Controlled catalysis
The present invention provides methods of using a novel sulfonated resin catalyst, showing improved performance. The catalyst has reduced or partial functionalization, throughout the sulfonated region of the polymer, leading to reduced by-product formation and other desirable features. This catalyst has particular usefulness in reactions or processes sensitive to high acidity, e.g., esterification-transesterification.
1. A method of catalyzing a reaction comprising:
(a) selecting a first reactant and a second reactant; and
(b) combining the first reactant, second reactant, and a Bronsted-acid resin catalyst containing aromatic groups; and
(c) carrying out the reaction to form a product;
wherein the Bronsted-acid resin catalyst is an ion exchange resin that is sulfonated essentially uniformly throughout the resin, the degree of sulfonation is less than 51% of the aromatic groups of the resin, the variation in sulfur density throughout the resin is within 14%, and the reaction is selected from the group consisting of esterification, transesterification, etherification, phenol condensation with carbonyl compounds, phenol C-alkylation, and olefin oligomerization reactions.
2. The method of claim 1 , wherein the reaction is (a) an esterification reaction or (b) a transesterification reaction of an ester with an alcohol or carboxylic acid.
3. The method of claim 2 , wherein the first reactant is a C1 to C24 alcohol or C1 to C24 olefin.
4. The method of claim 2 , wherein the second reactant is a C1 to C24 organic acid or C2 to C76 organic ester or polyester.
5. The method of claim 2 , wherein a reactant is a triglyceride.
6. The method of claim 1 , wherein the product is a bisphenol, the first reactant is a C6 to C20 phenolic compound and the second reactant is a C1 to C24 carbonyl compound.
7. The method of claim 1 , wherein the product is an olefin oligomer, and the first and second reactants are independently C2 to C10 compounds.
8. The method of claim 7 , wherein the olefin oligomer comprises an iso-olefin.
9. The method of claim 7 , wherein the first and second reactants are independently C4 to C10 compounds.
10. The method of claim 1 , wherein the product is a phenol alkylate, the first reactant is a phenol, and the second reactant is an olefin.
11. The method of claim 1 , wherein the reaction is better controlled compared to the same reaction using a fully-functionalized resin catalyst.
12. The method of claim 1 , wherein the resin catalyst is a macroporous resin.
13. The method of claim 1 , wherein the resin catalyst contains macropores having an average diameter of at least 150 Angstroms.
14. The method of claim 1 , wherein the resin has a controlled, selected, permanent, micropore structure.
15. A method of catalyzing a reaction comprising:
(a) contacting a copolymer having aromatic groups with a solvent that swells or permeates the copolymer;
(b) sulfonating the copolymer to form a Bronsted-acid resin catalyst wherein the resin is sulfonated essentially uniformly throughout the resin and 51% or less of the aromatic groups are sulfonated, the variation in sulfur density throughout the resin being within 14%, to form a catalyst;
(c) selecting a first reactant and a second reactant;
(d) combining a first reactant, a second reactant, and the Bronsted-acid resin catalyst; and
(e) reacting the first and second reactant to form a product,
wherein the reaction is selected from the group consisting of esterification, transesterification, etherification, phenol condensation with carbonyl compounds, phenol C-alkylation, and olefin oligomerization reactions.
16. The method claim 15 , wherein the solvent that swells the copolymer for sulfonating the copolymer is a mostly-inert solvent.
17. The method of claim 15 wherein the solvent is methylene chloride.
18. The method of claim 1 , wherein 33% or less of the aromatic groups are sulfonated.
19. The method of claim 1 , wherein 20% or less of the aromatic groups are sulfonated.
20. The method of claim 15 , wherein 33% or less of the aromatic groups are sulfonated.
21. The method of claim 15 , wherein 20% or less of the aromatic groups are sulfonated.
22. The method of claim 1 , wherein the reaction is a transesterification reaction.
23. The method of claim 22 , wherein 33% or less of the aromatic groups are sulfonated.
24. The method of claim 22 , wherein 20% or less of the aromatic groups are sulfonated.
25. A method of catalyzing a reaction, comprising:
reacting a first reactant and a second reactant in the presence of a Bronsted-acid resin catalyst containing aromatic groups to form a product;
wherein the Bronsted-acid resin catalyst is an ion exchange resin that is sulfonated essentially uniformly throughout the resin, the degree of sulfonation is less than 20% of the aromatic groups of the resin, the variation in sulfur density throughout the resin is within 25%, and the reaction is selected from the group consisting of esterification, transesterification, etherification, phenol condensation with carbonyl compounds, phenol C-alkylation, and olefin oligomerization reactions.