Carboxy-terminated oligomeric polyester compositions and method for making

Abstract

The present invention provides carboxy-terminated oligomeric polyester compositions useful in the preparation of “weatherable” polymeric materials, for example weatherable copolyestercarbonates. In one aspect the present invention provides an oligomeric polyester composition comprising structural units derived from at least one diacid, at least one diaryl carbonate and at least one diol. The structural units derived from the diacid are present in a molar excess of from about 10% to about 40% based on a ratio of moles of diacid-derived structural units to moles of diol-derived structural units present in the oligomeric polyester composition. The oligomeric polyester composition is further characterized by the presence of atleast some phenoxy end groups.

1 . A composition comprising at least one carboxy-terminated oligomeric polyester, said polyester comprising structural units derived from at least one diacid, at least one diaryl carbonate and at least one diol, wherein the structural units derived from the diacid are present in a molar excess of from about 10% to about 40% based on a ratio of moles of diacid-derived structural units to moles of diol-derived structural units present in said composition, wherein said polyester comprises at least some phenoxy end groups.  
   
   
       2 . The composition according to  claim 1  wherein, said polyester is characterized by a ratio of carboxy end-groups to a total number of end-groups, said ratio of carboxy end-groups to the total number of end-groups being greater than 70%.  
   
   
       3 . The composition according to  claim 1 , wherein said polyester comprises structural units of the formula I,  
     
       
         
         
             
             
         
       
     
     wherein, R 1  is independently at each occurrence a C 1 -C 20  aliphatic radical, C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical; and R 2  is independently at each occurrence a C 2 -C 20  aliphatic radical, C 4 -C 20  cycloaliphatic radical, a C 6 -C 20  aromatic radical or a linking group having formula II,  
     
       
         
         
             
             
         
       
     
     wherein each G 1  is independently at each occurrence a C 6 -C 20  aromatic radical; E is independently at each occurrence a bond, a C 3 -C 20  cycloaliphatic radical, a C 6 -C 20  aromatic radical, a C 1 -C 20  aliphatic radical, a sulfur-containing linkage, a selenium-containing linkage, a phosphorus-containing linkage, or an oxygen atom; “t” is a number greater than or equal to one; “s” is either zero or one; and “u” is a whole number including zero, wherein at least one of “t”, “s”, and “u” is not equal to zero.  
   
   
       4 . The composition according to  claim 1  wherein said diacid has formula III,  
       HOOC—R 1 —COOH   Formula III  
     wherein R 1  is a C 1 -C 20  aliphatic radical, C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical.  
   
   
       5 . The composition according to  claim 4  wherein said diacid is selected from the group consisting of diacids of formula IV and formula V,  
     
       
         
         
             
             
         
       
     
     wherein R 3  and R 4  are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, C 3 -C 12 cycloaliphatic radical, or a C 6 -C 12  aromatic radical; “b” is an integer from 0 to 4; and “c” is an integer from 0 to 4.  
   
   
       6 . The composition according to  claim 1  wherein said diaryl carbonate has formula VI  
     
       
         
         
             
             
         
       
     
     wherein R 5  and R 6  are independently at each occurrence a halogen atom, a nitro group, a cyano group, C 1 -C 20  aliphatic radical, C 3 -C 20  cycloaliphatic radical, or a C 6 -C 20  aromatic radical; “d” is an integer from 0 to 5; and “e” is an integer from 0 to 5.  
   
   
       7 . The composition according to  claim 6  wherein said diaryl carbonate has formula VII  
     
       
         
         
             
             
         
       
     
   
   
       8 . The composition according to  claim 1  wherein said diol has formula VIII  
       HO—R 2 —OH   Formula VIII  
     wherein R 2  is a C 2 -C 20  aliphatic radical, C 4 -C 20  cycloaliphatic radical, a C 6 -C 20  aromatic radical, or a linking group having formula II  
     
       
         
         
             
             
         
       
     
     wherein each G 1  is independently at each occurrence a C 6 -C 20  aromatic radical; E is independently at each occurrence a bond, a C 3 -C 20  cycloaliphatic radical, a C 6 -C 20  aromatic radical, a C 1 -C 20  aliphatic radical, a sulfur-containing linkage, a selenium-containing linkage, a phosphorus-containing linkage, or an oxygen atom; “t” is a number greater than or equal to one; “s” is either zero or one; and “u” is a whole number including zero, wherein at least one of t, s, and u is not equal to zero.  
   
   
       9 . The composition according to  claim 8  wherein R 2  is an aromatic radical of formula IX  
     
       
         
         
             
             
         
       
     
     wherein R 7  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 14  aliphatic radical, a C 4 -C 14  cycloaliphatic radical, or a C 6 -C 14  aromatic radical; and “f” is an integer from 0 to 4.  
   
   
       10 . The composition according to  claim 1 , wherein the structural units derived from the diacid are present in a molar excess corresponding to from about 20% to about 40% excess based on a ratio of moles of diacid-derived structural units to moles of diol-derived structural units present in said composition.  
   
   
       11 . A composition comprising at least one carboxy-terminated oligomeric polyester, said polyester consisting essentially of structural units derived from at least one diacid, at least one diaryl carbonate and at least one diol, wherein the structural units derived from the diacid are present in a molar excess of from about 10% to about 40% based on a ratio of moles of diacid-derived structural units to moles of diol-derived structural units present in said composition, wherein said polyester comprises at least some phenoxy end groups.  
   
   
       12 . A method for preparing a composition comprising a carboxy-terminated oligomeric polyester, said method comprising heating a reaction mixture comprising at least one catalyst, at least one diacid, at least one diol, and at least one diaryl carbonate, wherein said at least one diacid, and said at least one diol, are present in an amount corresponding to a molar ratio of diacid to diol, said molar ratio being in a range between about 10% to about 40% excess diacid based on the amount of diol.  
   
   
       13 . The method according to  claim 12  wherein said diacid has formula III,  
       HOOC—R 1 —COOH   Formula III  
     wherein R 1  is a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical.  
   
   
       14 . The method according to  claim 13  wherein said diacid is selected from the group consisting of diacids of formula IV and formula V  
     
       
         
         
             
             
         
       
     
     wherein, R 3  and R 4  are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, a C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical; “b” is an integer from 0 to 4; and “c” is an integer from 0 to 4.  
   
   
       15 . The method according to  claim 12  wherein said diol has formula VIII  
       HO—R 2 —OH   Formula VIII  
     wherein R 2  is a C 2 -C 20  aliphatic radical, a C 4 -C 20  cycloaliphatic radical, a C 6 -C 20  aromatic radical, or a linking group having formula II,  
     
       
         
         
             
             
         
       
     
     wherein each G 1  is independently at each occurrence a C 6 -C 20  aromatic radical; E is independently at each occurrence a bond, a C 3 -C 20  cycloaliphatic radical, a C 6 -C 20  aromatic radical, a C 1 -C 20  aliphatic radical, a sulfur-containing linkage, a selenium-containing linkage, a phosphorus-containing linkage, or an oxygen atom; “t” is a number greater than or equal to one; “s” is either zero or one; and “u” is a whole number including zero, wherein at least one of “t”, “s” or “u” is not equal to zero.  
   
   
       16 . The method according to  claim 15  wherein R 2  is an aromatic radical of formula IX  
     
       
         
         
             
             
         
       
     
     wherein R 7  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 14  aliphatic radical, a C 4 -C 14  cycloaliphatic radical, or a C 6 -C 14  aromatic radical; and “f” is an integer from 0 to 4.  
   
   
       17 . The method according to  claim 12  wherein said diol is resorcinol.  
   
   
       18 . The method according to  claim 12  wherein said catalyst is a transition metal alkoxide Lewis acid catalyst.  
   
   
       19 . The method according to  claim 18  wherein said catalyst comprises alkoxides of Group IVB metals and derivatives of Group IVA metals, metal oxides, and metal carboxylates.  
   
   
       20 . The method according to  claim 18  wherein said catalyst is selected form the group consisting of titanium butoxide (Ti(OBu) 4 ), titanium isopropoxide (Ti(OiPr) 4 ), titanium phenoxide (Ti(OPh) 4 ), antimony trioxide, zirconium butoxide (Zr(OBu) 4 ), dialkyltin dialkoxides, dibutyltin oxide, dibutyltin diesters, tin phenoxide, and the like.  
   
   
       21 . The method according to  claim 17  wherein said catalyst is titanium butoxide (Ti(OBu) 4 ).  
   
   
       22 . The method according to  claim 12 , wherein said catalyst is present in an amount corresponding to from about 20 parts per million to about 1% based on the weight of diol employed.  
   
   
       23 . The method according to  claim 12 , wherein said reaction mixture further comprises a co-catalyst, said co-catalyst comprising a metal hydroxy phosphate.  
   
   
       24 . The method according to  claim 23 , wherein said co-catalyst comprises sodium hydroxy phosphate.  
   
   
       25 . The method according to  claim 23 , wherein said co-catalyst is present in a molar ration ranging from about 2:1 to about 10:1 based on the moles of catalyst employed.  
   
   
       26 . The method according to  claim 12 , wherein said heating comprises heating at a temperature of from about 140 to about 300° C.  
   
   
       27 . The method according to  claim 12 , wherein said at least one diaryl carbonate and at least one diol are present in an amount corresponding to a molar ratio of diaryl carbonate to diol, said molar ratio of diaryl carbonate to diol being in a range between about 1.5 to 1 to about 2.5 to 1.  
   
   
       28 . The method according to  claim 12  wherein said diaryl carbonate has formula VI  
     
       
         
         
             
             
         
       
     
     wherein R 5  and R 6  are independently at each occurrence a halogen atom, a nitro group, a cyano group, C 1 -C 20  aliphatic radical, C 3 -C 20  cycloaliphatic radical, or a C 6 -C 20  aromatic radical; “d” is an integer from 0 to 5; and “e” is an integer from 0 to 5.  
   
   
       29 . A composition comprising a carboxy-terminated oligomeric polyester, said polyester comprising structural units of formula X,  
     
       
         
         
             
             
         
       
     
     wherein R 8  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical; “n” is an integer from 0 to 4, R 9  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, a C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical; and “m” is an integer from 0 to 4; 
 said polyester being characterized by a ratio of carboxy end-groups to a total number of end-groups, said ratio being greater than about 70 percent.  
 
   
   
       30 . The composition according to  claim 29  wherein “n” and “m” are zero.  
   
   
       31 . A composition comprising components A, B and optionally C: 
 (i) component A comprising at least one carboxy-terminated oligomeric polyester comprising structural units having formula X                          wherein R 8  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical; “n” is an integer from 0 to 4, R 9  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, a C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical; and “m” is an integer from 0 to 4, said oligomeric polyester being characterized by a ratio of carboxy end-groups to a total number of end-groups, said ratio being greater than about 70 percent;    (ii) component B comprising at least one “organic species” comprising one or more functional groups, said functional groups being chemically reactive with the carboxy end-groups of the oligomeric polyester of component A; and optionally    (iii) component C is one or more catalysts which promote chemical reaction between the carboxy end-groups of the oligomeric polyester of component A and the “organic species” of component B; and    wherein said carboxy-terminated oligomeric polyester comprising structural units having formula X is prepared by a method, said method comprising heating a reaction mixture comprising at least one catalyst, at least one diacid, at least one diol, and at least one diaryl carbonate, wherein said at least one diacid, and said at least one diol, are present in an amount corresponding to a molar ratio of diacid to diol is in a range between about 10% to about 40% excess diacid based on the amount of diol, said at least one diacid being selected from the group consisting of diacids IV and V                          wherein, R 3  and R 4  are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, a C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical; “b” is an integer from 0 to 4; and “c” is an integer from 0 to 4; and at least one diol having structure XI,                          wherein R 7  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 14  aliphatic radical, a C 4 -C 14  cycloaliphatic radical, or a C 6 -C 14  aromatic radical; and “f” is an integer from 0 to 4; and    diphenyl carbonate; wherein said diacid, and diol, are present in an amount corresponding to from about 10% to about 40% excess diacid based on the amount of diol.    
   
   
       32 . A composition comprising reaction product of components A, B and optionally C: 
 (i) component A comprising at least one carboxy-terminated oligomeric polyester comprising structural units having formula X                          wherein R 8  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical; “n” is an integer from 0 to 4, R 9  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, a C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical; and “m” is an integer from 0 to 4, said oligomeric polyester being characterized by a ratio of carboxy end-groups to a total number of end-groups, said ratio being greater than about 70 percent;    (ii) component B comprising at least one “organic species” comprising one or more functional groups, said functional groups being chemically reactive with the carboxy end-groups of the oligomeric polyester of component A; and optionally    (iii) component C is one or more catalysts which promote chemical reaction between the carboxy end-groups of the oligomeric polyester of component A and the “organic species” of component B; and    wherein said carboxy-terminated oligomeric polyester comprising structural units having formula X is prepared by a method, said method comprising heating a reaction mixture comprising at least one catalyst, at least one diacid, at least one diol, and at least one diaryl carbonate, wherein said at least one diacid, and said at least one diol, are present in an amount corresponding to a molar ratio of diacid to diol is in a range between about 10% to about 40% excess diacid based on the amount of diol, said at least one diacid being selected from the group consisting of diacids IV and V                          wherein, R 3  and R 4  are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, a C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical; “b” is an integer from 0 to 4; and “c” is an integer from 0 to4; and at least one diol having structure XI,                          wherein R 7  is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 14  aliphatic radical, a C 4 -C 14  cycloaliphatic radical, or a C 6 -C 14  aromatic radical; and “f” is an integer from 0 to 4; and    diphenyl carbonate; wherein said diacid, and diol, are present in an amount corresponding to from about 10% to about 40% excess diacid based on the amount of diol.