Anti-bacterial metallo ionomer polymer nanocomposite filaments and methods of making the same

• US 10,405,540 B2
• Filed: 07/06/2016
• Issued: 09/10/2019
• Est. Priority Date: 07/06/2016
• Status: Active Grant

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Farrugia, Valerie M., Keoshkerian, Barkev, Chretien, Michelle N.
• Primary Examiner(s): Rickman, Holly C
• Assistant Examiner(s): Chau, Lisa
• Application Number:
  US15/203,648
• Publication Number:
  US 20180007892A1
• Time in Patent Office: 1,161 Days
• CPC Class Codes: A01N 25/26 in coated particulate form
• CPC Class Codes: A01N 59/16 Heavy metals; Compounds thereof
• CPC Class Codes: B29C 64/118 using filamentary material being melted, e.g. fused deposition modelling [FDM]
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: C08J 2325/14 with unsaturated esters
• CPC Class Codes: C08J 2433/04 esters
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C09K 5/14 Solid materials, e.g. powdery or granular
• CPC Class Codes: D01F 1/103 Agents inhibiting growth of microorganisms
• CPC Class Codes: D01F 6/16 from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
• CPC Class Codes: D01F 6/22 from polystyrene
• CPC Class Codes: D01F 6/36 comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
• CPC Class Codes: D01F 6/42 comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
• CPC Class Codes: D01F 6/52 of polymers of unsaturated carboxylic acids or unsaturated esters
• CPC Class Codes: D01F 6/56 of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys

Abstract

A composite filament includes a core particle comprising a styrene/acrylate polymer resin, and a shell comprising a styrene/acrylate ionomer resin, wherein the styrene/acrylate ionomer resin comprises a metal ion acrylate monomer, and methods of making thereof. Various articles can be manufactured from such composite filaments.

Claims

1. A composite filament comprising:

a core particle comprising a styrene/acrylate polymer resin and optionally a first metal ion acrylate monomer, wherein the styrene/acrylate polymer resin comprises a copolymer of styrene monomer, acrylate monomer, or mixtures thereof; and

a shell comprising a styrene/acrylate ionomer resin, wherein the styrene/acrylate ionomer resin comprises a copolymer of styrene monomer, acrylate monomer, or mixtures thereof, further wherein the styrene/acrylate ionomer resin comprises a second metal ion acrylate monomer;

wherein a total amount of metal presented in the composite filament ranges in a concentration of from about 0.5 ppm to about 50,000 ppm; and

further wherein the composite filament has a diameter of from about 0.5 mm to about 5 mm.

2. The composite filament of claim 1, wherein the second metal ion acrylate monomer of the shell comprises a silver.

3. The composite filament of claim 1, wherein the styrene/acrylate ionomer resin of the shell comprises a silver monomer selected from a silver acrylate monomer, a silver methacrylate monomer or combinations thereof.

4. The composite filament of claim 3, wherein the silver monomer is present in the shell resin from about 0.01% to about 10% by weight of the styrene/acrylate ionomer resin in the shell.

5. The composite filament of claim 1, wherein the styrene/acrylate ionomer resin of the shell comprises a co-monomer selected from methyl methacrylate, butyl acrylate, diacrylate, cyclohexyl methacrylate, styrene, methacrylic acid, dimethylaminoethyl methacrylate or combinations thereof.

6. The composite filament of claim 1, wherein the styrene/acrylate polymer resin of the core is selected from the group consisting of styrene acrylates, styrene butadienes, styrene methacrylates, and combinations thereof.

7. The composite filament of claim 6, wherein the styrene/acrylate polymer resin of the core is selected from the group consisting of poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid) and combinations thereof.

8. The composite filament of claim 1 having a glass transition temperature (Tg) of from about −

5°

C. to about 150°

C.

9. The composite filament of claim 1 having a thermal conductivity of from about 0.04 W/(mK) to about 50 W/(mK).

10. The composite filament of claim 1 having a tensile strength of from about 10 MPa to about 200 MPa.

11. The composite filament of claim 1 further comprises an additive selected from the group consisting of a wax, a pigment, a ceramic, a carbon fiber, a nanotube, or a combination thereof.

12. A method of producing a composite filament, comprising:

polymerizing a first mixture comprising a first styrene/acrylate copolymer to form a core styrene/acrylate polymer resin and optionally a first metal ion acrylate monomer in an organic-free solvent;

heating the core styrene/acrylate polymer resin, wherein the styrene/acrylate polymer resin comprises a copolymer of styrene monomer, acrylate monomer, or mixtures thereof;

adding a shell styrene/acrylate ionomer resin by polymerizing a second mixture comprising a second styrene/acrylate copolymer and initiator to the core styrene/acrylate polymer resin to form a shell disposed about the core styrene/acrylate polymer resin, thereby forming an emulsion of composite particles, wherein the shell styrene/acrylate ionomer resin comprises a second metal ion acrylate monomer;

wherein the styrene/acrylate ionomer resin comprises a copolymer of styrene monomer, acrylate monomer, or mixtures thereof,

aggregating the emulsion of composite particles to form aggregated particles;

coalescing the aggregated particles to form coalesced particles;

washing the coalesced particles, thereby forming a composite powder;

extruding the composite powder to produce the composite filament;

wherein a total amount of metal presented in the composite filament ranges in a concentration of from about 0.5 ppm to about 50.000 ppm; and

further wherein the composite filament has a diameter of from about 0.5 mm to about 5 mm.

13. The method of claim 12, wherein the metal is silver, copper, gold, palladium, or mixtures thereof.

14. The method of claim 12, wherein the styrene/acrylate ionomer resin of the shell comprises a silver monomer selected from a silver acrylate monomer, a silver methacrylate monomer or combinations thereof.

15. The method of claim 12, wherein the core styrene/acrylate polymer resin is selected from the group consisting of poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), polystyrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid) and combinations thereof.

16. The method of claim 12, wherein the aggregating is conducted at a temperature of from about 30°

C. to about 80°

C.

17. The method of claim 12, wherein the coalescing is conducted at a temperature of from about 30°

C. to about 95°

C.

18. An article comprising:

a composite filament comprising;

a core particle comprising a styrene/acrylate polymer resin and optionally a first metal ion acrylate monomer, wherein the styrene/acrylate polymer resin comprises a copolymer of styrene monomer, acrylate monomer, or mixtures thereof; and

a shell comprising a styrene/acrylate ionomer resin, wherein the styrene/acrylate ionomer resin comprises a copolymer of styrene monomer, acrylate monomer, or mixtures thereof, further wherein the styrene/acrylate ionomer resin comprises a second metal ion acrylate monomer;

wherein a total amount of metal presented in the composite filament ranges in a concentration of from about 0.5 ppm to about 50,000 ppm; and

further wherein the composite filament has a diameter of from about 0.5 mm to about 5 mm.

19. The article of claim 18, wherein the styrene/acrylate polymer resin of the core is selected from the group consisting of poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), polystyrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid) and combinations thereof.

20. The article of claim 18, wherein the article is selected from the group consisting of a biochemical sensor, an optical detector, an antibacterial, a textile, a cosmetic, an electronic component, a fiber, and a cryogenic superconducting material.