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

Patent metadata

Field	Value
Publication number	US-10405540-B2
Application number	US-201615203648-A
Country	US
Kind code	B2
Filing date	Jul 6, 2016
Priority date	Jul 6, 2016
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

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.

First claim

What is claimed is:

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-acryli

Assignees

• Xerox Corp

Inventors

• Farrugia Valerie M
• Keoshkerian Barkev
• Chretien Michelle N

Classifications

• D01F6/36

  comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent · CPC title

• D01F6/16

  from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate · CPC title

• D01F6/22

  from polystyrene · CPC title

• B29C64/118

  using filamentary material being melted, e.g. fused deposition modelling [FDM] · CPC title

• D01F6/42

  comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent · CPC title