Heterogeneous organotin catalysts
View Patent ↗Supported heterogeneous organotin catalysts of the formula X1, X2, or X3: wherein Z is a spacer group; Y is an insoluble phenyl-group containing copolymer; R 1 , R 2 , R 3 , R 5 , and R 6 are independently selected from halogen, alkyl, alkylene, phenyl, vinyl, allyl, naphthyl, aralkyl, and Z; and R 4 is alkyl, alkylene, phenyl, vinyl, allyl, naphthyl, or aralkyl.
1. A process for the esterification of an aromatic dicarboxylic acid or an ester-forming derivative thereof, and an aliphatic diol or an ester-forming derivative thereof, which process comprises reacting the aromatic dicarboxylic acid or an ester-forming derivative thereof, and the aliphatic diol or an ester-forming derivative thereof, in a reaction mixture comprising an effective amount of an organotin compound of the formula X1, X2, or X3:
wherein
Z is (CH 2 ) m —;
m is a number of from 4 to 24;
and Y is an insoluble phenyl-group containing copolymer,
R 1 , R 2 , R 3 are independently selected from the group consisting of halogen, C 1 -C 18 alkyl, C 1 -C 18 alkylene, phenyl, vinyl, allyl, naphthyl, and aralkyl, with the proviso that at least one of R 1 , R 2 , or R 3 is a halogen;
R 4 is C 1 -C 18 alkyl, C 1 -C 18 alkylene, phenyl, vinyl, allyl, naphthyl, or aralkyl;
R 5 and R 6 are independently selected from the group consisting of halogen, C 1 -C 18 alkyl, C 1 -C 18 alkylene, phenyl, vinyl, allyl, naphthyl, and aralkyl, with the proviso that at least one of R 5 or R 6 is a halogen;
with the proviso that when m is 4 or 6, two of R 1 , R 2 , and R 3 are not chlorine.
2. A process as recited in claim 1 additionally comprising the step of separating the organotin compound from the reaction mixture by a phase separation means.
3. A process for the esterification of an aromatic dicarboxylic acid or an ester-forming derivative thereof, and an aliphatic dial or an ester-forming derivative thereof, which process comprises reacting the aromatic dicarboxylic acid or an ester-forming derivative thereof, and the aliphatic dial or an ester-forming derivative thereof, in a reaction mixture comprising an effective amount of an organotin compound resulting from a process comprising the steps of:
(a) reacting a suitable metal with a poly (styrene-co-divinylbenzene) copolymer under conditions effective to replace the phenyl-hydrogen in the poly(styrene-co-divinylbenzene) copolymer with the suitable metal, to produce a metalated poly(styrene-co-divinylbenzene) copolymer;
(b) reacting the metalated poly(styrene-co-divinylbenzene) copolymer with a dihalogen spacer molecule, under conditions effective to produce a spacer-halogen poly(styrene-co-divinylbenzene) copolymer, and
(c) grafting the spacer-halogen poly(styrene-co-divinylbenzene) copolymer with an organotin hydride under conditions effective to yield the organotin compound having the formula X1, X2, or X3;
wherein
Z is —(CH 2 ) m —;
m is a number of from 4 to 24;
and Y is an insoluble phenyl-group containing copolymer,
R 1 , R 2 , R 3 are independently selected from the group consisting of halogen, C 1 -C 18 alkyl, C 1 -C 18 alkylene, phenyl, vinyl, allyl, naphthyl, and aralkyl, with the proviso that at least one of R 1 , R 2 , or R 3 is a halogen;
R 4 is C 1 -C 18 alkyl, C 1 -C 18 alkylene, phenyl, vinyl, allyl, naphthyl, or aralkyl;
R 5 and R 6 are independently selected from the group consisting of halogen, C 1 -C 18 alkyl, C 1 -C 18 alkylene, phenyl, vinyl, allyl, naphthyl, and aralkyl, with the proviso that at least one of R 5 or R 6 is a halogen;
with the proviso that when m is 4 or 6, two of R 1 , R 2 and R 3 are not chlorine.
4. The process of claim 1 wherein R 1 , R 2 , R 3 , R 5 , and R 6 are halogen or C 4 -C 8 alkyl, and R 4 is C 4 -C 8 alkyl.
5. The process of claim 1 wherein R 1 , R 2 , R 3 , R 5 , and R 6 are chlorine, butyl, or octyl, and R 4 is butyl.
6. The process of claim 1 wherein m is a number from 4 to 11.