Thermoplastic composites comprising water-soluble peo graft polymers for use as a sacrificial support in 3d additive manufacturing

Abstract

A method for preparing a vapor sensitive sacrificial support material. The method may include decomposing a polycondensed PEO polymer with heat in the presence of a graphene-like material to release PEO polymer radicals from the polycondensed PEO polymer, such that at least a portion of the PEO polymer radicals become trapped on at least a portion of a surface of the graphene-like material to form a coated graphene-like material, which may be defined as a structural reinforcement material. The method may further include forming the vapor sensitive water-soluble thermoplastic polyethylene oxide graft polymer. The vapor sensitive water-soluble thermoplastic polyethylene oxide graft polymer may include a polyethylene oxide polymer backbone. The vapor sensitive water-soluble thermoplastic polyethylene oxide graft polymer may further include one or more nanoscopic particulate processing aids. The structural reinforcement material may be uniformly dispersed in the vapor sensitive water-soluble thermoplastic polymer composite.

What is claimed is: 
     
         1 . A method for preparing a vapor sensitive sacrificial support material comprising:
 decomposing a polycondensed PEO polymer with heat in the presence of a graphene-like material to release PEO polymer radicals from the polycondensed PEO polymer, wherein at least a portion of the PEO polymer radicals become trapped on at least a portion of a surface of the graphene-like material to form a coated graphene-like material, defined as a structural reinforcement material;   forming the vapor sensitive water-soluble thermoplastic polyethylene oxide graft polymer comprising:
 a polyethylene oxide polymer backbone; and 
 from about 0.05% to about 10% by weight of the polyethylene oxide polymer backbone of at least one polar vinyl monomer grafted to the polyethylene oxide polymer backbone; and 
 one or more nanoscopic particulate processing aids uniformly dispersed in the graft polymer in an amount of from about 0.05 to about 10% by weight of the vapor sensitive water-soluble thermoplastic polymer composite; 
 wherein the structural reinforcement material is uniformly dispersed in the vapor sensitive water-soluble thermoplastic polymer composite in an amount of from about 0.1 to about 20% by weight of the vapor sensitive water-soluble thermoplastic polymer composite. 
   
     
     
         2 . The method of  claim 1 , wherein the vapor sensitive water-soluble thermoplastic polymer composite is formable into a 3D printable sacrificial support material. 
     
     
         3 . The method of  claim 1 , wherein the vapor sensitive water-soluble thermoplastic polyethylene oxide graft polymer composite has a viscosity in the range of about 100 to about 10,000 Pa-sec. when measured at a shear rate in the range of about 1×10 1  to about 1×10 4  reciprocal seconds. 
     
     
         4 . The method of  claim 1 , wherein water-soluble is defined as at least one of a composite, composition, substance, and material that is soluble in that it melts, liquefies, dissolves, disintegrates, falls apart, or solubilizes when brought into contact with an aqueous fluid. 
     
     
         5 . The method of  claim 1 , wherein the vapor sensitive water-soluble thermoplastic polymer composite has an initial electrical resistance value that increases when the vapor sensitive water-soluble thermoplastic polymer composite is exposed to solvent vapor. 
     
     
         6 . The method of  claim 5 , wherein the solvent vapor comprises at least one of dichloromethane, chloroform, tetrahydrofuran, carbon tetrachloride, acetonitrile, alcohols, and cyclohexane. 
     
     
         7 . The method of  claim 5 , wherein the electrical resistance of the vapor sensitive water-soluble thermoplastic polymer composite returns to the initial electrical resistance value when the vapor sensitive water-soluble thermoplastic polymer composite is exposed to dry air. 
     
     
         8 . The method of  claim 2 , wherein the 3D printable sacrificial support material is in the form of a filament, film, powder, pellet, or suspended in solvent. 
     
     
         9 . The method of  claim 1 , wherein the graphene-like material comprises at least one of graphene, graphene nanoplatelets, graphene oxide, graphite, functionalized graphene nanoplatelets, plasma treated graphene nanoplatelets; reduced graphene oxide, partially reduced graphene oxide, carbon fibers, carbon nanotubes, and carbon black. 
     
     
         10 . The method of  claim 1 , wherein the catalytic thermal initiator comprises at least one of 4,4′-azobis (4-cyanopentanoyl dichloride), alkyl, dialkyl, diaryl, arylalkyl peroxides, di-t-butyl peroxide, cumyl peroxide, 1,1-di-t-butylperoxy, hexane, acyl peroxide, acetyl peroxide, benzoyl peroxide, hydroperoxide, cumyl hydroperoxide, p-methane hydroperoxide, perester, peroxyester, t-butyl peroxypivalate, t-butyl perbenzoateetc, alkylsulfonyl peroxide, dialkyl peroxymonocarbonate, dialkyl peroxycarbonate, ketone peroxide, azo compound, 2,2′-azobisisobutyronitrile (AIBN), and 1,1′-azobis (cyclohexanecarbonitrile). 
     
     
         11 . The method of  claim 2 , wherein the 3D printable sacrificial support material is at least one of a filament for a fused filament fabrication (FFF) technique, a powder or pellet for a selective laser sintering (SLS) technique, is suspended in a solvent for an inkjet 3D printing technique, and a pellet, powder, or crushed for an injection molding 3D printing technique. 
     
     
         12 . The method of  claim 1 , wherein the one or more nanoscopic particulate processing aids comprise at least one of titanium dioxide nanopowder, alumina nanopowder, silica nanopowder, fumed silica, zirconia nanopowder, vanadia nanopowder, antimony oxide nanopowder, tin oxide nanopowder, ceria nanopowder, and zinc oxide nanopowder. 
     
     
         13 . The method of  claim 1 , wherein the vapor sensitive water-soluble thermoplastic polymer composite includes at least one plasticizer in an amount of from about 0.1 to about 10% by weight of the vapor sensitive water-soluble thermoplastic polymer composite. 
     
     
         14 . A 3D printable sacrificial support material for use in printing a 3D article, the 3D printable sacrificial support material comprising:
 a vapor sensitive water-soluble thermoplastic polymer composite comprising:
 a vapor sensitive water-soluble thermoplastic polyethylene oxide graft polymer having: 
 a polyethylene oxide polymer backbone; and 
 from about 0.05% to about 10% by weight of the polyethylene oxide polymer backbone of at least one polar vinyl monomer grafted to the polyethylene oxide polymer backbone; 
 one or more nanoscopic particulate processing aids uniformly dispersed in the graft polymer in an amount of from about 0.05 to about 10% by weight of the vapor sensitive water-soluble thermoplastic polymer composite; 
 at least one plasticizer in an amount of from about 0.1 to about 10% by weight of the vapor sensitive water-soluble thermoplastic polymer composite; and 
 a structural reinforcement material uniformly dispersed in the vapor sensitive water-soluble thermoplastic polymer composite in an amount of from about 0.1 to about 20% by weight of the vapor sensitive water-soluble thermoplastic polymer composite; 
 wherein the structural reinforcement material comprises a graphene-like material that includes polycondensed polyethylene oxide polymer radicals carried on at least a portion of a surface of the graphene-like material; and 
   wherein the vapor sensitive water-soluble thermoplastic polymer composite has an initial electrical resistance value that increases when the vapor sensitive water-soluble thermoplastic polymer composite is exposed to solvent vapor;   wherein the electrical resistance of the vapor sensitive water-soluble thermoplastic polymer composite return to the initial electrical resistance value when the vapor sensitive water-soluble thermoplastic polymer composite is exposed to dry air; and   wherein water-soluble is defined as at least one of a composite, composition, substance, and material that is soluble in that it melts, liquefies, dissolves, disintegrates, falls apart, or solubilizes when brought into contact with an aqueous fluid.   
     
     
         15 . The 3D printable sacrificial support material of  claim 14 , wherein the vapor sensitive water-soluble thermoplastic polymer composite has a viscosity in the range of about 100 to about 10,000 Pa-sec. when measured at a shear rate in the range of about 1×10 1  to about 1×10 4  reciprocal seconds. 
     
     
         16 . The 3D printable sacrificial support material of  claim 14 , wherein the solvent vapor comprises at least one of dichloromethane, chloroform, tetrahydrofuran, carbon tetrachloride, acetonitrile, alcohols, and cyclohexane. 
     
     
         17 . The 3D printable sacrificial support material of  claim 14 , wherein the 3D printable sacrificial support material is in the form of a filament, film, powder, pellet, or suspended in solvent. 
     
     
         18 . The 3D printable sacrificial support material of  claim 14 , wherein the graphene-like material comprises at least one of graphene, graphene nanoplatelets, graphene oxide, graphite, functionalized graphene nanoplatelets, plasma treated graphene nanoplatelets; reduced graphene oxide, partially reduced graphene oxide, carbon fibers, carbon nanotubes, and carbon black. 
     
     
         19 . The 3D printable sacrificial support material of  claim 14 , wherein the 3D printable sacrificial support material is at least one of a filament for a fused filament fabrication (FFF) technique, a powder or pellet for a selective laser sintering (SLS) technique, is suspended in a solvent for an inkjet 3D printing technique, and a pellet, powder, or crushed for an injection molding 3D printing technique. 
     
     
         20 . The 3D printable sacrificial support material of  claim 14 , wherein the one or more nanoscopic particulate processing aids comprise at least one of titanium dioxide nanopowder, alumina nanopowder, silica nanopowder, fumed silica, zirconia nanopowder, vanadia nanopowder, antimony oxide nanopowder, tin oxide nanopowder, ceria nanopowder, and zinc oxide nanopowder.