Organosilica materials and uses thereof

Patent metadata

Field	Value
Publication number	US-10022700-B2
Application number	US-201514966284-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 12, 2014
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

Methods of preparing organosilica materials, which are a polymer comprising of at least one independent cyclic polyurea monomer of Formula

wherein each R 1 is a Z 1 OZ 2 Z 3 SiZ 4 group, wherein each Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer unit; each Z 2 and Z 3 independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group or an oxygen atom bonded to a silicon atom of another monomer unit; and each Z 4 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea are provided herein. Methods of preparing and processes of using the organosilica materials, e.g., for gas separation, color removal, etc., are also provided herein.

First claim

What is claimed is:

1. An organosilica material, which is a polymer of at least one independent cyclic polyurea monomer of Formula

wherein each R 1 independently is a Z 1 OZ 2 Z 3 SiZ 4 group, wherein
each Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer unit; each Z 2 and Z 3 independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group or an oxygen atom bonded to a silicon atom of another monomer unit; and each Z 4 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and at least one other monomer of an independent unit of Formula [Z 5 OZ 6 SiCH 2 ] 3 (II), wherein each Z 5 represents a hydrogen atom, a C 1 -C 4 alkyl or a bond to a silicon atom of another monomer, and each Z 6 represents a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; and optionally at least one other monomer selected from the group consisting of:
(i) an independent unit of Formula Z 7 OZ 8 Z 9 Z 10 Si (III), wherein Z 7 represents a hydrogen atom, a C 1 -C 4 alkyl group or a bond to a silicon atom of another monomer; and Z 8 , Z 9 and Z 10 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;
(ii) an independent unit of Formula Z 11 Z 12 Z 13 Si—R 2 —SiZ 11 Z 12 Z 13 (IV), wherein each Z 11 independently represents a hydroxyl group, a C 1 -C 4 alkoxy group or an oxygen bonded to a silicon atom of another comonomer; each Z 12 and Z 13 independently represent a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group or an oxygen bonded to a silicon atom of another monomer; and R 2 a C 1 -C 8 alkylene group, a C 2 -C 8 alkenylene group, a C 2 -C 8 alkynylene group, a nitrogen-containing C 2 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkyl and an optionally substituted C 4 -C 20 heterocycloalkyl group;
(iii) an independent unit of Formula M 1 (OZ 14 ) 3 (V), wherein M 1 represents a Group 13 metal and each Z 14 independently represents a hydrogen atom, a C 1 -C 6 alkyl or a bond to a silicon atom of another monomer;
(iv) an independent unit of Formula (Z 15 O) 2 M 2 -O—Si(OZ 16 ) 3 (VI), wherein M 2 represents a Group 13 metal and each Z 15 and each Z 16 independently represent a hydrogen atom, a C 1 -C 6 alkyl group or a bond to a silicon atom of another monomer; and
(v) a combination thereof.

2. The organosilica material of claim 1 , wherein each Z 1 represents a hydrogen atom, a C 1 -C 2 alkyl group or a bond to a silicon atom of another monomer unit; each Z 2 and Z 3 independently represent a hydroxyl group, a C 1 -C 2 alkyl group, a C 1 -C 2 alkoxy group or an oxygen atom bonded to a silicon atom of another monomer unit and each Z 4 represents a C 1 -C 4 alkylene group bonded to a nitrogen atom of the cyclic polyurea.

3. The organosilica material of claim 1 , wherein each Z 1 represents a hydrogen atom, methyl or a bond to a silicon atom of another monomer unit; each Z 2 and Z 3 independently represent a hydroxyl group, methoxy or an oxygen atom bonded to a silicon atom of another monomer unit and each Z 4 represents —CH 2 CH 2 CH 2 — bonded to a nitrogen atom of the cyclic polyurea.

4. The organosilica material of claim 1 , wherein each Z 5 represents a hydrogen atom, a C 1 -C 2 alkyl or a bond to a silicon atom of another comonomer, and each Z 6 represents a hydroxyl group, a C 1 -C 2 alkyl group, a C 1 -C 2 alkoxy group or an oxygen bonded to a silicon atom of another monomer.

5. The organosilica material of claim 4 , wherein each Z 5 represent a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z 6 represents a hydroxyl group, methyl, ethoxy or an oxygen bonded to a silicon atom of another monomer.

6. The organosilica material of claim 4 , wherein each Z 5 represent a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z 6 represents a hydroxyl group, ethoxy or an oxygen bonded to a silicon atom of another monomer.

7. The organosilica material of claim 4 , wherein each Z 5 represent a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z 6 represents methyl.

8. The organosilica material of claim 1 , wherein at least one independent unit of Formula (III) is present, wherein Z 7 represents a hydrogen atom, a C 1 -C 2 alkyl group or a bond to a silicon atom of another comonomer; and Z 8 , Z 9 and Z 10 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 2 alkyl group, C 1 -C 2 alkoxy group, a nitrogen-containing C 3 -C 10 alkyl group, a nitrogen-containing C 4 -C 10 heteroaralkyl group, or a nitrogen-containing optionally substituted C 4 -C 10 heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer.

9. The organosilica material of claim 8 , wherein Z 7 represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atom of another comonomer; and Z 8 , Z 9 and Z 10 are each independently selected from the group consisting of a hydroxyl group, methoxy, ethoxy, methyl,

and an oxygen bonded to a silicon atom of another monomer.

10. The organosilica material of claim 1 , wherein at least one independent unit of Formula (IV) is present, wherein each Z 11 represents a hydroxyl group, C 1 -C 2 alkoxy group or an oxygen bonded to a silicon atom of another comonomer; each Z 12 and Z 13 independently represent a hydroxyl group, a C 1 -C 2 alkoxy group, a C 1 -C 2 alkyl group or an oxygen bonded to a silicon atom of another monomer; and each R 2 is selected from the group consisting a C 1 -C 4 alkylene group, a C 2 -C 4 alkenylene group, a C 2 -C 4 alkynylene group and a nitrogen-containing C 4 -C 10 alkyl group.

11. The organosilica material of claim 10 , wherein each Z 11 independently represents a hydroxyl group, methoxy, ethoxy or an oxygen bonded to a silicon atom of another monomer; each Z 12 and Z 13 independently represent a hydroxyl group, methoxy, ethoxy, methyl or an oxygen bonded to a silicon atom of another monomer; and each R 2 is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —HC═CH—,

12. The organosilica material of claim 1 , wherein at least one independent unit of Formula (V) is present, wherein M 1 is Al or B and each Z 14 independently represents a hydrogen atom, a C 1 -C 4 alkyl group or a bond to a silicon atom or another monomer.

13. The organosilica material of claim 1 , wherein at least one independent unit of Formula (VI) is present, wherein M 2 is Al or B; and each Z 15 and each Z 16 independently represent a hydrogen atom, a C 1 -C 4 alkyl group or a bond to a silicon atom of another monomer.

14. The organosilica material of claim 1 , wherein the organosilica material is mesoporous and has an average pore diameter of about 2.0 nm to about 25.0 nm.

15. The organosilica material of claim 1 , wherein the organ

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Podsiadlo Paul
• Li Quanchang
• Calabro David Charles
• Zhang Lei
• Benitez Kiara M
• Gupta Himanshu
• Xu Xiaochun
• Weigel Scott J
• Lacy Darryl Donald
• Kaul Bal
• Gleeson James William
• Lai Wenyih Frank
• Afeworki Mobae
• Weston Simon Christopher
• Griffin David A
• Nines Meghan

Classifications

• C08G77/60

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title

• B01J20/28011

  Other properties, e.g. density, crush strength · CPC title

• B01J31/0274

  containing silicon (ligands in coordination complexes B01J31/1608) · CPC title

• B01D2253/25

  Coated, impregnated or composite adsorbents · CPC title

• C08G77/26

  nitrogen-containing groups · CPC title