Reactive Block Copolymers as Additives for the Preparation of Silicate-Polymer Composites

Abstract

A process for making a block copolymer compatibilizer comprises reacting an acrylic and/or vinyl monomer that has functional groups with one or more vinyl monomers in the presence of a free radical initiator and a stable free radical to form a reaction product that includes residual unreacted acrylic and/or vinyl monomer, and reacting one or more vinyl monomers with the reaction product to form a second block that incorporates the residual unreacted acrylic monomer. The block copolymer is used to compatibilize a clay nanocomposite material with a thermoplastic or thermoset resin. The block copolymer can be used with existing, commercially-available clays, or the block copolymer can be formed with a polar block that is miscible in a polar dispersion medium for use as a intercalate in producing a clay nanocomposite material.

1 . A polymer/clay nanocomposite material having a composition, comprising:
 a) an organic clay;   b) a block copolymer having a composition that includes a first block, the first block comprising monomeric units of a functionalized acrylic monomer and/or a functionalized vinyl monomer and monomeric units of a vinyl monomer, and a second block, the second block comprising monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic monomer and/or the functionalized vinyl monomer from the first block; and   c) a thermoplastic matrix.   
     
     
         2 . The polymer/clay nanocomposite material of  claim 1 , further comprising a functionalized polyolefin. 
     
     
         3 . The polymer/clay nanocomposite material of  claim 1 , wherein the organic clay is selected from the group consisting of natural, synthetic, modified clay intercalated with an intercalant and mixtures thereof. 
     
     
         4 . The polymer/clay nanocomposite material of  claim 1 , wherein the first block of the block copolymer is a random copolymer having a total length between 1 and 720 monomeric units, and wherein the second block of the block copolymer has a length between 100 and 2000 monomeric units. 
     
     
         5 . The polymer/clay nanocomposite material of  claim 1 , wherein the functionalized acrylic monomer and/or the functionalized vinyl monomer has one or more functional groups selected from the group consisting of epoxy, acid, anhydride, amine, amide and hydroxyl groups. 
     
     
         6 . The polymer/clay nanocomposite material of  claim 1 , wherein the thermoplastic polymer is selected from the group consisting of hydrogenated homopolymers, partially hydrogenated homopolymers, random tapered or block copolymers of conjugated dienes and monovinyl aromatic compounds, vinyl aromatic homopolymers and copolymers, polyphenylene ether, polyvinyl methyl ether and tetramethyl polycarbonate, polyacrylates and their copolymers with vinyl aromatic polymers, poly(vinyl chloride), poly(vinylidene chloride), polyolefins, aliphatic and aromatic polycarbonates, polyesters, polyamides, polyimides, polyacetals, polyphenylene ether, polyphenylene sulfides, polysulfones, polyether sulfones, vinylidene polymers, fluoropolymers, polysiloxanes and mixtures thereof. 
     
     
         7 . The polymer/clay nanocomposite material of  claim 2 , wherein the functionalized polyolefin is previously treated with 0.01 to 10% of an acid molecule. 
     
     
         8 . The polymer/clay nanocomposite material of  claim 7 , wherein the acid molecule is a Lewis acid. 
     
     
         9 . The polymer/clay nanocomposite material of  claim 8 , wherein the functionalized polyolefin is a maleated polyolefin, and wherein the thermoplastic matrix is polypropylene. 
     
     
         10 . The polymer/clay nanocomposite material of  claim 1 , wherein the organic clay is intercalated and/or exfoliated by the block copolymer. 
     
     
         11 . The polymer/clay nanocomposite material of  claim 1 , wherein the polymer/clay nanocomposite material has a composition, comprising:
 a) 3-15% wt of the organic clay;   b) 1.5-30% wt of the block copolymer; and   c) 55-95.5% wt of the thermoplastic matrix.   
     
     
         12 . The polymer/clay nanocomposite material of  claim 1 , further comprising a functionalized polyolefin, thereby forming a polyolefin/clay nanocomposite, wherein the polyolefin/clay nanocomposite material has a composition, comprising:
 a) 3-10% wt of the organic clay;   b) 1.5-20% wt of the block copolymer;   c) 1.5-50% wt of the functionalized polyolefin; and   d) 20-94% wt of the thermoplastic matrix, wherein the thermoplastic matrix is a polyolefin.   
     
     
         13 . A process for making a polymer/clay nanocomposite material, comprising the steps of:
 mixing an organic clay and a block copolymer together in a ratio between the clay and the block copolymer of between 100:1 and 1:1000 to form a nanocomposite concentrate; and   mixing the nanocomposite concentrate and a thermoplastic polymer to form a polymer/clay nanocomposite,   wherein the block copolymer has a composition that includes a first block, the first block comprising monomeric units of a functionalized acrylic monomer and/or a functionalized vinyl monomer and monomeric units of a vinyl monomer, and a second block, the second block comprising monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic monomer and/or the functionalized vinyl monomer from the first block.   
     
     
         14 . A process for making a polymer/clay nanocomposite material, comprising the steps of:
 mixing an organic clay and a block copolymer together in a ratio between the clay and the block copolymer of between 100:1 and 1:1000 to form a nanocomposite concentrate;   mixing the nanocomposite concentrate and a functional polyolefin to form a polyolefin masterbatch; and   mixing the polyolefin masterbatch and a thermoplastic polymer to obtain a polymer/clay nanocomposite material.   
     
     
         15 . The process of  claim 14 , wherein the block copolymer has a composition that includes a first block, the first block comprising monomeric units of a functionalized acrylic monomer and/or a functionalized vinyl monomer and monomeric units of a vinyl monomer, and a second block, the second block comprising monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic monomer and/or the functionalized vinyl monomer from the first block. 
     
     
         16 . The process of  claim 14 , wherein the block copolymer is made from a process, comprising the steps of:
 reacting an acrylic and/or vinyl monomer having functional groups and one or more vinyl monomers in the presence of a free radical initiator and a stable free radical in a first step to form a reaction product, wherein the reaction product includes residual unreacted acrylic and/or vinyl monomer; and   reacting in a second step one or more vinyl monomers with the reaction product from the first step to form a second block, wherein the second block incorporates the residual unreacted acrylic and/or vinyl monomer.   
     
     
         17 . A polymer/clay nanocomposite material having a composition comprising
 a) an organic clay;   b) a block copolymer having a composition that includes a first block, the first block comprising monomeric units of a functionalized acrylic monomer and/or a functionalized vinyl monomer and monomeric units of a vinyl monomer, and a second block, the second block comprising monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic monomer and/or the functionalized vinyl monomer from the first block; and   c) one or more components that can polymerize to render a thermoset matrix.   
     
     
         18 . The polymer/clay nanocomposite material of  claim 17 , wherein the organic clay has an organic intercalant selected from the group consisting of substituted ammonium ions, organophosphonium ions and organosulfonium ions. 
     
     
         19 . The polymer/clay nanocomposite material of  claim 17 , wherein the thermoset matrix is selected from the group consisting of polyamide resins, phenolic resins, epoxy resins, unsaturated polyester resins, alkyd resins, furan resins, urea resins, melamine resins, polyurethane resins and aniline resins. 
     
     
         20 . A process for making a modified clay mineral, comprising the steps of:
 adding a block copolymer in a neutral form to a layered natural and/or synthetic clay mineral having exchangeable inorganic cations to form a mixture, wherein the clay mineral is dispersed in a dispersion medium,   wherein the block copolymer has a composition comprising first and second blocks, wherein the first block comprises monomeric units of a functionalized acrylic and/or functionalized vinyl monomer and monomeric units of a vinyl monomer, wherein the second block comprises monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic and/or functionalized vinyl monomer in the first block; and   modifying the pH of the mixture in order to protonate at least one monomer in the block copolymer to form an organic cation for exchange with the inorganic cations in the clay mineral, wherein the clay mineral is intercalated and/or exfoliated by the block copolymer.   
     
     
         21 . A process for making a modified clay mineral, comprising:
 dispersing a layered natural and/or synthetic clay mineral having exchangeable inorganic cations in a dispersion medium; and   adding a block copolymer to the dispersion medium that contains the clay mineral,   wherein the block copolymer has a composition comprising first and second blocks, wherein the first block comprises monomeric units of a functionalized acrylic and/or functionalized vinyl monomer and monomeric units of a vinyl monomer, wherein the second block comprises monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic and/or functionalized vinyl monomer in the first block, and   wherein the block copolymer is charged.   
     
     
         22 . The process of  claim 20 , wherein additional inorganic or organic cations are added. 
     
     
         23 . The process of  claim 21 , wherein additional inorganic or organic cations are added. 
     
     
         24 . The process of  claim 20 , wherein the dispersion medium is selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, ethyleneglycol, 1,4-butanediol, glycerin, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone, methyl ethyl ketone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, ether, carbon tetrachloride, n-hexane, and combinations thereof. 
     
     
         25 . The process of  claim 21 , wherein the dispersion medium is selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, ethyleneglycol, 1,4-butanediol, glycerin, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone, methyl ethyl ketone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, ether, carbon tetrachloride, n-hexane, and combinations thereof. 
     
     
         26 . A composition for a polymer/clay nanocomposite material, comprising:
 a thermoplastic matrix; and   a modified clay mineral, wherein the modified clay mineral has a composition, comprising:   a) 67-99% wt of a layered natural and/or synthetic clay mineral having exchangeable cations; and   b) 0.5-33% wt of a block copolymer having a composition, comprising: a first block comprising monomeric units of a functionalized acrylic and/or functionalized vinyl monomer and monomeric units of a vinyl monomer; and a second block comprising monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic and/or functionalized vinyl monomer in the first block,   wherein the layered natural and/or synthetic clay mineral is intercalated and/or exfoliated by the block copolymer.   
     
     
         27 . A composition for a polymer/clay nanocomposite material, comprising:
 one or more components that can polymerize to form a thermoset matrix; and   a modified clay mineral, wherein the modified clay mineral has a composition, comprising:   a) 67-99% wt of a layered natural and/or synthetic clay mineral having exchangeable cations; and   b) 0.5-33% wt of a block copolymer having a composition, comprising: a first block comprising monomeric units of a functionalized acrylic and/or functionalized vinyl monomer and monomeric units of a vinyl monomer; and a second block comprising monomeric units of one or more vinyl monomers and monomeric units of the functionalized acrylic and/or functionalized vinyl monomer in the first block,   wherein the layered natural and/or synthetic clay mineral is intercalated and/or exfoliated by the block copolymer.