Silver polyester-sulfonated nanoparticle composite filaments and methods of making the same

• US 9,877,485 B2
• Filed: 04/13/2016
• Issued: 01/30/2018
• Est. Priority Date: 04/13/2016
• Status: Active Grant

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Farrugia, Valerie M., Keoshkerian, Barkev, Chrtien, Michelle N.
• Primary Examiner(s): Justice, Gina
• Application Number:
  US15/098,255
• Publication Number:
  US 20170295795A1
• Time in Patent Office: 657 Days
• Field of Search: None
• CPC Class Codes: A01N 55/02 containing metal atoms
• 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 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: C08K 2003/0806 Silver
• CPC Class Codes: C08K 3/08 Metals
• CPC Class Codes: C09D 167/00 Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09D177/12; based on polyester-imides C09D179/08; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 5/14 Paints containing biocides, e.g. fungicides, insecticides or pesticides C09D5/16 takes precedence
• CPC Class Codes: C09D 7/61 inorganic
• CPC Class Codes: D01F 1/103 Agents inhibiting growth of microorganisms
• CPC Class Codes: D01F 6/84 from copolyesters

Abstract

A composite filament includes a sulfonated polyester matrix and a plurality of silver nanoparticles dispersed within the matrix and methods of making thereof. Various articles can be manufactured from such composite filaments.

Claims

1. A composite filament for use in fused deposition modelling, comprising:

a sulfonated polyester matrix; and

a plurality of silver nanoparticles dispersed within the matrix,

wherein the silver nanoparticle is present in the composite filament in a range 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 sulfonated polyester has a glass transition (Tg) temperature of from about 45°

C. to about 95°

C.

3. The composite filament of claim 1, wherein the sulfonated polyester matrix comprises a branched polymer.

4. The composite filament of claim 1, wherein the sulfonated polyester matrix comprises a linear polymer.

5. The composite filament of claim 1, wherein the composite filament is in the form of a cylinder having a diameter of about 0.5 mm to about 5.0 mm.

6. The composite filament of claim 1, wherein the sulfonated polyester matrix comprises hydrogen or a salt of a random sulfonated polyester, wherein the sulfonated polyester is selected from poly(1,2-propylene-5-sulfoisophthalate), poly(neopentylene-5-sulfoisophthalate), poly(diethylene-5-sulfoisophthalate), copoly(1,2-propylene-5-sulfoisophthalate)-copoly-(1,2-propylene-terephthalate phthalate), copoly(1,2-propylene-diethylene-5-sulfoisophthalate)-copoly-(1,2-propylene-diethylene-terephthalate phthalate), copoly(ethylene-neopentylene-5-sulfoisophthalate)-copoly-(ethylene-neopentylene-terephthalate-phthalate), copoly(propoxylated bisphenol A)-copoly-(propoxylated bisphenol A-5-sulfoisophthalate), copoly(ethylene-terephthalate)-copoly-(ethylene-5-sulfo-isophthalate), copoly(propylene-terephthalate)-copoly-(propylene-5-sulfo-isophthalate), copoly(diethylene-terephthalate)-copoly-(diethylene-5-sulfo-isophthalate), copoly(propylene-diethylene-terephthalate)-copoly-(propylene-diethylene-5-sulfoisophthalate), copoly(propylene-butylene-terephthalate)-copoly(propylene-butylene-5-sulfo-isophthalate), copoly(propoxylated bisphenol-A-fumarate)-copoly(propoxylated bisphenol A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-fumarate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-maleate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), copoly(propylene-diethylene terephthalate)-copoly(propylene-5-sulfoisophthalate), copoly(neopentyl-terephthalate)-copoly-(neopentyl-5-sulfoisophthalate), and mixtures thereof.

7. The composite filament of claim 6, wherein the salt is selected from the group consisting of sodium, lithium and potassium.

8. The composite of claim 1, wherein the sulfonated polyester matrix comprises a polyol monomer unit selected from the group consisting of trimethylolpropane, 1,2-propanediol, diethylene glycol, and combinations thereof.

9. The composite of claim 1, wherein the sulfonated polyester matrix comprises a diacid monomer unit selected from the group consisting of terephthalic acid, sulfonated isophthalic acid, and combinations thereof.

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

heating a sulfonated polyester resin in an organic-free solvent;

adding a solution of silver (I) ion to the heated resin in the organic-free solvent to form a mixture;

adding a solution of a reducing agent to the mixture, thereby forming an emulsion of particles comprising a sulfonated polyester matrix and a plurality of silver nanoparticles disposed within the sulfonated polyester matrix;

aggregating the emulsion of particles to form aggregated particles;

coalescing the aggregated particles to form coalesced particles;

washing the coalesced particles, thereby forming a composite powder; and

extruding the composite powder to produce the composite filament.

11. The method of claim 10, wherein the heating of the sulfonated polyester resin is conducted at a temperature from about 65°

C. to about 90°

C.

12. The method of claim 10, wherein the aggregating is conducted at a temperature of from about 30°

C. to about 80°

C.

13. The method of claim 10, wherein the coalescing is conducted at a temperature of from about 30°

C. to about 95°

C.

14. The method of claim 10, wherein a source of silver (I) ion is selected from silver nitrate, silver sulfonate, silver fluoride, silver perchlorate, silver lactate, silver tetrafluoroborate, silver oxide and silver acetate.

15. The method of claim 10, wherein the reducing agent is selected from ascorbic acid, trisodium citrate.

16. The method of claim 10, wherein the sulfonated polyester resin is a branched polymer.

17. The method of claim 10, wherein the sulfonated polyester resin is a linear polymer.

18. The method of claim 10, wherein the sulfonated polyester matrix comprises hydrogen or a salt of a random sulfonated polyester, wherein the sulfonated polyester is selected from poly(1,2-propylene-5-sulfoisophthalate), poly(neopentylene-5-sulfoisophthalate), poly(diethylene-5-sulfoisophthalate), copoly(1,2-propylene-5-sulfoisophthalate)-copoly-(1,2-propylene-terephthalate phthalate), copoly(1,2-propylene-diethylene-5-sulfoisophthalate)-copoly-(1,2-propylene-diethylene-terephthalate phthalate), copoly(ethylene-neopentylene-5-sulfoisophthalate)-copoly-(ethylene-neopentylene-terephthalate-phthalate), copoly(propoxylated bisphenol A)-copoly-(propoxylated bisphenol A-5-sulfoisophthalate), copoly(ethylene-terephthalate)-copoly-(ethylene-5-sulfo-isophthalate), copoly(propylene-terephthalate)-copoly-(propylene-5-sulfo-isophthalate), copoly(diethylene-terephthalate)-copoly-(diethylene-5-sulfo-isophthalate), copoly(propylene-diethylene-terephthalate)-copoly-(propylene-diethylene-5-sulfoisophthalate), copoly(propylene-butylene-terephthalate)-copoly(propylene-butylene-5-sulfo-isophthalate), copoly(propoxylated bisphenol-A-fumarate)-copoly(propoxylated bisphenol A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-fumarate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-maleate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), copoly(propylene-diethylene terephthalate)-copoly(propylene-5-sulfoisophthalate), copoly(neopentyl-terephthalate)-copoly-(neopentyl-5-sulfoisophthalate), and mixtures thereof.

19. An article comprising:

a composite filament comprising;

a sulfonated polyester matrix; and

a plurality of silver nanoparticles dispersed within the matrix;

wherein the silver nanoparticle is present in the composite filament in a range 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.

20. The article of claim 19, 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.