Suspension homopolymerization of an isocyanurates

Abstract

Compositions comprising a cross-linked isocyanurate homopolymer or other cross-linked triazine homopolymers in the form of a microbead that is porous or non-porous; methods of making; and methods of using the compositions are disclosed.

1 . A composition comprising a cross-linked isocyanurate homopolymer in the form of a microbead. 
   
   
       2 . A method of separating an analyte from a mixture in the form of a liquid, the method comprising:
 providing a housing having an interior;   providing a stationary phase, having a surface, disposed in the interior, the surface comprising a homopolymer of a monomer interacting both hydrophobically and hydrophilically with the analyte in the homopolymer; and   disposing the liquid in the interior in contact with the surface.   
   
   
       3 . The composition of  claim 1 , wherein the cross-linked isocyanurate homopolymer is formed from a suspension homopolymerization of an isocyanurate monomer using a free radical-type initiator. 
   
   
       4 . The composition of  claim 1 , wherein the microbead has an average diameter of from about 1 micron to about 200 microns. 
   
   
       5 . The composition of  claim 1 , wherein the microbead is non-porous. 
   
   
       6 . The composition of  claim 1 , wherein the microbead has pores wherein the diameter of a pore is from about 1 angstrom to about 10 6  angstroms. 
   
   
       7 . The composition of  claim 3 , wherein the free radical-type initiator is an azo-type initiator. 
   
   
       8 . The composition of  claim 7 , wherein the azo-type initiator is an azobis(alkylnitrile) initiator. 
   
   
       9 . The composition of  claim 8 , wherein the azobis(alkylnitrile) initiator is 2,2′-azobis(2-methylbutyronitrile) having the formula: 
     
       
         
         
             
             
         
       
     
   
   
       10 . The composition of  claim 8 , wherein the azobis(alkylnitrile) initiator is chosen from at least one of azodiisobutyronitrile, azodiisovaleronitrile, 2,2′-azobis(isobutyronitrile), and combinations thereof. 
   
   
       11 . The composition of  claim 7 , wherein azo-type initiator is chosen from at least one of dimethylazodiisobutyrate, 2,2′-azobis(N,N′-dimethyleneisobutyamidine)dihydrochloride, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine), 1,1′-azobis(1-cyclohexanecarbo-nitrile), 4,4′-azobis(4-cyanopentanoic acid), 2,2′-azobis(isobutyramide)dihydrate, and 2,2′-azobis(2-methylpropane), and combinations thereof. 
   
   
       12 . The composition of  claim 3 , wherein the free radical-type initiator is chosen from at least one of peroxybenzoic acid, cyanopentanoic acid, a peroxy-pivalate, dodecylbenzene peroxide, benzoyl peroxide, di-t-butyl hydroperoxide, t-butyl peracetate, acetyl peroxide, dicumyl peroxide, cumyl hydroperoxide, dimethyl bis(butylperoxy)hexane, potassium persulfate, ammonium persulfate, and potassium hydrogen persulfate, and combinations thereof. 
   
   
       13 . The composition of  claim 1 , wherein the homopolymer is a homopolymer of the isocyanurate monomer 1,3,5-triallyl-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione having the structural formula: 
     
       
         
         
             
             
         
       
     
   
   
       14 . The composition of  claim 1 , wherein the homopolymer is a homopolymer of the isocyanurate monomer tris(2-(acryloyloxy)ethyl) isocyanurate having the structural formula: 
     
       
         
         
             
             
         
       
     
   
   
       15 . An apparatus adapted to separate a component from a mixture, the apparatus comprising:
 a surface bearing a homopolymeric cross-linked isocyanurate; and   a housing adapted to contain the surface and receive the mixture.   
   
   
       16 . The apparatus of  claim 15  wherein the surface is on microbeads. 
   
   
       17 . The apparatus of  claim 16  wherein the microbeads are affixed to a matrix. 
   
   
       18 . The apparatus of  claim 16  wherein the surface is on a porous monolith. 
   
   
       19 . The apparatus of  claim 15  wherein the housing is a chromatographic column. 
   
   
       20 . The apparatus of  claim 15  wherein the housing is a solid-phase extraction cartridge. 
   
   
       21 . A method of preparing a homopolymeric isocyanurate microbead, the method comprising:
 dispersing an isocyanurate monomer in a first organic solvent to form an organic phase;   combining a suspension promoter and a first liquid to form an immiscible liquid, the immiscible liquid being immiscible with the organic phase;   mixing the immiscible liquid and the organic phase to form a suspension of monomer-containing droplets in the immiscible liquid; and   activating polymerization of the monomer in the droplets, thereby converting the droplets to a plurality of homopolymeric isocyanurate microbeads.   
   
   
       22 . The method of  claim 21  wherein the first liquid is water. 
   
   
       23 . The method of  claim 21  wherein the first liquid is an organic liquid. 
   
   
       24 . The method of  claim 21  further comprising adding potassium dichromate to the first liquid. 
   
   
       25 . The method of  claim 21  wherein the suspension promoter is methylcellulose. 
   
   
       26 . The method of  claim 21  wherein the droplets are at a temperature and the activating polymerization comprises raising the temperature, and further comprising dispersing a first initiator in the first organic solvent before mixing the insoluble liquid phase and the organic phase. 
   
   
       27 . The method of  claim 26  wherein the first initiator is 2,2′-azobis(2-methylbutyronitrile). 
   
   
       28 . The method of  claim 26  wherein the activating polymerization further comprises adding a second initiator to the suspension. 
   
   
       29 . The method of  claim 28  wherein the first and second initiators are the same. 
   
   
       30 . The method of  claim 21  wherein the activating polymerization comprises adding an initiator to the droplets. 
   
   
       31 . The method of  claim 21  further comprising dispersing a hydrophobic porogen in the first organic solvent before mixing the immiscible liquid and the organic phase. 
   
   
       32 . The method of  claim 21  wherein the first organic solvent comprises at least one of dodecanol, cyclohexane and toluene. 
   
   
       33 . The method of  claim 21  wherein the first organic solvent comprises a porogen. 
   
   
       34 . The method of  claim 21  wherein the first organic solvent is a mixture of at least two distinct organic liquids. 
   
   
       35 . The method of  claim 21  further comprising mixing an acid with the suspension after the activating polymerization. 
   
   
       36 . The method of  claim 21  further comprising:
 isolating the microbeads from the suspension; and   washing the isolated microbeads with a second organic solvent.   
   
   
       37 . The method of  claim 21  further comprising mixing an acid with the microbeads. 
   
   
       38 . The method of  claim 21  further comprising mixing an acid with the suspension to form an acidified mixture and wherein the activating polymerization comprises:
 dispersing a first initiator in the first organic solvent before mixing the immiscible liquid and the organic phase; and adding a second initiator to the acidified mixture.   
   
   
       39 . The method of  claim 21  wherein the activating polymerization comprises
 providing a medium bearing an initiator;   dispersing the medium over the microbeads;   evaporating the medium to leave initiator-coated microbeads; and   substantially completing polymerization of the initiator-coated microbeads, thereby hardening the microbeads.   
   
   
       40 . The method of  claim 39  wherein substantially completing polymerization of the initiator-coated microbeads comprises maintaining the initiator-coated microbeads in a substantially oxygen-free environment. 
   
   
       41 . The method of  claim 21  wherein the isocyanurate monomer is triallylisocyanurate. 
   
   
       42 . The method of  claim 41  wherein the first organic solvent comprises at least one of dodecanol, cyclohexane, and toluene, and the method further comprises dispersing 2,2′-azobis(2-methylbutyronitrile) in the first organic solvent before mixing of the immiscible liquid and the organic phase. 
   
   
       43 . The method of  claim 42  wherein the first liquid is water. 
   
   
       44 . The method of  claim 43  further comprising:
 isolating the microbeads from the suspension; and   after isolating the microbeads, adding an acid to the microbeads to form an acidified mixture.   
   
   
       45 . The method of  claim 44  further comprising:
 separating the microbeads from the acidified mixture; and   after separating the microbeads, mixing the microbeads with a second organic solvent to wash the microbeads.   
   
   
       46 . The method of  claim 45  wherein the activating polymerization comprises
 providing a medium bearing 2,2′-azobis(2-methylbutyronitrile);   dispersing the medium over the microbeads;   evaporating the solvent to leave the microbeads coated with 2,2′-azobis(2-methylbutyronitrile); and   substantially completing polymerization of the microbeads coated with 2,2′-azobis(2-methylbutyronitrile) in a substantially oxygen-free environment, thereby hardening the microbeads.   
   
   
       47 . The method of  claim 46  further comprising adding potassium dichromate and ammonium hydroxide to the first liquid. 
   
   
       48 . The method of  claim 21  wherein the first initiator is an azo-type initiator. 
   
   
       49 . The method of  claim 21  further comprising adding ammonium hydroxide to the first liquid. 
   
   
       50 . The method of  claim 39  wherein substantially completing polymerization of the initiator-coated microbeads comprises heating the microbeads. 
   
   
       51 . A method for separating an analyte from a mixture in the form of a liquid, the method comprising:
 providing a housing having an open interior, the open interior packed with a stationary phase comprising a cross-linked isocyanurate homopolymer;   passing the liquid through the interior of the housing; and   collecting an eluent leaving the housing.   
   
   
       52 . The method of  claim 51  wherein the housing is a solid-phase extraction cartridge. 
   
   
       53 . A method of making a porous monolith of isocyanurate homopolymer, comprising:
 providing an organic phase comprising an isocyanurate monomer, an initiator, and a hydrophobic porogen;   placing the organic phase in a container;   effecting substantially complete polymerization of the monomer in the container to form the porous monolith of cross-linked isocyanurate homopolymer.