Organosilica materials, methods of making, and uses thereof

Patent metadata

Field	Value
Publication number	US-2017355822-A1
Application number	US-201615178961-A
Country	US
Kind code	A1
Filing date	Jun 10, 2016
Priority date	Jun 10, 2016
Publication date	Dec 14, 2017
Grant date	—

Abstract

Organosilica materials made from monomers including at least a source of silica that is reactive to polymerize, optionally in combination with at least one additional cyclic monomer. Methods for making such organosilica materials are also described herein.

First claim

What is claimed is:

1 . A method of producing an organosilica material comprising:
(a) providing an aqueous mixture that contains essentially no structure directing agent and/or porogen; (b) adding into the aqueous mixture to form a solution at least one compound of: (i) Formula (I), [Z 15 Z 16 SiCH 2 ] 3 , wherein each Z 15 can be a C 1 -C 4 alkoxy group and each Z 16 can be a C 1 -C 4 alkoxy group or a C 1 -C 4 alkyl group; and/or (ii) a cyclic polyurea monomer of formula (IV),

wherein each R 1 independently is a X 5 OX 6 X 7 SiX 8 group, wherein each X 5 represents a C 1 -C 4 alkyl group; X 6 and X 7 each independently represent a C 1 -C 4 alkyl group or a C 1 -C 4 alkoxy group; and each X 8 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and (iii) an additional comonomer comprising a source of silica that is reactive to polymerize with the at least one compound of Formula (I) and/or Formula (IV);
(c) aging the solution to produce a pre-product; and
(d) drying the pre-product to obtain an organosilica material which is a polymer comprising at least one independent monomer of Formula (I) and/or Formula (IV) as described herein that are linked to the silica through at least one silyl ether bond.

2 . The method of claim 1 , wherein at least one compound of Formula (I) is added to the aqueous mixture, and each Z 15 represents a C 1 -C 2 alkoxy group.

3 . The method of claim 1 , wherein at least one compound of Formula (I) is added to the aqueous mixture, and each Z 16 represents a C 1 -C 4 alkoxy group.

4 . The method of claim 1 , wherein at least one compound of Formula (I) is added to the aqueous mixture, and each Z 16 represents a C 1 -C 2 alkoxy group.

5 . The method of claim 1 , wherein at least one compound of Formula (I) is added to the aqueous mixture, and the at least one compound of Formula (I) is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane.

6 . The method of claim 1 , wherein at least one compound of Formula (IV) is added to the aqueous mixture, and wherein: each X 5 represents a C 1 -C 2 alkyl group; X 6 and X 7 each independently represent a C 1 -C 2 alkyl group or a C 1 -C 2 alkoxy group; and each X 8 represents a C 1 -C 4 alkylene group bonded to a nitrogen atom of the cyclic polyurea monomer.

7 . The method of claim 1 , wherein at least one compound of Formula (IV) is added to the aqueous mixture, and the at least one compound of Formula (IV) is tris(3-trimethoxysilylpropyl)isocyanurate.

8 . The method of claim 1 , wherein at least one compound of Formula (I) is added to the aqueous mixture, and wherein each Z 15 represents a hydroxyl group, a C 1 -C 2 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer and each Z 16 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.

9 . The method of claim 1 , wherein at least one compound of Formula (I) is added to the aqueous mixture, and each Z 15 represents a hydroxyl group, ethoxy, or an oxygen atom bonded to a silicon atom of another monomer and each Z 16 represent a hydroxyl group, ethoxy, or an oxygen atom bonded to a silicon atom of another monomer.

10 . The method of claim 1 , wherein at least one compound of Formula (IV) is added to the aqueous mixture, and wherein: each X 5 represents a hydrogen atom, a C 1 -C 2 alkyl group or a bond to a silicon atom of another monomer; X 6 and X 7 each 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; and X 8 represents a C 1 -C 4 alkylene group bonded to a nitrogen atom of the cyclic polyurea monomer.

11 . The method of claim 1 , wherein at least one compound of Formula (IV) is added to the aqueous mixture, and wherein: each X 5 represents a hydrogen atom, methyl or a bond to a silicon atom of another monomer unit; X 6 and X 7 each independently represent a hydroxyl group, methoxy or an oxygen atom bonded to a silicon atom of another monomer unit and X 8 represents —CH 2 CH 2 CH 2 — bonded to a nitrogen atom of the cyclic polyurea monomer.

12 . The method of claim 1 , wherein the source of silica comprises a particulate silica having an average particle size up to about 150 nm and/or having a particle size distributions such that a d95 is up to about 250 nm.

13 . The method of claim 12 , wherein the source of silica comprises a particulate silica having an average particle size from about 3 nm to about 50 nm and/or having a particle size distributions such that a d95 is from about 5 nm to about 60 nm.

14 . The method of claim 12 , wherein the source of silica comprises a colloidal silica.

15 . The method of claim 1 , further comprising adding to the aqueous mixture at least one compound selected from the group consisting of:
(i) a further compound of Formula (I); (ii) a further compound of Formula (IV); (iii) a compound of Formula (II) Z 5 OZ 6 Z 7 Z 8 Si, wherein each Z 5 can be a hydrogen atom, a C 1 -C 4 alkyl group or a bond to a silicon atom of another monomer; and Z 6 , Z 7 and Z 8 each independently can be 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; (iv) a compound of of Formula (III), Z 9 Z 10 Z 11 Si—R—SiZ 9 Z 10 Z 11 , wherein each Z 9 independently can be a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; Z 10 and Z 11 each independently can a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer, and each R can be selected from the group consisting 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 1 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkyl, and an optionally substituted C 4 -C 20 heterocycloalkyl group; (v) a compound of Formula (V), M 1 (OZ 12 ) 3 , wherein M 1 represents a Group 13 metal and each Z 12 independently represents a hydrogen atom, a C 1 -C 6 alkyl, or a bond to a silicon atom of another monomer; (vi) a compound of Formula (VI), (Z 13 O) 2 M 2 -O—Si(OZ 14 ) 3 , wherein M 2 represents a Group 13 metal and Z 13 and Z 14 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group or a bond to a silicon atom of another monomer; and (vii) a combination thereof.

16 . The method of claim 1 , wherein the aqueous mixture comprises a base and has a pH from about 8 to about 14.

17 . The method of claim 16 , wherein the base is ammonium hydroxide, a metal hydroxide, or a metal hydrogen carbonate.

18 . The method of claim 1 , wherein the aqueous mixture comprises an acid and has a pH from about 0.01 to about 6.0.

19 . The method of claim 18 , wherein the acid is an inorganic acid.

20 . An organosilica material made according to the method of claim 1 .

21 . An organosilica material comprising a polymer of at least one independent monomer comprising:
(i) a monomer of formula (I), [Z 15 Z 16 SiCH 2 ] 3 , wherein each

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Calabro David C
• Johnson Ivy D
• Li Quanchang
• Podsiadlo Paul
• Weston Simon C
• Afeworki Mobae

Classifications

• C01B33/113 Primary

  Silicon oxides; Hydrates thereof {(preparing monoxide by reduction of siliceous material C01B33/182)} · CPC title

• C01B37/00

  Compounds having molecular sieve properties but not having base-exchange properties · CPC title

• C08G77/04

  Polysiloxanes · CPC title

• C08G77/26

  nitrogen-containing groups · CPC title

• C08G77/06 Primary

  Preparatory processes · CPC title