Functionalized ethylene/vinyl or vinylidene aromatic interpolymers

Abstract

Novel substantially random functionalized interpolymers and processes for making them are disclosed. The novel interpolymers include those prepared from ethylene and vinyl aromatic monomers such as ethylene-styrene interpolymers which are then functionalized with a variety of electrophilic and nucleophilic reagents.

What is claimed is:  
     
         1 . A substantially random interpolymer comprising; 
 (a) from 0 to about 64.95 mole percent of repeating units represented by the following formula (I):                           wherein Y is independently selected from the group consisting of hydrogen, substituted and unsubstituted alkyl radicals, benzyl radicals, aryl radicals, and aralkyl radicals containing up to 18 carbon atoms, —Br, —CH 2 X, —C(O)R 6 , —(Z)—CO 2 H, —(Z)—SO 3 H, —NO 2 , —C(O)OR 6 , —(Z)—OR 6 , —N(R 6 ) 2 , —(Z)—N(R 6 ) 2 , —P(OR 6 ) 2 , —(Z)—P(OR 6 ) 2 , —P(R 6 ) 2 , —(Z)—P(R 6 ) 2 , —P(O)(R 6 ) 2 , —(Z)—P(O)(R 6 ) 2 , —P(O)(OR 6 ) 2 , —(Z)—P(O)(R 6 ) 2 , —(Z)—SR 6 , —CN, —(Z)—CN, —CO 2 H, —C(O)N(R 6 ) 2 , —(Z)—C(O)N(R 6 ) 2 , ionomeric salts of —CO 2   − , —(Z)—CO 2   − , —(Z)—SO 3   − , —N + (R 6 ) 3 , —(Z)—N + (R 6 ) 3 , —P + (R 6 ) 3 , —(Z)—P + (R 6 ) 3 , —(Z)—S + (R 6 ) 2 , and mixtures thereof; R 1  is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; R 2  is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; R 6  is independently selected from the group of radicals consisting of hydrogen, substituted or unsubstituted alkyl radicals containing from 1 to 18 carbon atoms, and substituted or unsubstituted aryl radicals; X is a halogen; and Z is alkylene or arylene; and n has a value from zero to 4;    (b) from about 0.05 to about 65 mole percent of repeating units represented by the following formula (II)                           wherein Y, R 1 , R 2 , n, and X are as described for I with the proviso that at least one Y is not hydrogen or a substituted or unsubstituted alkyl radical;    (c) from 0 to about 25 mole percent of repeating units represented by the following formula (III):                           wherein R 1  and R 2  are as described for I and A 1  is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons or R 2  and A 1  together form a ring system wherein the ring system formed by A 1  and R 2  is optionally substituted with one or more substituents selected from substituted and unsubstituted alkyl radicals, benzyl radicals, aryl radicals, and aralkyl radicals containing up to 18 carbon atoms, —Br, —CH 2 X, —C(O)R 6 , —(Z)—CO 2 H, —(Z)—SO 3 H, —NO 2 , —C(O)OR 6 , —(Z)—OR 6 , —N(R 6 ) 2 , —(Z)—N(R 6 ) 2 , —P(OR 6 ) 2 , —(Z)—P(OR 6 ) 2 , —P(R 6 ) 2 , —(Z)—P(R 6 ) 2 , —P(O)(R 6 ) 2 , —(Z)—P(O)(R 6 ) 2 , —P(O)(OR 6 ) 2 , —(Z)—P(O)(R 6 ) 2 , —(Z)—SR 6 , —CN, —(Z)—CN, —CO 2 H, —C(O)N(R 6 ) 2 , —(Z)—C(O)N(R 6 ) 2 , ionomeric salts of —CO 2   − , —(Z)—CO 2   − , —(Z)—SO 3   − , —N + (R 6 ) 3 , —(Z)—N + (R 6 ) 3 , —P + (R 6 ) 3 , —(Z)—P + (R 6 ) 3 , —(Z)—S + (R 6 ) 2 , and mixtures thereof, wherein R 6 , X, and Z are as defined above for 1; and    (d) from 35 to 99.95 mole percent of repeating units represented by the following formula (IV);                           wherein R 3  and R 4  are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 18 carbon atoms, with the proviso that R 3  and R 4  are different alkyl radicals.    
     
     
         2 . The substantially random interpolymer of  claim 1  comprising from 0 to about 50 mole percent of repeating units of formula I; from about 0.5 to about 50 mole percent of repeating units of formula II; from 0 to about 5 mole percent of repeating units of formula III; and from about 50 to about 99.5 mole percent of repeating units of formula IV.  
     
     
         3 . The substantially random interpolymer of  claim 2  wherein Z is alkylene having from 1 to 4 carbon atoms or phenylene.  
     
     
         4 . The substantially random interpolymer of  claim 1  comprising from 0.5 to 50 mole percent of repeating units of formula II and from about 50 to about 99.5 mole percent of repeating units of Formula IV.  
     
     
         5 . The substantially random interpolymer of  claim 4  wherein the Y group which is not hydrogen or a substituted or unsubstituted alkyl radical is substituted at the para position.  
     
     
         6 . The substantially random interpolymer of  claim 5  wherein the Y group is selected from the group consisting of —Br, —CH 2 X, —C(O)R 6 , —(Z)—CO 2 H, —(Z)—SO 3 H, —NO 2 .  
     
     
         7 . The substantially random interpolymer of  claim 5  wherein Y is independently selected from the group consisting of unsubstituted or substituted alkylcarbonyl, arylcarbonyl, and aralkyl groups; alkyl groups substituted with carboxylic acid or sulfonic acid groups; NO 2 ; NH 2 , acyl, substituted or unsubstituted phenylcarbonyl and carboxyalkylcarbonyl; substituted or unsubstituted carboxybenzyl; —C(O)Me, —CO 2 H, —C(O)—pC 6 H 4 —Me, —CH(OH)—pC 6 H 4 —Me, —CH(R 5 )CH 2 CH 2 CO 2 H, —CH(R 5 )CH 2 CH 2 SO 3 H, —CH(R 5 )—pC 6 H 4 —CO 2 H, C(O)CH 2 CH 2 CO 2 H; ionomeric salts of —CO 2   − , —(Z)—CO 2   − , —(Z)—SO 3   − , —N + (R 6 ) 3 , —(Z)—N + (R 6 ) 3 , —P + (R 6 ) 3 , —(Z)—P + (R 6 ) 3 , —(Z)—S + (R 6 ) 2 , and mixtures thereof and mixtures thereof, and wherein R 5  is hydrogen or an alkyl group.  
     
     
         8 . A substantially random interpolymer comprising repeating units derived from 
 (1) monomer units derived from 
 (i) at least one vinyl or vinylidene aromatic monomer, or  
 (ii) at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer;  
 (iii) a combination of at least one vinyl or vinylidene aromatic monomer and at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and  
   (2) monomer units derived from 
 (i) ethylene, or  
 (ii) C 3-20  α-olefin;  
   (iii) or a combination (i) and (ii)    wherein the aromatic group of one or more of said vinyl or vinylidene aromatic monomers is functionalized subsequent to interpolymer formation with one or more substituents selected from the group consisting of benzyl radicals, aryl radicals, and aralkyl radicals containing up to 18 carbon atoms, —Br, —CH 2 X, —C(O)R 6 , —(Z)—CO 2 H, —(Z)—SO 3 H, —NO 2 , —C(O)OR 6 , —(Z)—OR 6 , —N(R 6 ) 2 , —(Z)—N(R 6 ) 2 , —P(OR 6 ) 2 , —(Z)—P(OR 6 ) 2 , —P(R 6 ) 2 , —(Z)—P(R 6 ) 2 , —P(O)(R 6 ) 2 , —(Z)—P(O)(R 6 ) 2 , —P(O)(OR 6 ) 2 , —(Z)—P(O)(R 6 ) 2 , —(Z)—SR 6 , —CN, —(Z)—CN, —CO 2 H, —C(O)N(R 6 ) 2 , —(Z)—C(O)N(R 6 ) 2 , ionomeric salts of —CO 2   − , —(Z)—CO 2   − , —(Z)—SO 3   − , —N − (R 6 ) 3 , —(Z)—N + (R 6 ) 3 , —P + (R 6 ) 3 , —(Z)—P + (R 6 ) 3 , —(Z)—S + (R 6 ) 2 , and mixtures thereof; R 1  is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; R 2  is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; R 6  is independently selected from the group of radicals consisting of hydrogen, substituted or unsubstituted alkyl radicals containing from 1 to 18 carbon atoms, and substituted or unsubstituted aryl radicals; X is a halogen; and Z is alkylene or arylene; and n has a value from zero to 4.    
     
     
         9 . The substantially random interpolymer of  claim 8  which further comprises monomer units derived from one or more ethylenically unsaturated polymerizable monomers other than (1) or (2).  
     
     
         10 . The substantially random interpolymer of  claim 9  wherein the monomers other than (1) or (2) are norbornene and C 1-10  alkyl or C 6-10  aryl substituted norbornenes.  
     
     
         11 . The substantially random interpolymer of  claim 8  which comprises from 5 to 65 mole percent of monomer units derived from said vinyl or vinylidene aromatic monomer and wherein 1 to 100 percent of said monomer units derived from said vinyl or vinylidene aromatic monomer are substituted with one or more of said substituents.  
     
     
         12 . The substantially random interpolymer of  claim 8  wherein said vinyl or vinylidene aromatic monomer is styrene and X is chlorine.  
     
     
         13 . The substantially random interpolymer of  claim 8  wherein Component (1) is styrene and Component (2) is ethylene.  
     
     
         14 . The substantially random interpolymer of  claim 13  wherein said substituent is —CH 2 X.  
     
     
         15 . A method for functionalizing a substantially random interpolymer comprising 
 (1) monomer units derived from 
 (i) at least one vinyl or vinylidene aromatic monomer, or  
 (ii) a combination of at least one vinyl or vinylidene aromatic monomer and at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and  
   (2) monomer units derived from 
 (i) ethylene, or  
 (ii) C 3-20  α-olefin;  
 (iii) or a combination (i) and (ii)  
 said method comprising;  
   reacting halomethyl ether and said interpolymer under conditions sufficient to produce a substantially random, halomethylated interpolymer, and    transforming the halomethyl groups on the halomethylated interpolymer to functional groups selected from the group consisting of phosphonium, ammonium, ester, ether, cyano, hydroxyl, and mixtures thereof.    
     
     
         16 . The method of  claim 15  wherein the halomethyl ether is a halomethyl alkyl ether.  
     
     
         17 . The method of  claim 15  wherein the halomethyl ether is a chloromethyl alkyl ether selected from the group consisting of chloromethyl methyl ether and chloromethyl ethyl ether and wherein the halomethyl ether and the interpolymer are reacted in the presence of a Lewis acid catalyst and a solvent wherein said catalyst is selected from the group consisting of tin tetrachloride, zinc chloride, and mixtures thereof and said solvent is selected from the group consisting of 1,2-dichloroethane, trichloromethane, methylene chloride, and mixtures thereof.  
     
     
         18 . The method of  claim 17  wherein the ratio of halomethyl ether to catalyst is such that halomethylation is maximized and gellation is minimized.  
     
     
         19 . The method of  claim 15  wherein the interpolymer further comprises monomer units derived from one or more ethylenically unsaturated polymerizable monomers other than (1) or (2) wherein said monomers are selected from the group consisting of propylene, 1-hexene, 1-octene, 1-butene, 4-methyl-1-pentene, vinyl toluene, alpha-methyl-styrene, or t-butyl styrene.  
     
     
         20 . A method for functionalizing a substantially random interpolymer comprising 
 (1) monomer units derived from 
 (i) at least one vinyl or vinylidene aromatic monomer, or  
 (ii) a combination of at least one vinyl or vinylidene aromatic monomer and at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and  
   (2) monomer units derived from 
 (i) ethylene, or  
 (ii) C 3-20  α-olefin;  
 (iii) or a combination (i) and (ii)  
 said method comprising reacting the substantially random interpolymer with an electrophile under conditions sufficient to produce an interpolymer having one or more functional groups substituted on the aromatic group wherein such functional groups are selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted alkylcarbonyl, and substituted or unsubstituted arylcarbonyl.  
   
     
     
         21 . A method for functionalizing a substantially random interpolymer comprising 
 (1) monomer units derived from 
 (i) at least one vinyl or vinylidene aromatic monomer, or  
 (ii) a combination of at least one vinyl or vinylidene aromatic monomer and at least one sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and  
   (2) monomer units derived from 
 (i) ethylene, or  
 (ii) C 3-20  α-olefin;  
 (iii) or a combination (i) and (ii)  
 said method which comprises:  
   reacting a nitrating agent and said interpolymer under conditions sufficient to produce a substantially random, nitrated interpolymer, and    transforming the nitro groups on the nitrated interpolymer to amino groups.