Fiber modified with particulate through a coupling agent

Abstract

An article is provided that includes a polymeric fiber that has an excess number of surface active reactive moieties relative to the number of surface reactive moieties found on the fiber in a native state. A particle is bonded covalently to the fiber through an intermediate coupling agent. Multiple particles can be covalently bonded to the fiber, the multiple particles can be bonded uniformly or asymmetrically around the fiber diameter. A process for modifying a fiber includes creating surface activated reactive moieties thereon. The activated fiber is then exposed to a liquid solution containing a coupling agent to form a covalent bond. The coupling agent is also reacted with a particle in a liquid solution to form a covalent bond between the coupling agent and the particle. The coupling agent is covalently bonded to either a particle and then bonded to the fiber, or vice versa.

1 . An article comprising:
 a polymeric fiber having in a native state a number of surface reactive moieties, said fiber being activated to have a plurality of surface activated reactive moieties, said plurality of reactive moieties being greater than the number of native surface reactive moieties;   a particle; and   a coupling agent intermediate between said particle and said fiber, said coupling agent forming a first covalent bond to one of said plurality of surface activated reactive moieties and a second covalent bond to said particle.   
     
     
         2 . The article of  claim 1  wherein said polymeric fiber is selected from a group consisting of: polyamides, polyolefins, polyesters, block copolymers, styrene butadiene copolymers, mixed olefin copolymers, polycarbonates, polystyrene, fluoropolymers, polyvinyls, polyurethanes, polysiloxanes; polycarbonate/polydimethyl siloxane copolymers, poly p(-phenylenebenzobisoxazole), carbon fibers, include silk, cellulose, wool, cotton, linen, hemp, ramie, and jute. 
     
     
         3 . The article of  claim 1  wherein said polymeric fiber is a polyamide. 
     
     
         4 . The article of  claim 1  wherein said plurality of surface activated reactive moieties comprise a heteroatom selected from the group consisting of: nitrogen, sulfur, oxygen and chlorine, iodine, bromine, or fluorine. 
     
     
         5 . The article of  claim 1  wherein the plurality of surface activated reactive moieties are chemically distinct from the number of native surface reactive moieties. 
     
     
         6 . The article of  claim 1  wherein the plurality of surface activated reactive moieties comprise amine groups. 
     
     
         7 . The article of  claim 1  wherein said particle has catalytic activity. 
     
     
         8 . The article of  claim 1  further comprising a plurality of particles coating said fiber. 
     
     
         9 . The article of  claim 8  wherein the plurality of particles asymmetrically coat said fiber about a fiber diameter. 
     
     
         10 . The article of  claim 1  further comprising a reagent covalently bonded to said particle. 
     
     
         11 . The article of  claim 8  wherein the plurality of particles are selected from the group consisting of: colloidal silica; silica alumina; silica magnesia; magnesium silicate; magnetic cobalt containing alloys; magnetic niobium containing alloys; metal-oxides, -sulfides, -carbides, -nitrides, -arsenides, -phosphides, silicon; nanolatex; epoxidized rubber, polystyrene nanospheres, barium strontium titanate (Ba,Sr)TiO 3 , and combinations thereof. 
     
     
         12 . The article of  claim 8  wherein the plurality of particles comprises colloidal silica. 
     
     
         13 . The article of  claim 1  wherein said coupling agent has the formula:
   (X) m —R—(Y) n   (I)   
       where X is independently in each occurrence a moiety reactive with an activated polymeric fiber surface 
       
         
           
           
               
               
           
         
       
       NHR 1 —, HS—, HO—, R 2 OOC—, C(R 1 ) 2 ═CR 1 —, —R 1 C═CH—HC═CR 2 , OCN—, XOC—(X═Cl, Br, I), R 1 ≡C—, N 3 —, 
       
         
           
           
               
               
           
         
       
       m is an integer 1, 2 or 3; R 1  is independently in each occurrence hydrogen or C 1 -C 4  alkyl; R 2  is an electron, hydrogen, C 1 -C 4  alkyl; R 3  is independently in each occurrence hydrogen; C 0 -C 4  alkyl having a substituent from the group sulfonate, carboxyl, hydroxyl, amine, C 1 -C 4  substituted aryl; C 7 -C 14  aralkyl; and two adjacent R 3  substituents combined to form a six-member ring joined to a base phenonyl group, the combined adjacent R 3  substituents having at least three cycloalkyl or aryl carbons and a fourth ring forming carbon, oxygen, sulfur or nitrogen atom or NR 1  group; R is a linear backbone of a C 2 -C 24  alkyl, C 6 -C 24 , aryl, C 6 -C 24  cycloalkyl, ethers-, esters-, thioethers- and amides- of C 2 -C 24  alkyl, and solubility enhancing substituent of R 4  where the substituent is sulfonyl; Y is SiR 3-p   5 —(OR 5 ) p , chlorosilyl, or X with the proviso that when Y is independently in each occurrence X, R is less than eight linear carbon atoms in the backbone to the nearest X; p is an integer 1, 2 or 3; R 5  is independently in each occurrence hydrogen or C 1 -C 4  alkyl with the proviso that R 5  is not in all occurrences hydrogen; and m is an integer 1, 2 or 3. 
     
     
         14 . The article of  claim 13  where m is 1 and n is 1. 
     
     
         15 . The article of  claim 14  where X is one of NHR 1 —, HS—R 2 OOC—, and C(R 1 ) 2 ═CR 1 —. 
     
     
         16 . The article of  claim 15  where R 3  in every occurrence is hydrogen and Y is 
       
         
           
           
               
               
           
         
       
     
     
         17 . The article of  claim 13  where Y in every occurrence is Si—R 5   3-p (OR 5 ) p . 
     
     
         18 . The article of  claim 14  where both X and Y are 
       
         
           
           
               
               
           
         
       
     
     
         19 . A process for modifying a fiber comprising:
 activating a polymeric fiber surface to create a plurality of surface activated reactive moieties thereon;   exposing the plurality of surface activated reactive moieties to a liquid solution of a coupling agent;   inducing the formation of a covalent bond between said coupling agent and at least one of the plurality of surface activated reactive moieties;   exposing said coupling agent to a plurality of particles in liquid solution; and   inducing formation of a covalent bond between said coupling agent and at least one of the plurality of particles.   
     
     
         20 . The process of  claim 19  wherein activating said polymeric fiber occurs within a plasma. 
     
     
         21 . The process of  claim 19  wherein activating said polymeric fiber occurs in an atmosphere containing a reaction gas. 
     
     
         22 . The process of  claim 19  wherein the step of exposing said coupling agent to the plurality of particles occurs prior to exposure of said polymeric fiber to said liquid solution of said coupling agent. 
     
     
         23 . The process of  claim 19  wherein exposing said polymeric fiber to said liquid solution of said coupling agent occurs prior to exposure of said coupling agent to the plurality of particles. 
     
     
         24 . The process of  claim 19  wherein said coupling agent has the formula
   (X) m —R—(Y) n   (I)   
       where X is independently in each occurrence a moiety reactive with an activated polymeric fiber surface 
       
         
           
           
               
               
           
         
       
       NHR 1 —, HS—, HO—, R 2 OOC—, C(R 1 ) 2 ═CR 1 —, R 1 C═CH—HC═CR 2 , OCN—, XOC—(X═Cl, Br, I), R 1 ≡C—, N 3 —, 
       
         
           
           
               
               
           
         
       
       m is an integer 1, 2 or 3; R 1  is independently in each occurrence hydrogen or C 1 -C 4  alkyl; R 2  is an electron, hydrogen, C 1 -C 4  alkyl; R 3  is independently in each occurrence hydrogen; C 0 -C 4  alkyl having a substituent from the group sulfonate, carboxyl, hydroxyl, amine, C 1 -C 4  substituted amine, and quaternary amine; C 6 -C 12  aryl; C 7 -C 14  aralkyl; and two adjacent R 3  substituents combined to form a six-member ring joined to a base phenonyl group, the combined adjacent R 3  substituents having at least three cycloalkyl or aryl carbons and a fourth ring forming carbon, oxygen, sulfur or nitrogen atom or NR 1  group; R is a linear backbone of a C 2 -C 24  alkyl, C 6 -C 24  aryl, C 6 -C 24  cycloalkyl, ethers-, esters-, thioethers- and amides- of C 2 -C 24  alkyl, and solubility enhancing substituent of R 4  where the substituent is sulfonyl; Y is SiR 3-p   5 —(OR 5 ) p  chlorosilyl or X with the proviso that when Y is independently in each occurrence X, R is less than eight linear carbon atoms in the backbone to the nearest X; p is an integer 1, 2 or 3; R 5  is independently in each occurrence hydrogen and C 1 -C 4  alkyl with the proviso that R 5  is not in all occurrences hydrogen; and m is an integer 1, 2 or 3. 
     
     
         25 . The process of  claim 19  wherein activating said polymeric fiber occurs through UV irradiation. 
     
     
         26 . The process of  claim 24  where X is 
       
         
           
           
               
               
           
         
       
       and wherein activation is by UV irradiation in the presence of said coupling agent. 
     
     
         27 . The process of  claim 26  wherein said polymeric fiber is formed as an opaque sheet having a first side and an opposing side wherein activation is performed preferentially on the first side of the sheet. 
     
     
         28 . The process of  claim 27  further comprising the step of activating the opposing side of said sheet after the plurality of particles are covalently bonded to the first side and covalently bonding a second plurality of particles to said opposing side. 
     
     
         29 . The process of  claim 21  further comprising covalently bonding a reagent to at least one of the plurality of particles, said reagent reactive towards a substance. 
     
     
         30 . The process of  claim 19  wherein the plurality of particles further comprise a passivating ligand coat and said coupling agent covalently bonds to said passivating ligand coat.