Unsaturated ester substituted polymers with reduced halogen content

#Cross-reference is hereby made to the following copending applications:

#Copending application U.S. Ser. No. 10/322,110, filed Dec. 17, 2002, entitled “Process for Preparing Substituted Polyarylene Ethers,” with the named inventor Timothy P. Bender, the disclosure of which is totally incorporated herein by reference, discloses processes for preparing polymers of the formula wherein m is 0 or 1, X is chlorine, bromine, or iodine, and n, e, and f are each, independently of the others, integers wherein e may be 0 and n and f are each at least 1, said process comprising providing a first reaction mixture which comprises a first solvent, a compound of the formula wherein Y is a chlorine or fluorine atom, a compound of the formula and optionally, a compound of the formula heating the first reaction mixture and removing generated water therefrom, thereby forming an intermediate polymer of the formula providing a second reaction mixture which comprises a second solvent, the intermediate polymer, and a N-halosuccinimide, wherein the halogen atom in the N-halosuccinimide is the same as the halogen atom that is X; and heating the second reaction mixture, thereby forming the polymer.

#Copending application U.S. Ser. No. 10/040,850, filed Jan. 9, 2002, entitled “Process for Preparing Polyarylene Ethers,” with the named inventors Timothy P. Bender, Christine DeVisser, Richard A. Burt, Paul F. Smith, and Marko D. Saban, the disclosure of which is totally incorporated herein by reference, discloses a process for preparing a polymer of the formula wherein x is an integer of 0 or 1, A is one of several specified groups, such as B is one of several specified groups, such as or mixtures thereof, and n is an integer representing the number of repeating monomer units, said process comprising (A) providing a reaction mixture which comprises (i) a solvent, (ii) a compound of the formula (iii) a compound of the formula (iv) a compound of the formula wherein a is an integer of from 1 to 5, R′ is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group, an alkoxy group, an aryloxy group, an arylalkyloxy group, an alkylaryloxy group, a polyalkyleneoxy group, or a mixture thereof, and (v) a carbonate base; and (B) heating the reaction mixture and removing generated water from the reaction mixture, thereby effecting a polymerization reaction.

#The FIGURE illustrates the progress of the reaction carried out in Example III.

#Disclosed herein is a polymer of the formula wherein x is an integer of 0 or 1, n is an integer representing the number of repeating monomer units, R1, R2, R3, and R4 each, independently of the others, is an alkyl group (including saturated, unsaturated, linear, branched, cyclic, unsubstituted, and substituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in one embodiment with at least 1 carbon atom, and in another embodiment with at least about 2 carbon atoms, and in one embodiment with no more than about 11 carbon atoms, in another embodiment with no more than about 5 carbon atoms, in yet another embodiment with no more than about 3 carbon atoms, and in still another embodiment with no more than about 2 carbon atoms, although the number of carbon atoms can be outside of these ranges, an aryl group (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the aryl group), in one embodiment with at least about 6 carbon atoms, and in one embodiment with no more than about 28 carbon atoms, in another embodiment with no more than about 16 carbon atoms, in yet another embodiment with no more than about 13 carbon atoms, and in still another embodiment with no more than about 10 carbon atoms, such as phenyl or the like, an arylalkyl group (including unsubstituted and substituted arylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 29 carbon atoms, in another embodiment with no more than about 17 carbon atoms, in yet another embodiment with no more than about 13 carbon atoms, and in still another embodiment with no more than about 9 carbon atoms, such as benzyl or the like, or an alkylaryl group (including unsubstituted and substituted alkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 29 carbon atoms, in another embodiment with no more than about 17 carbon atoms, in yet another embodiment with no more than about 13 carbon atoms, and in still another embodiment with no more than about 9 carbon atoms, such as tolyl or the like, X1, X2, X3, and X4, each, independently of the others, is a halogen atom, such as fluorine, chlorine, bromine, or iodine, a′, b′, c′, and d′ are each, independently of the others, integers of 0, 1, 2, 3, or 4, each UE group, independently of the others, is an unsaturated ester group, e, f, g, and h are each, independently of the others, integers of 0, 1, 2, 3, or 4, provided that at least one of e, f, g, and h is equal to or greater than 1 in at least some of the monomer repeat units of the polymer, each SE group, independently of the others, is a saturated ester group, and i, j, k, and m are each, independently of the others, integers of 0, 1, 2, 3, or 4, provided that at least one of i, j, k, and m is equal to or greater than 1 in at least some of the monomer repeat units of the polymer, provided that the sum of a′+e+i is less than or equal to 4, provided that the sum of b′+f+j is less than or equal to 4, provided that the sum of c′+g+k is less than or equal to 4, and provided that the sum of d′+h+m is less than or equal to 4, A is wherein R is a hydrogen atom, an alkyl group (including saturated, unsaturated, linear, branched, cyclic, unsubstituted, and substituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in one embodiment with at least 1 carbon atom, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 10 carbon atoms, and in another embodiment with no more than about 5 carbon atoms, although the number of carbon atoms can be outside of this range, an aryl group (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, sulfur, nitrogen, silicon, phosphorus, or the like, either may or may not be present in the aryl group), in one embodiment with at least about 6 carbon atoms, and in one embodiment with no more than about 18 carbon atoms, in another embodiment with no more than about 12 carbon atoms, and in yet another embodiment with no more than about 6 carbon atoms, although the number of carbon atoms can be outside of this range, an arylalkyl group (including unsubstituted and substituted arylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 9 carbon atoms, and in yet another embodiment with no more than about 7 carbon atoms, although the number of carbon atoms can be outside of this range, such as benzyl or the like, or an alkylaryl group (including unsubstituted and substituted alkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 9 carbon atoms, and in yet another embodiment with no more than about 7 carbon atoms, although the number of carbon atoms can be outside of this range, such as tolyl or the like, or mixtures thereof, or mixtures thereof, B is wherein v is an integer of from 1 to about 20, and preferably from 1 to about 10, —(CH2O)t— wherein t is an integer of from 1 to about 20, and preferably from 1 to about 10, wherein z is an integer of from 2 to about 20, and preferably from 2 to about 10, wherein u is an integer of from 1 to about 20, and preferably from 1 to about 10, wherein w is an integer of from 1 to about 20, and preferably from 1 to about 10, wherein Ra and Rb each, independently of the other, are hydrogen atoms, alkyl groups (including saturated, unsaturated, linear, branched, cyclic, unsubstituted, and substituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in one embodiment with at least 1 carbon atom, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 10 carbon atoms, and in yet another embodiment with no more than about 5 carbon atoms, although the number of carbon atoms can be outside of this range, aryl groups (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, sulfur, nitrogen, silicon, phosphorus, or the like, either may or may not be present in the aryl group), in one embodiment with at least about 6 carbon atoms, and in one embodiment with no more than about 18 carbon atoms, in another embodiment with no more than about 12 carbon atoms, and in yet another embodiment with no more than about 6 carbon atoms, although the number of carbon atoms can be outside of this range, arylalkyl groups (including unsubstituted and substituted arylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 9 carbon atoms, and in yet another embodiment with no more than about 7 carbon atoms, although the number of carbon atoms can be outside of this range, such as benzyl or the like, or alkylaryl groups (including unsubstituted and substituted alkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 9 carbon atoms, and in yet another embodiment with no more than about 7 carbon atoms, although the number of carbon atoms can be outside of this range, such as tolyl or the like, or mixtures thereof, and p is an integer of 0 or 1, wherein r is an integer of 0 or 1, wherein y is 0 or 1: (2) Ar is (3) G is an alkyl group selected from alkyl or isoalkyl groups containing from about 2 to about 10 carbon atoms; (4) Ar′ is wherein s is 0, 1, or 2, and (6) q is 0 or 1; or mixtures thereof, and wherein the substituents on the substituted alkyl groups, substituted aryl groups, substituted arylalkyl groups, and substituted alkylaryl groups can be (but are not limited to) hydroxy groups, halogen atoms, amine groups, pyridine groups, pyridinium groups, phosphine groups, cyano groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfonate groups, sulfide groups, sulfoxide groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, azide groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring.

#In one embodiment, the unsaturated ester groups are of the formula wherein R5, R6, and R7 each, independently of the others, is a hydrogen atom, an alkyl group (including saturated, unsaturated, linear, branched, cyclic, unsubstituted, and substituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in one embodiment with at least 1 carbon atom, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 10 carbon atoms, and in yet another embodiment with no more than about 5 carbon atoms, although the number of carbon atoms can be outside of this range, aryl groups (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, sulfur, nitrogen, silicon, phosphorus, or the like, either may or may not be present in the aryl group), in one embodiment with at least about 6 carbon atoms, and in one embodiment with no more than about 18 carbon atoms, in another embodiment with no more than about 12 carbon atoms, and in yet another embodiment with no more than about 6 carbon atoms, although the number of carbon atoms can be outside of this range, arylalkyl groups (including unsubstituted and substituted arylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 9 carbon atoms, and in yet another embodiment with no more than about 7 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzyl or the like, alkylaryl groups (including unsubstituted and substituted alkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 9 carbon atoms, and in yet another embodiment with no more than about 7 carbon atoms, although the number of carbon atoms can be outside of this range, such as tolyl or the like, or mixtures thereof, and wherein the substituents on the substituted alkyl groups, substituted aryl groups, substituted arylalkyl groups, and substituted alkylaryl groups can be (but are not limited to) hydroxy groups, halogen atoms, amine groups, pyridine groups, pyridinium groups, phosphine groups, cyano groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfonate groups, sulfide groups, sulfoxide groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, azide groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring. Specific examples of suitable unsaturated ester groups include (but are not limited to) esters of acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, ethacrylic acid, oleic acid, linoleic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, 3-hexene-1,6-dicarboxylic acid, and the like, as well as mixtures thereof.

#For purposes of the present discussion, the term “saturated ester groups” includes those containing aryl or aromatic portions as well as those containing saturated aliphatic portions; “unsaturated” in the present polymers indicates that the group does not contain unsaturated aliphatic or alkyl portions. In one embodiment, the saturated ester groups are of the formula wherein R8 is a hydrogen atom, a saturated alkyl group (including linear, branched, cyclic, unsubstituted, and substituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in one embodiment with at least 1 carbon atom, and in one embodiment with no more than about 30 carbon atoms, and in another embodiment with no more than about 6 carbon atoms, although the number of carbon atoms can be outside of this range, aryl groups (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, sulfur, nitrogen, silicon, phosphorus, or the like, either may or may not be present in the aryl group), in one embodiment with at least about 6 carbon atoms, and in one embodiment with no more than about 30 carbon atoms, in another embodiment with no more than about 12 carbon atoms, and in yet another embodiment with no more than about 6 carbon atoms, although the number of carbon atoms can be outside of this range, arylalkyl groups (including unsubstituted and substituted arylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group, wherein the alkyl portion of the arylalkyl group is saturated), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 35 carbon atoms, and in another embodiment with no more than about 15 carbon atoms, although the number of carbon atoms can be outside of this range, such as benzyl or the like, alkylaryl groups (including unsubstituted and substituted alkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group, wherein the alkyl portion of the alkylaryl group is saturated), in one embodiment with at least about 7 carbon atoms, and in one embodiment with no more than about 35 carbon atoms, and in another embodiment with no more than about 15 carbon atoms, although the number of carbon atoms can be outside of this range, such as tolyl or the like, or mixtures thereof, and wherein the substituents on the substituted alkyl groups, substituted aryl groups, substituted arylalkyl groups, and substituted alkylaryl groups can be (but are not limited to) hydroxy groups, halogen atoms, amine groups, pyridine groups, pyridinium groups, phosphine groups, cyano groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfonate groups, sulfide groups, sulfoxide groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, azide groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring. Specific examples of suitable saturated ester groups include (but are not limited to) esters of acetic acid, propionic acid, butanoic acid, higher branched and linear alkyl carboxy acids, cyclohexanoic acid, other higher and lower cycloalkylcarboxylic acids, polyhydrogenated naphthalene carboxylic acid, other polycyclic saturated carboxylic acids, and the like as well as mixtures thereof.