Intramolecular pi-stacking structure directing agents and molecular sieves synthesized therefrom

Patent metadata

Field	Value
Publication number	US-12466738-B2
Application number	US-202017772065-A
Country	US
Kind code	B2
Filing date	Jul 22, 2020
Priority date	Nov 1, 2019
Publication date	Nov 11, 2025
Grant date	Nov 11, 2025

Abstract

A method of making a molecular sieve may include: reacting a source selected from the group consisting of: a source of a tetrahedral element in the presence of a structure directing agent (SDA) selected from the group consisting of: Ar+-L-Ar, Ar+-L-Ar-L-Ar+, Ar+-L-Ar-L-NR3+, and ArAr+-L-Ar+Ar, where Ar+ is to a N-containing cationic aromatic ring, Ar is to a non-charged aromatic ring, L is a methylene chain of 3-6 carbon atoms, NR3+ is to a quaternary ammonium, and ArAr+ and Ar+Ar are a fused aromatic ring structure comprising both a N-containing cationic portion and a non-charged portion, to produce the molecular sieve.

First claim

What is claimed:

1 . A method comprising:
reacting, in a reaction mixture, a source of a tetrahedral element in the presence of a structure directing agent (SDA) selected from the group consisting of: Ar + -L-Ar, Ar + -L-Ar-L-Ar + , and Ar + -L-Ar-L-NR3 + , where Ar + is to a N-containing cationic aromatic ring, Ar is to a non-charged aromatic ring, L is a methylene chain of 3-6 carbon atoms, and NR3 + is to a quaternary ammonium, to produce a molecular sieve.

2 . The method of claim 1 , wherein the N-containing cationic aromatic ring is selected from the group consisting of: pyridinium, a substituted pyridinium, imidazolium, a substituted imidazolium, pyrazolium, a substituted pyrazolium, pyrazinium, a substituted pyrazinium, pyrimidinium, and a substituted pyrimidinium.

3 . The method of claim 1 , wherein the non-charged aromatic ring is selected from the group consisting of: phenyl, a substituted phenyl, naphthyl, and a substituted naphthyl.

4 . The method of claim 1 , wherein the SDA is selected from the group consisting of:

where R 1 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 2 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 2 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 2 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 4 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl and R 6 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 4 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl and R 6 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 4 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl and R 6 -R 10 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 2 -R 9 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 2 -R 9 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 2 -R 9 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;

where R 1 -R 4 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl and R 6 -R 13 are independently H, C 1 -C 6 alkyl (branched or linear), or C 5 -C 6 cycloalkyl; and wherein N + is counterbalanced by OH − , F − , Cl − , Br − , or I − ;
and any combination thereof.

5 . The method of claim 1 , wherein the reaction mixture is an aqueous reaction mixture; wherein the tetrahedral element comprises Si; and wherein the aqueous reaction mixture has a molar ratio of atomic Si to the structure directing agent of about 1 to about 20 and wherein the aqueous reaction mixture has a molar ratio of water to atomic Si of about 2 to about 80.

6 . The method of claim 1 , wherein the source of tetrahedral element is selected from the group consisting of: silicon sources, germanium sources, aluminum sources, boron sources, phosphorus sources, and any combination thereof.

7 . The method of claim 1 , wherein the reaction mixture further comprises a source of hydroxide ions.

8 . The method of claim 1 , wherein the reaction mixture further comprises a source of halide ions.

9 . The method of claim 1 , wherein the reaction mixture further comprises a source of alkali/alkaline earth metal ions.

10 . The method of claim 1 , wherein the reaction mixture further comprises molecular sieve seeds.

11 . The method of claim 1 , wherein reacting is at a temperature of about 75° C. to about 200° C.

12 . The method of claim 1 , wherein the molecular sieve has a composition selected from the group consisting of: silica, aluminosilicate, borosilicate, aluminoborosilicate, germanosilicate, aluminophosphate, silicoaluminophosphate, and metalloaluminophophates.

13 . The method of claim 1 , wherein the molecular sieve has a framework selected from the group consisting: of a RHO framework, a LTA framework, ITE framework, a RTH framework, an ITE/RTH intergrowth framework,

Assignees

• Exxonmobil Technology & Engineering Company

Inventors

• Burton Allen W
• Vroman Hilda B
• Falkowski Joseph M
• Terefenko Eugene
• Marella Michael A
• Mabon Ross

Classifications

• C01B39/54

  Phosphates, e.g. APO or SAPO compounds · CPC title

• C01B39/50

  Zeolites wherein inorganic bases or salts occlude channels in the lattice framework, e.g. sodalite, cancrinite, nosean, hauynite {(ultramarine C09C1/32)} · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• C01B39/145

  using at least one organic template directing agent · CPC title

• C01B37/007

  Borosilicates · CPC title