Preparation of metallic comonomers for polystyrene

Abstract

A method for making a polystyrene ionomer comprises: preparing a metallic comonomer within styrene monomer to form a reaction mixture; and placing the reaction mixture under conditions suitable for the formation of a polymer composition. The metallic comonomer can be a metal acrylate, formed by contacting a metal complex and an acrylate precursor.

What is claimed: 
     
         1 - 26 . (canceled) 
     
     
         27 . A method comprising:
 providing a first feed comprising styrene monomer and a metal complex;   providing a second feed comprising styrene monomer and an acrylate precursor;   mixing the first feed and the second feed to form a reaction mixture;   introducing the reaction mixture to a contacting vessel for a residence time sufficient for in situ formation of a metal acryalate; and   introducing the reaction mixture to a polymerization reactor.   
     
     
         28 . (canceled) 
     
     
         29 . The method of  claim 27 , wherein the residence time ranges from 15 minutes to 1 hour. 
     
     
         30 . The method of  claim 27 , further comprising polymerizing the reaction mixture in the polymerization reactor to form a polystyrene ionomer. 
     
     
         31 . The method of  claim 30 , wherein the polymerizing of the reaction mixture is carried out in a solution or mass polymerization process. 
     
     
         32 . The method of  claim 30 , wherein the polymerizing of the reaction mixture is carried out at a temperature ranging from 70° C. to 240° C. 
     
     
         33 . The method of  claim 27 , wherein the metal complex is a compound having a general chemical formula M(NR 5 R 6 ) n , wherein n is a metal formal oxidation state and R 5  and R 6  are each independently alkyl groups, aryl groups, substituted alkyl groups, substituted aryl groups, derivatives thereof or combinations thereof. 
     
     
         34 . The method of  claim 27 , wherein the metal complex is an organometallic compound represented by the formula MA n L y , wherein M is a main group or transition element of groups 3 to 12 of the periodic table, wherein A is a monoanioic ligand, wherein n is a metal formal oxidation state from +2 to +6, and wherein L is an optional additional ligand. 
     
     
         35 . The method of  claim 27 , wherein the acrylate precursor comprises an acrylic acid, and wherein the metal complex is an organometallic compound that irreversibly reacts with the acrylic acid selected from dibutylmagnesium (MgBu 2 ), triethyl aluminum (AlEt 3 ), tetrabenzyl zirconium, TaMg 5 , WMe 6 , and [Zn(CH 2 Ph 4 )]. 
     
     
         36 . The method of  claim 27 , wherein the acrylate precursor comprises an acrylic acid, and wherein the metal complex is a material that liberates conjugate acids weaker than the acrylic acid. 
     
     
         37 . The method of  claim 27 , wherein the metal complex is a compound having a general chemical formula M(OR 4 ) n , wherein n is a metal formal oxidation state and R 4  an alkyl group, aryl group, substituted alkyl group, substituted aryl group, derivative thereof or combinations thereof. 
     
     
         38 . The method of  claim 27 , wherein the metal complex is a non-homoleptic alkoxide and amide complex having the structure Zr(OPh) n ,(OBu) 4-6 . 
     
     
         39 . The method of  claim 27 , wherein the metal complex is a material that upon reaction with the acrylate precursor produce species with a decreased acidity with respect to the starting compounds. 
     
     
         40 . The method of  claim 39 , wherein the material comprises a metal alkoxide comprising an aryl group, a metal amide comprising an aryl group, or a compound comprising a siloxide. 
     
     
         41 . The method of  claim 27 , wherein the metal complex is Mg(OEt) 2 , Al(OiPr) 3 , Ti(OBu) 4 , Ta(NMe 2 ) 5 , W(OiBu) 6  or Ti(NEt 2 ) 4 . 
     
     
         42 . The method of  claim 27 , wherein the metal complex comprises Ti(OBu) n (NEt 2 ) 4-n , or Zr(CH 2 Ph) 2 (OPh) 2 . 
     
     
         43 . The method of  claim 27 , wherein the metal complex comprises MgAl 2 (OR) x  or MgZr(OR) x . 
     
     
         44 . The method of  claim 27 , wherein the metal complex is selected from the group consisting of dibutylmagnesium (MgBu 2 ), triethyl aluminum (AlEt 3 ), tetrabenzyl zirconium (Zr(CH 2 Ph 4 )), Mg(OEt) 2 , Ti(OBu) 4 , Ti(NEt 2 ) 4 , Zr(OPh) n (OBu) 4-n  wherein n is at least 1, Ti(OBu) n (NEt 2 ) 4-n  wherein n is at least 1, Zn(CH 2 Ph) 2 (OPh) 2 , Mg(Et) 2 , Mg(BuEt), Mg(n-Hex), Al(Me) 3 , Al(iPr) 3 , or combinations thereof. 
     
     
         45 . The method of  claim 27 , wherein the metal complex is selected from the group consisting of dibutylmagnesium (MgBu 2 ), triethyl aluminum (AlEt 3 ), tetrabenzyl zirconium (Zr(CH 2 Ph 4 )), Mg(OEt) 2 , Ti(OBu) 4 , Ti(NEt 2 ) 4 , Zn(CH 2 Ph) 2 (OPh) 2 , Mg(Et) 2 , Mg(BuEt), Mg(n-Hex), Al(Me) 3 , Al(iPr) 3 , or combinations thereof. 
     
     
         46 . The method of  claim 27 , wherein the acrylate precursor comprises an acrylic acid. 
     
     
         47 . The method of  claim 27 , wherein the metal acrylate is Zr[O 2 C(CH 3 )═CH 2 ] 2 (OiPr) 2 .