Polymer surface modification

• US 7,368,163 B2
• Filed: 12/14/2005
• Issued: 05/06/2008
• Est. Priority Date: 04/06/2001
• Status: Expired due to Fees

• Current Assignee: Fluidigm Corporation
• Original Assignee: Fluidigm Corporation
• Inventors: Xiao, Shoujun, Unger, Marc A., Huang, Jiang
• Primary Examiner(s): Zimmer; Marc S.
• Application Number:
  US11/304,316
• Publication Number:
  US 20060093836A1
• Time in Patent Office: 874 Days
• Field of Search: None
• US Class Current: 428/304.4
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/327 Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3272 Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: B01L 2200/12 Specific details about manufacturing devices
• CPC Class Codes: B01L 2300/16 Surface properties and coatings
• CPC Class Codes: B01L 2300/163 Biocompatibility
• CPC Class Codes: B01L 3/502707 characterised by the manufacture of the container or its components by shaping or joining plastic parts B29C59/00, B29C65/00; by laminating B32B37/00; manufacture of microstructural devices in general B81C
• CPC Class Codes: B32B 3/26 characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids foam layer B32B5/18; layer of synthetic resin characterised by fillers that create voids or cavities B32B27/205; characterised by an apertured layer
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08F 263/04 on to polymers of vinyl acetate
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 279/02 on to polymers of conjugated dienes
• CPC Class Codes: C08F 287/00 Macromolecular compounds obtained by polymerising monomers on to block polymers
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08J 5/12 Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
• CPC Class Codes: C08J 7/12 Chemical modification
• CPC Class Codes: F04B 43/043 Micropumps
• CPC Class Codes: F04B 43/14 having plate-like flexible members
• CPC Class Codes: Y10T 428/139 : Open-ended, self-supporting conduit, cylinder, or tube-type article
• CPC Class Codes: Y10T 428/1393 : Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/24661 : Forming, or cooperating to form cells
• CPC Class Codes: Y10T 428/24744 : Longitudinal or transverse tubular cavity or cell
• CPC Class Codes: Y10T 428/249953 : Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/249958 : Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249978 : Voids specified as micro
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31667 : Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

The present invention is directed to a surface modified polymer comprising a surface which is covalently bonded to a surface modifying compound. Formation of the covalent bond between the polymer and the surface modifying compound is achieved by a reaction between an intrinsic functional group that is present in the polymer and the functional group of the surface modifying compound. By using a polymer having an intrinsic functional group, a separate surface activation step is avoided.

Claims

1. A polymer article comprising:

a plurality of bulk polymer layers that includes a first polymer layer formed from a first silicone elastomer having a first functional group, and a second layer formed from a second silicone elastomer having a second-functional group, wherein the first and second functional groups are complementary functional groups that react to form a covalent bond,

wherein the first reactive functional group is contributed by a polymer used to prepare the first silicone elastomer, and the second reactive-functional group is contributed by a crosslinking agent used to prepare the second silicone elastomer, wherein the first and second silicone elastomers are derived from the same polymer and crosslinking agent, with the first elastomer having an excess of the group contributed by the polymer and the second elastomer having an excess of the group contributed by the crosslinking agent, and

wherein the two polymer layers are covalently bonded together through the reaction of the complementary functional groups in each of the layers.

2. The polymer article of claim 1, wherein the first and second reactive functional groups are selected from the group consisting of an olefin group, a silane group, a hydroxyl group, an isocynate group, and epoxy group, and an amine group.

3. The polymer article of claim 1, wherein the first and second polymers comprise poly(dimethylsiloxane) units.

4. The polymer article of claim 1 wherein the first polymer that is a precursor for the first elastomer has a vinylsiloxane unit and the crosslinking agent that is a precursor for the second elastomer has a hydrogensiloxane unit.

5. The polymer article of claim 4 wherein the first polymer is poly(dimethylsiloxane-co-vinylmethylsiloxane and the crosslinking agent is poly(dimethylsiloxane-co-methylhydrogensiloxane).

6. The polymer article of claim 1, wherein the first elastomer layer comprises a channel extending from an exterior surface of the first layer and into a bulk polymer matrix of the first layer, wherein the channel defines an inner surface that includes the first reaction functional group.

7. The polymer article of claim 6, wherein a surface modifying compound is covalently bound to the first reactive functional groups on the inner surface of the channel.

8. The polymer article of claim 6, wherein the surface modifying compound is a biocompatible compound.

9. The polymer article of claim 6, wherein the surface modifying compound is selected from the group consisting of polyethylene glycol, poly(methyl methacrylate), poly (ethylene vinyl acetate), poly (2-hydroxyethyl methacrylate), polyvinylpyrrolidone, CH2═

CH—

PEG, and CH2═

CH—

(CH2)n-poly(tetrafluoroethylene).

10. A polymer article comprising:

a plurality of layers of bulk polymer material, wherein the bulk polymer material comprises reactive functional groups dispersed therein, wherein at least two of the plurality of layers of the bulk polymer material are comprised of different polymer materials, and wherein at least one of the plurality of layers of the bulk polymer matrix comprises a silicone elastomer;

an exterior surface;

a channel extending from an exterior surface of the bulk polymer matrix through the bulk polymer matrix, the channel defining an inner surface; and

,

a surface-modifying compound that is covalently bonded to the bulk polymer matrix by reaction with reactive functional groups dispersed along the interior surface of the channel,

wherein an interface between two of the layers is formed by covalent bonding through polymerization of complementary reactive functional groups of the two layers.

11. The polymer article of claim 10, wherein the silicone elastomer is derived from a polymer comprising a poly(dimethylsiloxane) unit.

12. The polymer article of claim 11 wherein the silicone elastomer is derived from a polymer comprising a dimethylsiloxane unit and at least one other siloxane monomer unit.

13. The polymer article of claim 12, where the at least one other siloxane unit is a vinylsiloxane unit or a hydrogensiloxane unit.

14. The polymer article of claim 12, wherein the silicone elastomer is derived from a polymer containing a dimethylsiloxane unit, a second siloxane monomer unit having a reactive group, and a crosslinking agent containing a moiety that is chemically complimentary to the second siloxane unit of the polymer.

15. The polymer article of claim 14 wherein the ratio of reactive of the reactive groups contributed by the second siloxane monomer unit to the complimentary group of the crosslinking agent is greater than 10 to 1.

16. A method of making a polymer article, the method comprising:

forming a first polymer layer from a silicone elastomer derived from a first silicone polymer having a first reactive functional group and a crosslinking agent having a second reactive functional group, wherein the number of the first reactive groups is more than the number of the second reactive groups;

forming a second polymer layer derived from the same polymer having a first reactive functional group and crosslinking agent having a second reactive functional group wherein the number of second reactive groups is more than the number of first reactive groups; and

contacting opposing surfaces of the first and second polymer layers, wherein at least a portion of the first reactive groups in the first polymer layer form a covalent bond with at least a portion of the second reactive functional groups in the second polymer layer.

17. The method of claim 16 wherein the first silicone polymer contains a vinylsiloxane unit and the crosslinking agent contains a hydrogensiloxane unit.

18. The method of claim 16, wherein the first reactive functional group is an olefin group and the second reactive functional group is a silicon-bound hydrogen group.

19. The method of claim 17, wherein, in the first polymer layer, the number of the first reactive groups exceeds the number of the second reactive group by a ratio of 10 to 1 or higher.

20. The method of claim 17, wherein, in the second polymer layer, the number of the second reactive groups exceeds the number of the first reactive group by a ratio of 10 to 1 or higher.

21. The method of claim 16, wherein the method comprises forming a channel in the first polymer layer that extends from an exterior surface of the first layer and into a bulk polymer matrix of the first layer, wherein the channel defines an inner surface that includes the first reaction functional group.

22. The method of claim 21, wherein the method comprises contacting the first reactive functional groups on the inner surface of the channel with a surface modifying compound, wherein the surface modifying compound becomes covalently bound to the inner surface of the channel.

23. The method of claim 22, wherein the surface modifying compound is a biocompatible compound.

24. The method of claim 22, wherein the surface modifying compound is selected from the group consisting of polyethylene glycol, poly(methyl methacrylate), poly (ethylene vinyl acetate), poly (2-hydroxyethyl methacrylate), polyvinylpyrrolidone, CH2═

CH—

PEG, and CH2═

CH—

(CH2)n-poly(tetrafluoroethylene).