Hyperbranched polyamine and its use to exfoliate inorganic clay into random form of nanosilicate platelet

Abstract

The present invention relates to the preparation of hyperbranched polyamines and its use to exfoliate inorganic clays into random form of nanosilicate platelets. The hyperbranched polyamines serving as exfoliating agent are prepared by polymerizing poly(oxypropylene)-triamine and diglycidyl ether of bisphenol-A (DGEBA). Hydrophilic amine groups of the exfoliating agent are acidified and then reacted with the layered inorganic silicate clay through cation exchange reaction and physical clay exfoliation to give random form of nanosilicate platelets.

1 . A method for producing hyperbranched polyamine, comprising a step of: 
 (a) mixing and reacting poly(oxypropylene)-triamine with diglycidyl ether of bisphenol-A (DGEBA) to produce amine-terminated BPA epoxy oligomers (AEO) having more than two amine functional groups, wherein the poly(oxypropylene)-triamine has a molecular weight ranging from 100 to 10,000, and the amine functional groups are secondary or primary.    
     
     
         2 . The method of  claim 1 , wherein the DGEBA of the step (a) has a formula as follows:  
       
         
           
           
               
               
           
         
       
       wherein b=0˜2.  
     
     
         3 . The method of  claim 1 , wherein the poly(oxypropylene)-triamine of the step (a) is a product of Huntsman Chemical Co., having trademark Jeffamine® POP-T403, POP-T3000 or POP-T5000.  
     
     
         4 . The method of  claim 1 , wherein the poly(oxypropylene)-triamine of jthe step (a) has a formula as follows:  
       
         
           
           
               
               
           
         
       
       wherein each of a, a′ and a″ has a respective value in the range of 4˜5, 16˜17 or 27˜28 with a proviso that |a-a′|<2, |a-a″|<2 and |a′-a″|<2.  
     
     
         5 . The method of  claim 1 , wherein the poly(oxypropylene)-triamine and DGEBA of the step (a) have a molar ratio ranging from 0.3:1 to 1:1.  
     
     
         6 . The method of  claim 1 , wherein the poly(oxypropylene)-triamine reacts with the DGEBA at 20˜200° C. for 8˜24 hours in the step (a).  
     
     
         7 . A hyperbranched polyamine which is a product produced by the method of  claim 1 .  
     
     
         8 . A hyperbranched polyamine, having a formula as follows:  
       
         
           
           
               
               
           
         
       
       wherein each of a, a′ and a″ has a respective value in the range of 4˜5, 16˜17 or 27˜28 with a proviso that |a-a′|<2, |a-a″|<2 and |a′-a″|<2, and b=1˜3.  
     
     
         9 . A method for producing random form of nanosilicate platelets by exfoliating inorganic clay with a hyperbranched polyamine, comprising steps of: 
 (b) mixing and acidifying an exfoliating agent with an inorganic acid to form an acidified exfoliating agent, wherein the exfoliating agent is hyperbranched polyamine (amine-terminated BPA epoxy oligomers; AEO) having more than two amine functional groups at two ends thereof and is obtained by reacting poly(oxypropylene)-triamine having molecular weight ranging from 100 to 1,000 with DGEBA, wherein the amine functional groups are secondary or primary;    (c) intercalating layered inorganic silicate clay with the acidified exfoliating agent to form a first mixture; and    (d) dissolving the first mixture in a first solvent, and reacting with at least one equivalent of a hydroxide or chloride of alkali metal or alkaline-earth metal through a displacement reaction to form a second mixture containing nanosilicate platelets.    
     
     
         10 . The method of  claim 9 , wherein the inorganic acid of the step (b) is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid.  
     
     
         11 . The method of  claim 9 , wherein the exfoliating agent and the inorganic acid of the step (b) have an equivalent ratio NH 2 : H + =0.5:1˜3:1.  
     
     
         12 . The method of  claim 9 , wherein the exfoliating agent is mixed and acidified with the inorganic acid of the step (b) at 30˜70° C.  
     
     
         13 . The method of  claim 9 , wherein the layered inorganic silicate clay of the step (c) is montmorillonite, mica, kaolin, vermiculite, K10 montmorillonite, synthetic clay SWN or layered double hydroxides (LDH).  
     
     
         14 . The method of  claim 9 , wherein the layered inorganic silicate clay of the step (c) is swelled synthetic fluoride mica or montmorillonite.  
     
     
         15 . The method of  claim 9 , wherein the layered inorganic silicate clay of the step (c) has a cationic exchange capacity (CEC) ranging from 0.5 to 2.0 mequiv/g.  
     
     
         16 . The method of  claim 9 , wherein the acidified exfoliating agent and the layered inorganic silicate clay of the step (c) have an equivalent ratio NH 2 :CEC>1.  
     
     
         17 . The method of  claim 9 , wherein the hyperbranched polyamine in the acidified exfoliating agent and CEC of the layered inorganic silicate clay of the step (c) have an equivalent ratio ranging from 0.3:1 to 5:1.  
     
     
         18 . The method of  claim 9 , wherein the intercalation reaction of the step (c) is performed at 70˜90° C. for 3˜5 hours.  
     
     
         19 . The method of  claim 9 , wherein the first solvent of the step (d) is methanol.  
     
     
         20 . The method of  claim 9 , wherein the first mixture and the first solvent of the step (d) are mixed in a volume ratio ranging from 0.03:1 to 30:1.  
     
     
         21 . The method of  claim 9 , wherein the hydroxide or chloride of alkali metal or alkaline-earth metal of the step (d) is NaOH or KOH.  
     
     
         22 . The method of  claim 9 , wherein the first mixture and the hydroxide or chloride of alkali metal or alkaline-earth metal of the step (d) have an equivalent ratio ranging from 0.3:1 to 3:1.  
     
     
         23 . The method of  claim 9 , wherein the displacement reaction of the step (d) is performed at 50˜70° C. for 1˜3 hours.  
     
     
         24 . The method of  claim 9 , wherein the step (d) is repeated.  
     
     
         25 . The method of  claim 9 , further comprising a step after the step (d): 
 (e) mixing the second mixture with water and a second solvent for extraction and an extract containing nanosilicate platelets is obtained.    
     
     
         26 . The method of  claim 25 , wherein the second solvent of the step (e) is toluene.  
     
     
         27 . The method of  claim 25 , wherein the first solvent is methanol and the second solvent is toluene in the step (e), and volume ratio of methanol:toluene:water ranges from 0.3:0.3:1 to 3:3:1.  
     
     
         28 . The method of  claim 25 , wherein the extraction of the step (e) is performed at 30˜70° C. for 1˜3 hours.  
     
     
         29 . The method of  claim 25 , further comprising a step after the step (e): 
 (f) removing the first solvent, the second solvent, or both from the extract containing the nanosilicate platelets.    
     
     
         30 . A random form of nanosilicate platelets which is a product produced by the method of  claim 29 .  
     
     
         31 . The random form of nanosilicate platelets of  claim 30 , which has an organic/inorganic ratio ranging from 10/90 to 90/10.  
     
     
         32 . The random form of nanosilicate platelets of  claim 30 , which comprises Si (20˜50 wt %), Mg (10˜30 wt %), Al (0˜10 wt %), Na (1˜10 wt %), Fe (0˜1.0 wt %) and F (1˜15 wt %).  
     
     
         33 . The random form of nanosilicate platelets of  claim 30 , which has a diameter ranging from 50 to 1500 nm, and a thickness ranging from 0.5 to 1.5 nm.  
     
     
         34 . The random form of nanosilicate platelets of  claim 30 , which is used for antiseptic treatment.