Porous Polymer and Synthetic Method Thereof

Abstract

The present invention relates to a porous polymer and a synthetic method thereof. The porous polymer has the following general formula: wherein, the positions marked with the numeral 1-10 are C, CH, N, or CH with its H being substituted by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group; the positions marked with letter a or b are C, N+, or B−.

1 . A porous polymer having the following general formula: 
       
         
           
           
               
               
           
         
         wherein, the positions marked with the numeral 1-10 being C, CH, N, or CH with its H being substituted by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group; the positions marked with letter a or b being C, N + , or B − . 
       
     
     
         2 . A synthetic method of the porous polymer of  claim 1  comprising the following steps:
 Step 1, adding bis(1,5-cycloocta-1,5-diene)nickel(0), 2, 2′-bipyridyl, and 1,5-cycloocta-1,5-diene with the molar ratio thereof being 1:(0-15):(0-15) to a solution of DMF (N,N-dimethyl-Formamide) or toluene, and heating the mixture at 20-140° C. for 0-10 hours; 
 Step 2, adding corresponding quantity of reactive monomer to the resultant solution, keeping the initial concentration of the monomer between 0.001M and 5M, and at the same time, making the initial molar ratio of bis(1,5-cycloocta-1,5-diene)nickel(0) to the monomer to be (2-18):1; 
 Step 3, stirring the above mentioned mixture at 20-140° C. for 10 minutes to 10 days; 
 Step 4, cooling the mixture to room temperature, and then adding conc. HCl to the mixture; 
 Step 5, filtrating the mixture to obtain the residue, then washing the residue with hot water. THF and CHCl3 respectively, and then drying the residue in vacuum for 4-40 hours at 80-200° C. to obtain the porous polymer. 
 
     
     
         3 . The synthetic method of  claim 2 , wherein the reaction is Yamamoto type Ullmann reaction. 
     
     
         4 . The synthetic method of  claim 2 , wherein Step 5 comprises the following steps:
 Step 5.1, treating the above mentioned crude polymer by 10-100 ml water at 50-100° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.2, treating the above mentioned crude polymer by 10-100 ml THF at 20-70° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.3, treating the above mentioned crude polymer by 10-100 ml CHCl3 at 20-60° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40 hours at 80-200° C., and then obtaining the pure porous polymer.   
     
     
         5 . The synthetic method of  claim 2 , wherein the general formula of the monomer is: 
       
         
           
           
               
               
           
         
         wherein, the positions marked with the numeral 1-10 being C, CH, N, or CH with its H being substituted by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group; the positions marked with letter a or b being C, N + , or B − . 
       
     
     
         6 . A synthetic method of the porous polymer of  claim 1  comprising the following steps:
 Step 1, adding NiCl2, NaBr, Zn powder, and PPh3 with the molar ratio thereof being 1:(0-15):(1-15):(0-15) to a solution of DMF or toluene, and heating the mixture at 20-140° C. for 0-10 hours; 
 Step 2, adding corresponding quantity of reactive monomer to the resultant solution, keeping the initial concentration of the monomer between 0.001M and 5M; 
 Step 3, stirring the above mentioned mixture at 20-140° C. for 10 minutes to 10 days; 
 Step 4, cooling the mixture to room temperature, and then adding conc. HCl to the mixture; 
 Step 5, filtrating the mixture to obtain the residue, then washing the residue with hot water, THF and CHCl3, respectively, and then drying the residue in vacuum for 4-40 hours at 80-200° C. to obtain the porous polymer. 
 
     
     
         7 . The synthetic method of  claim 6 , wherein the reaction is Ullmann coupling reaction. 
     
     
         8 . The synthetic method of  claim 6 , wherein Step 5 comprises the following steps:
 Step 5.1, treating the above mentioned crude polymer by 10-100 ml water at 50-100° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.2, treating the above mentioned crude polymer by 10-100 ml THF at 20-70° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.3, treating the above mentioned crude polymer by 10-100 ml CHCl3 at 20-60° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40 hours at 80-200° C., and then obtaining the pure porous polymer.   
     
     
         9 . The synthetic method of  claim 6 , wherein the general formula of the monomer is: 
       
         
           
           
               
               
           
         
         wherein, the positions marked with the numeral 1-10 being C, CH, N, or CH with its H being substituted by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group; the positions marked with letter a or b being C, N + , or B − . 
       
     
     
         10 . A synthetic method of the porous polymer of  claim 1  comprising the following steps:
 Step 1, adding monomer with its initial concentration being 0.001M-5M, and Pd(PPh3)4 with its initial molar concentration being 0.05%-50% of the molar concentration of the monomer to a solution of DMF or toluene, and stirring the mixture for 0-10 hours under nitrogen atmosphere; 
 Step 2, adding aqueous alkaline solution with its initial molar concentration being 4-200 times of the molar concentration of the monomer to the resultant solution; 
 Step 3, heating the above mentioned solution at 20-140° C. for 10 minutes to 10 days; 
 Step 4, cooling the mixture to room temperature, and then adding conc. HCl to the mixture; 
 Step 5, filtrating the mixture to obtain the residue, then washing the residue with hot water, THF and CHCl3, respectively, and then drying the residue in vacuum for 4-40 hours at 80-200° C. to obtain the porous polymer. 
 
     
     
         11 . The synthetic method of  claim 10 , wherein the reaction is Suzuki coupling reaction. 
     
     
         12 . The synthetic method of  claim 10 , wherein Step 5 comprises the following steps:
 Step 5.1, treating the above mentioned crude polymer by 10-100 ml water at 50-100° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.2, treating the above mentioned crude polymer by 10-100 ml THF at 20-70° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.3, treating the above mentioned crude polymer by 10-100 ml CHCl3 at 20-60° C. for 3-5 times and then isolating the above mentioned crude polymer by filtration;   Step 5.4, drying the polymer in vacuum at 3-10 mmHg for 4-40 hours at 80-200° C., and then obtaining the pure porous polymer.   
     
     
         13 . The synthetic method of  claim 10 , wherein the general formula of the monomer is: 
       
         
           
           
               
               
           
         
         wherein, the positions marked with the numeral 1-10 being C, CH, N, or CH with its H being substituted by methyl, ethyl, amido, carboxyl, methoxyl, hydroxyl, or ester group; the positions marked with letter a or b being C, N + , or B − .