Dendrimer particles and related mixed matrix filtration membranes, compositions, methods, and systems

Abstract

Described herein are mixed matrix filtration membranes and related, dendrimers, dendrimer particles, compositions, methods and systems and in particular mixed matrix filtration membranes with an embedded dendrimer particles and related compositions, methods, and systems wherein each dendrimer particle comprises at least two dendrimers each having at least two core chemical moieties having a core multiplicity Nc; branch cell units attached to the core chemical moiety or one to another, with the branch cell units attached one to another having a branch cells multiplicity Nb; and a number of surface functional groups Z presented on terminal branch cell units, wherein Z=NcNb G with G≦3.

1 . A mixed matrix filtration membrane comprising:
 a plurality of dendrimer particles embedded in a polymer matrix wherein each dendrimer particle comprises at least two dendrimers each having
 at least two core chemical moieties having a core multiplicity Nc; 
 branch cell units attached to the core chemical moiety or one to another, with the branch cell units attached one to another having a branch cells multiplicity Nb; and 
 a number of surface functional groups Z presented on terminal branch cell units, wherein Z=NcNb G  with G≦3, 
   
     
     
         2 . The mixed matrix filtration membrane of  claim 1 , comprising a polymer of formula 
       
         
           
           
               
               
           
         
       
       wherein
 Q 4 , Q 5  and Q 6  are independently a core, having a formula selected from: 
 
       
         
           
           
               
               
           
         
         wherein n 2  is an integer from 1 to 18; 
         R 35 -R 46  are independently a branch cell comprising a head attachment atom and one to four tail attachment atoms joined to form a chemical moiety wherein the head attachment atom and one to four tail attachment atoms are linked by covalent bond, the branch cell unit chemical moiety comprising amidoamine groups and/or ester hydroxyl groups; 
         FG1 and FG2 are terminal functional groups, independently selected from amines, hydroxyl group, carboxylic acids, azides, thiols, diacetylenyl, and acrylates; 
         m 5 , m 6 , or m 7  are independently an integer selected from 1-4; and 
         l 3  is equal to 2 m 5 ; l 4  is equal to 2 m 6 ; l 5  is equal to 2 m 7 . 
       
     
     
         3 . The mixed matrix filtration membrane of  claim 1 , wherein the polymeric aggregate is formed by a polymer according to Formula (I): 
       
         
           
           
               
               
           
         
       
       wherein:
 Q, Y, and Z comprise saturated aliphatic hydrocarbon, aromatic hydrocarbon, or unsaturated aliphatic hydrocarbons; 
 m, l, and k independently are integers ranging between 0-50; 
 at least one of m, l, k is not equal to zero; 
 j is an integer ranging between 50-500; and 
 at least one of Q (when Q≠0), Y (when Y≠0), or Z (when Z≠0), comprises the polymer component functional group. 
 
     
     
         4 . The mixed matrix filtration membrane of  claim 3 , wherein Q, Y, and Z are independently selected from the group consisting of Formulas II-XI: 
       
         
           
           
               
               
           
         
         wherein: 
         n=0 or 1; 
         m is an integer ranging from 0-15; 
         X is a functional group comprising an atom selected from O, S, N, P, or F; and 
         R 1 -R 18  are independently selected from: the polymer component functional group; hydrogen; 
         C 1 -C 20  linear, branched, saturated, unsaturated, or aryl hydrocarbon which are either substituted or unsubstituted with O, N, B, S, P; or substituted O, N, B, S, or P. 
       
     
     
         5 . The mixed matrix filtration membrane of  claim 1 , wherein the dendrimer particles embedded in the polymer matrix are in a concentration of greater than 20 wt %. 
     
     
         6 . The mixed matrix filtration membrane of  claim 1 , wherein the dendrimer particles embedded in the polymer matrix are in a concentration of greater than 40 wt %. 
     
     
         7 . The mixed matrix filtration membrane of  claim 1 , wherein the mixed matrix filtration membrane is a membrane absorber capable of binding metal. 
     
     
         8 . The mixed matrix filtration membrane of  claim 1 , wherein the membrane absorber is capable of binding metal with a mean percentage of bound metal of larger than 50%. 
     
     
         9 . A method of making a mixed matrix filtration membrane with embedded dendrimer-like particles, the method comprising:
 providing a base polymer substantially soluble in a base polymer solvent;   providing a particle precursor having a portion substantially soluble in the base polymer solvent and a portion substantially insoluble in the base polymer solvent, the polymeric particle precursor able to provide a dispersion of segregated domains in the base polymer solvent, the polymeric particle precursor comprising one dendrimer having
 one core chemical moiety with a core multiplicity Nc, 
 branch cell units attached to the core chemical moiety or one to another, and 
 a number of terminal functional groups Z presented on terminal branch cell units, 
 the number of branch cell unit being attached one to another have a branch cells multiplicity Nb, and the number of terminal functional groups Z presented on terminal branch cell units, wherein Z=NcNb G  with G≦3; 
   mixing a base polymer with a polymer particle precursor, and the base polymer solvent to provide a blend;   maintaining the blend for a time and under a condition to allow crosslinking of at least some of the terminal functional groups Z and in situ formation of dendrimer particles thus providing a dope solution; and   casting the dope solution to provide the mixed matrix filtration membrane with embedded dendrimer particles.   
     
     
         10 . The method of  claim 9 , wherein the maintaining comprises mixing the blend with a crosslinker and/or an initiator capable of reacting with the polymer particle precursor. 
     
     
         11 . The method of  claim 9 , wherein the polymeric particle precursor is a dendrimer having a general formula (XI): 
       
         
           
           
               
               
           
         
       
       wherein:
 Q 1  is a core, having a formula selected from: 
 
       
         
           
           
               
               
           
         
         
           wherein n 2  is an integer from 1 to 18 
           R 19 -R 22  are independently a branch cell unit comprising a head attachment atom and one to four tail attachment atoms joined to form a chemical moiety wherein the head attachment atom and one to four tail attachment atoms are linked by covalent bond, such as carbon-nitrogen bond of an amide, carbon-oxygen bond an ester, carbon-carbon single or double bond; 
           FG1 and FG2 are terminal functional groups, independently selected from amines, hydroxyl group, carboxylic acids, azides, thiols, diacetylenyl, and acrylates. 
           m 2  is an integer ranging from 1-4; and 
           l 1  is equal to 2m 1 . 
         
       
     
     
         12 . The method of  claim 9 , wherein the polymeric particle precursors comprise one or more polymeric particle precursor of general formula (XV): 
       
         
           
           
               
               
           
         
       
       wherein:
 m 3  is an integer from 1 to 4; 
 X 1  is N; 
 R 23 -R 26  are independently amidoamine groups; 
 FG1 and FG2 are terminal groups, independently selected from amines, hydroxyl group, carboxylic acids, azides, thiols, diacetylenyl, and acrylates, and connected to each of the R 23 , R 24 , R 25  and R 26 ; 
 n 3  is an integer from 1 to 18 and 
 l 2  is equal to 2m 3 . 
 
     
     
         13 . The method of  claim 9 , wherein the polymeric particle precursors comprise G0, G1 and/or G2 PAMAM. 
     
     
         14 . The method of  claim 9 , wherein the polymeric particle precursors comprise G1 and/or G2 poly(propyleneimine) (PPI). 
     
     
         15 . The method of  claim 9 , wherein the polymeric particle precursors have a molecular weight less than 5000 daltons. 
     
     
         16 . The method of  claim 9 , wherein the polymeric particle precursors have a number of terminal groups less than 30. 
     
     
         17 . The method of  claim 9 , wherein the polymeric particle precursors are crosslinked to one another to form the dendrimer particle. 
     
     
         18 . A system for making a filtration membrane with in-situ synthesized dendrimer particles, the system comprising
 a base polymer for the membrane matrix substantially soluble in a base polymer solvent, and polymeric particle precursors partially soluble in the base polymer solvent the base polymer solvent,   each polymeric particle precursor being capable to form a dispersion of segregated domains in the base polymer solvent, and comprising one core chemical moiety having a core multiplicity Nc, branch cell units attached to the core chemical moiety or one to another, and a number of surface functional groups Z presented on terminal branch cell units,   wherein in each polymeric particle precursor the branch cell units attached one to another having a branch cells multiplicity Nb, and the number of surface functional groups Z presented on terminal branch cell units, wherein Z=NcNb G  with G≦3, and   wherein the polymer particle precursor present corresponding functional groups.   
     
     
         19 . The system of  claim 18 , further comprising a crosslinker and/or an initiator capable of reacting with the polymer particle precursor. 
     
     
         20 . The system of  claim 18 , further comprising the base polymer solvent or a mixture of solvents compatible with the base polymer solvent capable of dissolving the base polymer and/or a non-solvent substantially incompatible with base polymer solvent or a mixture of non-solvents substantially incompatible with the base polymer solvent for the membrane polymer to promote phase separation and subsequent membrane formation.