20100113711A1
• Time in Patent Office: 420 Days
• Field of Search: 528/44
• US Class Current: 528/44
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 31/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/2865 Compounds having only one primary or secondary amino group; Ammonia
• CPC Class Codes: C08G 18/289 containing silicon
• CPC Class Codes: C08G 18/3228 acyclic
• CPC Class Codes: C08G 18/5024 containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/5039 containing amide groups
• CPC Class Codes: C08G 18/6283 Polymers of nitrogen containing compounds having carbon-to-carbon double bonds C08G18/6262, C08G18/6266 take precedence
• CPC Class Codes: C08G 18/6287 Polymers of sulfur containing compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08G 18/6795 Unsaturated polyethers
• CPC Class Codes: C08L 75/04 Polyurethanes

Abstract

Polymers whose surfaces are modified by endgroups that include amphipathic surface-modifying moieties. An amphipathic endgroup of a polymer molecule is an endgroup that contains at least two moieties of significantly differing composition, such that the amphipathic endgroup spontaneously rearranges its positioning in a polymer body to position the moiety on the surface of the body, depending upon the composition of the medium with which the body is in contact, when that re-positioning causes a reduction in interfacial energy. An example of an amphipathic surface-modifying endgroup is one that has both a hydrophobic moiety and a hydrophilic moiety in a single endgroup. For instance, a hydrophilic poly(ethylene oxide) terminated with a hydrophilic hydroxyl group is not surface active in air when the surface-modifying endgroup is bonded to a more hydrophobic base polymer. If the hydroxyl group on the oligomeric poly(ethylene oxide) is replaced by a hydrophobic methoxy ether terminus, the poly(ethylene oxide) becomes surface active in air, and allows the poly(ethylene oxide) groups to crystallize in the air-facing surface. In this example, immersion in water destroys the crystallinity as the poly(ethylene oxide) sorbs water and the hydrophobic methoxy group retreats below the surface of the polymer. Also disclosed are methods and articles of manufacture that make use of these polymers.

Claims

1. A polymeric composition of matter having the formula

A[BC]_nZ

wherein B is at least one polymeric block selected from the group consisting of polyurethanes, polyureas, polyamides, aromatic polyesters, aromatic polycarbonates, polystyrenes, and polyacrylates, C is at least one polymeric block selected from the group consisting of polyethers, silicones, aliphatic polyesters, polyisoprenes, optionally-hydrogenated polyisoprenes, polyisobutylenes, optionally-hydrogenated polybutadienes, polyethylenebutylenes, and aliphatic polycarbonates, A is a surface active endgroup selected from the group consisting of polydimethylsiloxane chains and poly(ethylene oxide) chains having one or more amino-, hydroxyl-, carboxyl-, phosphoryl choline-, acryloxy-, or methacryloxy-containing moieties along the chain or at the terminal position thereof, and Z is a surface active endgroup that may be the same as or different from A, or mixtures of said A, B, C and Z, wherein n is a number from 5 through 10⁵, and wherein said polymeric composition of matter has a weight average molecular weight in the range 5000-5,000,000 daltons.

2. The polymeric composition of claim 1, having a weight average molecular weight in the range 50,000-5,000,000 daltons.

3. The polymeric composition of matter of claim 1, wherein A and Z are methoxy ether-terminated polyethylene oxides having one or more crosslinkable reactive groups or groups capable of binding biologically-active molecules along the polyethyleneoxide chain.

4. The polymeric composition of matter in accordance with claim 1, having a polyurethane hard block, a polyoxyalkylene soft block, and at least two surface-modifying amphipathic moieties, wherein at least one of said moieties is a surface active endgroup having a chain that bears multiple pendant groups of different polarity or composition than the main chain of the surface active endgroup.

5. The polymeric composition of matter in accordance with claim 1, comprising a polyoxyalkylene chain having at least one surface-modifying amphipathic moiety, wherein said moiety is a surface active hydrophilic endgroup having a chain bearing multiple pendant hydrophobic groups, wherein the polyoxyalkylene polymer comprising the at least one surface-modifying amphipathic moiety has a molecular weight in the range 5000-5,000,000 daltons.

6. The polymeric composition of matter of claim 5, which has a plurality of acryloxy, methacryloxy, or other crosslinkable reactive groups along a polyethyleneoxide chain.

7. The polymeric composition of matter of claim 5, which has a plurality of amino, hydroxyl, carboxyl, or other groups capable of binding biologically-active molecules along a polyethyleneoxide chain.

8. The polymeric composition of matter of claim 1, which has a polyurethane or polyurea hard block, a polyoxyalkylene soft block, and at least two surface-modifying amphipathic moieties, wherein at least one of the said moieties is a surface active end group having a chain that bears polymerizable groups of different polarity or composition than the main chain of the surface active group.

9. The polymeric composition of matter of claim 8, wherein said hard block is at least one member selected from the group consisting of the reaction product of 4,4′

diphenymethanediisocyanate and ethylenediamine;

the reaction product of 4,4′

diphenymethanediisocyanate, ethylenediamine and 1,3-cyclohexanediamine;

the reaction product of 4,4′

diphenylmethanediisocyanate, ethylenediamine, and 2,2′

-bis(hydroxlmethyl)propionic acid and a prepolymer of 4,4′

diphenymethanediisocyanate and butanediol.

10. The polymeric composition of matter of claim 8 or 9, wherein said soft block is at least one member selected for the group consisting of a polyalkyleneoxide;

a polyalkylenecarbonate a polyethylenebutylene;

an optionally-hydrogenated polybutadiene;

an optionally-hydrogenated polyisoprene;

a polyisobutylene polyol, a polyamine, a blend of polytetramethylene oxide and polypropylene oxide-polyethylene oxide copolymer polyethers, and a methoxy ether-terminated polyethylene oxide having one or more acryl, methacryl, amino, hydroxyl or carboxyl groups.

11. The polymeric composition of matter of claim 10, wherein said polyalkyleneoxide is polytetramethylene oxide polyol or polyamine;

polyhexamethylene oxide polylol or polyamine.

12. The polymeric composition of matter of claim 10, wherein said polyalkylenecarbonate is polyhexamethylenecarbonate polyol or polyhexamethylenecarbonate polyamine;

polyhexamethylenecarbonate-co-ethylenecarbonate polyol or polyhexamethylenecarbonate-co-ethylenecarbonate polyamine.

13. The polymeric composition of matter of claim 10, wherein surface modifying amphipathic moieties are a methoxy ether-terminated polyethylene oxide having one or more acryl, methacryl, amino, hydroxyl, carboxyl, or phosphoryl choline groups along the polyethyleneoxide chain or at the terminal position of the polyethyleneoxide chain.

14. The polymeric composition of matter of claim 8 or 9, wherein surface modifying amphipathic moieties are a methoxy ether-terminated polyethylene oxide having one or more acryl or methacryl groups or amino, hydroxyl, carboxyl, or phosphoryl choline groups along the polyethyleneoxide chain or at the terminal position of the polyethyleneoxide chain.

15. The polymeric composition of matter of claim 1, which has a polyurethane hard block, a silicone soft block, and at least two surface-modifying amphipathic moieties, wherein at least one of the said moieties is a surface active end group having a chain that bears polymerizable groups of different polarity or composition than the main chain of the surface active group.

16. The polymeric composition of matter of claim 8 or 15, wherein said polymerizable group is a meth(acryloxy) group.

17. The polymeric composition of matter of claim 15, wherein said silicone soft block comprises polydimethylsiloxane.

18. The polymeric composition of matter of claim 1, wherein Z and/or A is a polyvinylpyrolidone group.