Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same

Abstract

The present invention relates to a high modulus macroscopic fiber comprising single-wall carbon nanotubes (SWNT) and an acrylonitrile-containing polymer. In one embodiment, the macroscopic fiber is a drawn fiber having a cross-sectional dimension of at least 1 micron. In another embodiment, the acrylonitrile polymer-SWNT composite fiber is made by dispersing SWNT in a solvent, such as dimethyl formamide or dimethyl acetamide, admixing an acrylonitrile-based polymer to form a generally optically homogeneous polyacrylonitrile polymer-SWNT dope, spinning the dope into a fiber, drawing and drying the fiber. Polyacrylonitrile/SWNT composite macroscopic fibers have substantially higher modulus and reduced shrinkage versus a polymer fiber without SWNT. A polyacrylonitrile/SWNT fiber containing 10 wt % SWNT showed over 100% increase in tensile modulus and significantly reduced thermal shrinkage compared to a control fiber without SWNT. With 10 wt % SWNT, the glass transition temperature of the polymer increased by more than 40° C.

1 . A method for making a macroscopic fiber comprising single-wall carbon nanotubes (SWNT) and an acrylonitrile-containing polymer, comprising: 
 (a) mixing SWNT and an acrylonitrile-containing polymer in a solvent to form a polymer-SWNT dope,    (b) spinning the polymer-SWNT dope to form a polymer-SWNT fiber; and    (c) drawing the polymer-SWNT fiber to form a drawn polymer-SWNT macroscopic fiber.    
     
     
         2 . The method of  claim 1  wherein the polymer is selected from the group consisting of polyacrylonitrile, poly(acrylonitrile-methyl acrylate), poly(acrylonitrile-methacrylic acid), poly(acrylonitrile-acrylic acid), poly(acrylonitrile-itaconic acid), poly(acrylonitrile-methyl methacrylate), poly(acrylonitrile-itaconic acid-methyl acrylate), poly(acrylonitrile-methacrylic acid-methyl acrylate), poly(acrylonitrile-vinyl pyridine), poly(acrylonitrile-vinyl chloride), poly(acrylonitrile-vinyl acetate), and combinations thereof.  
     
     
         3 . The method of  claim 1  wherein the polymer is selected from the group consisting of polyacrylonitrile, polyacrylonitrile copolymer and combinations thereof.  
     
     
         4 . The method of  claim 1  wherein the polymer is poly(acrylonitrile-methyl acrylate).  
     
     
         5 . The method of  claim 1  wherein the polymer is poly(acrylonitrile-itaconic acid-methyl acrylate).  
     
     
         6 . The method of  claim 1  wherein the polymer is poly(acrylonitrile-methyl methacrylate).  
     
     
         7 . The method of  claim 1  wherein the single-wall carbon nanotubes are derivatized with a functional group.  
     
     
         8 . The method of  claim 1  wherein the solvent is selected from the group consisting of dimethyl formamide, dimethylsulfoxide, ethylene carbonate, dimethylacetamide, dioxanone, chloroacetonitrile, dimethyl sulfone, propylene carbonate, malononitrile, succinonitrile, adiponitrile, γ-butyrolactone, acetic anhydride, ε-caprolactam, bis(2-cyanoethyl)ether, bis(4-cyanobutyl)sulfone, chloroacetonitrile/water, chloroacetonitrile, cyanoacetic acid, dimethyl phosphate, tetramethylene sulfoxide, glutaronitrile, succinonitrile, N-formylhexamethyleneimine, 2-hydroxyethyl methyl sulfone, N-methyl-β-cyanoethylformamide, methylene dithiocyanate, N-methyl-α,α,α,-trifluoroacetamide, 1-methyl-2-pyridone, 3,4-nitrophenol, nitromethane/water, N-nitrosopiperidine, 2-oxazolidone, 1,3,3,5-tetracyanopentane, 1,1,1-trichloro-3-nitro-2-propane, p-phenol-sulfonic acid, and combinations thereof.  
     
     
         9 . The method of  claim 1  wherein the solvent is a concentrated aqueous acid selected from the group consisting nitric acid and sulfuric acid.  
     
     
         10 . The method of  claim 1  wherein the solvent is a concentrated aqueous salt selected from the group consisting of zinc chloride, lithium bromide and sodium thiocyanate.  
     
     
         11 . The method of  claim 1  wherein the solvent comprises dimethyl formamide.  
     
     
         12 . The method of  claim 1  wherein the solvent comprises dimethyl acetamide.  
     
     
         13 . The method of  claim 1  wherein the dope comprises an anti-gelling agent.  
     
     
         14 . The method of  claim 13  wherein the anti-gelling agent comprises oxalic acid.  
     
     
         15 . The method of  claim 1  wherein the spinning is done by a method selected from the group consisting of gel spinning, wet spinning, dry spinning, dry-jet wet spinning and combinations thereof.  
     
     
         16 . The method of  claim 1  wherein the spinning is done by dry-jet wet spinning.  
     
     
         17 . The method of  claim 1  wherein the spinning is done by gel spinning.  
     
     
         18 . The method of  claim 1  wherein the drawn macroscopic fiber has a length in the range of about 2 times and about 100 times the length of the polymer-SWNT fiber before drawing.  
     
     
         19 . The method of  claim 1  wherein the single-wall carbon nanotubes are present in the drawn polymer-SWNT macroscopic fiber in a range of about 0.001 wt % and about 50 wt %.  
     
     
         20 . The method of  claim 1  wherein the single-wall carbon nanotubes are present in the drawn polymer-SWNT macroscopic fiber in a range of about 1 wt % and about 25 wt %.  
     
     
         21 . The method of  claim 1  wherein the single-wall carbon nanotubes are present in the drawn polymer-SWNT macroscopic fiber in the range of about 5 wt % and about 15 wt %.  
     
     
         22 . The method of  claim 1  wherein at least some of the single-wall carbon nanotubes are present in the macroscopic fiber as single-wall carbon nanotube ropes.  
     
     
         23 . The method of  claim 1  wherein the macroscopic fiber has a cross-sectional dimension of at least about 1 micron.  
     
     
         24 . The method of  claim 1  wherein the polymer-SWNT fiber has a glass transition temperature that is higher than the glass transition temperature of the polymer.  
     
     
         25 . The method of  claim 1  wherein the drawn polymer-SWNT macroscopic fiber has less shrinkage than a drawn fiber of the polymer.  
     
     
         26 . The method of  claim 1  wherein the drawn polymer-SWNT macroscopic fiber has a greater tensile modulus than a drawn fiber of the polymer.  
     
     
         27 . A method for making a macroscopic fiber comprising single-wall carbon nanotubes (SWNT) and an acrylonitrile-containing polymer, comprising: 
 (a) suspending SWNT in a solvent to form a SWNT-solvent suspension;    (b) admixing an acrylonitrile-containing polymer with the SWNT-solvent suspension to form a polymer-SWNT dope,    (c) spinning the polymer-SWNT dope to form a polymer-SWNT fiber; and    (d) drawing the polymer-SWNT fiber to form a drawn polymer-SWNT macroscopic fiber.    
     
     
         28 . The method of  claim 27  wherein the polymer is selected from the group consisting of polyacrylonitrile, poly(acrylonitrile-methyl acrylate), poly(acrylonitrile-methacrylic acid), poly(acrylonitrile-acrylic acid), poly(acrylonitrile-itaconic acid), poly(acrylonitrile-methyl methacrylate), poly(acrylonitrile-itaconic acid-methyl acrylate), poly(acrylonitrile-methacrylic acid-methyl acrylate), poly(acrylonitrile-vinyl pyridine), poly(acrylonitrile-vinyl chloride), poly(acrylonitrile-vinyl acetate), and combinations thereof.  
     
     
         29 . The method of  claim 27  wherein the polymer is selected from the group consisting of polyacrylonitrile, polyacrylonitrile copolymer and combinations thereof.  
     
     
         30 . The method of  claim 27  wherein the polymer is poly(acrylonitrile-methyl acrylate).  
     
     
         31 . The method of  claim 27  wherein the polymer is poly(acrylonitrile-itaconic acid-methyl acrylate).  
     
     
         32 . The method of  claim 27  wherein the polymer is poly(acrylonitrile-methyl methacrylate).  
     
     
         33 . The method of  claim 27  wherein the single-wall carbon nanotubes are derivatized with a functional group.  
     
     
         34 . The method of  claim 27  wherein the solvent is selected from the group consisting of dimethyl formamide, dimethylsulfoxide, ethylene carbonate, dimethylacetamide, dioxanone, chloroacetonitrile, dimethyl sulfone, propylene carbonate, malononitrile, succinonitrile, adiponitrile, γ-butyrolactone, acetic anhydride, ε-caprolactam, bis(2-cyanoethyl)ether, bis(4-cyanobutyl)sulfone, chloroacetonitrile/water, chloroacetonitrile, cyanoacetic acid, dimethyl phosphate, tetramethylene sulfoxide, glutaronitrile, succinonitrile, N-formylhexamethyleneimine, 2-hydroxyethyl methyl sulfone, N-methyl-β-cyanoethylformamide, methylene dithiocyanate, N-methyl-α,α,α,-trifluoroacetamide, 1-methyl-2-pyridone, 3,4-nitrophenol, nitromethane/water, N-nitrosopiperidine, 2-oxazolidone, 1,3,3,5-tetracyanopentane, 1,1,1 -trichloro-3-nitro-2-propane, p-phenol-sulfonic acid, and combinations thereof.  
     
     
         35 . The method of  claim 27  wherein the solvent is a concentrated aqueous acid selected from the group consisting nitric acid and sulfuric acid.  
     
     
         36 . The method of  claim 27  wherein the solvent is a concentrated aqueous salt selected from the group consisting of zinc chloride, lithium bromide and sodium thiocyanate.  
     
     
         37 . The method of  claim 27  wherein the solvent comprises dimethyl formamide.  
     
     
         38 . The method of  claim 27  wherein the solvent comprises dimethyl acetamide.  
     
     
         39 . The method of  claim 27  wherein the dope comprises an anti-gelling agent.  
     
     
         40 . The method of  claim 39  wherein the anti-gelling agent comprises oxalic acid.  
     
     
         41 . The method of  claim 27  wherein the spinning is done by a method selected from the group consisting of gel spinning, wet spinning, dry spinning, dry-jet wet spinning and combinations thereof.  
     
     
         42 . The method of  claim 27  wherein the spinning is done by dry-jet wet spinning.  
     
     
         43 . The method of  claim 27  wherein the spinning is done by gel spinning.  
     
     
         44 . The method of  claim 27  wherein the drawn macroscopic fiber has a length in the range of about 2 times and about 100 times the length of the polymer-SWNT fiber before drawing.  
     
     
         45 . The method of  claim 27  wherein the single-wall carbon nanotubes are present in the drawn polymer-SWNT macroscopic fiber in a range of about 0.001 wt % and about 50wt %.  
     
     
         46 . The method of  claim 27  wherein the single-wall carbon nanotubes are present in the drawn polymer-SWNT macroscopic fiber in a range of about 1 wt % and about 25 wt %.  
     
     
         47 . The method of  claim 27  wherein the single-wall carbon nanotubes are present in the drawn polymer-SWNT macroscopic fiber in the range of about 5 wt % and about 15 wt %.  
     
     
         48 . The method of  claim 27  wherein at least some of the single-wall carbon nanotubes are present in the fiber as single-wall carbon nanotube ropes.  
     
     
         49 . The method of  claim 27  wherein the macroscopic fiber has a cross-sectional dimension of at least about 1 micron.  
     
     
         50 . The method of  claim 27  wherein the polymer-SWNT fiber has a glass transition temperature that is higher than the glass transition temperature of the polymer.  
     
     
         51 . The method of  claim 27  wherein the drawn polymer-SWNT macroscopic fiber has less shrinkage than a drawn fiber of the polymer.  
     
     
         52 . The method of  claim 27  wherein the drawn polymer-SWNT macroscopic fiber has a greater tensile modulus than a drawn fiber of the polymer.  
     
     
         53 - 66 . (canceled)