Vapor phase methods of forming supported highly branched polyamines

• US 9,427,726 B2
• Filed: 02/27/2015
• Issued: 08/30/2016
• Est. Priority Date: 10/13/2011
• Status: Active Grant

• Current Assignee: Global Thermostat Operations LLC
• Original Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Inventors: Chaikittisilp, Watcharop, Jones, Christopher W.
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US14/633,967
• Publication Number:
  US 20150165417A1
• Time in Patent Office: 550 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/262 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: B01J 20/28 characterised by their form or physical properties
• CPC Class Codes: B01J 20/28023 Fibres or filaments fibres or filaments in the form of membranes B01J20/28038; B01J20/28007 takes precedence
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3278 Polymers being grafted on the carrier
• CPC Class Codes: B01J 2220/84 Capillaries
• CPC Class Codes: C08G 83/001 Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

Methods of making supported polyamines, supported polyamines, and the like, are disclosed.

Claims

1. A method of making a structure comprising a polyamine supported on a solid substrate, the method comprising:

contacting a monomer having a nitrogen-containing heterocycle with a solid substrate material, wherein the monomer is in the vapor phase; and

forming a hyperbranched polyamine polymer on a surface of the solid substrate material.

2. The method of claim 1, wherein the hyperbranched polyamine polymer is formed at a temperature of about 0°

to 200°

C. for a time period of about 2 h to 200 h.

3. The method of claim 1, wherein the monomer is selected from the group consisting of:

an aziridine monomer, an azetidine monomer, a pyrrolidine monomer, and a diazetidine monomer, and a combination thereof.

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

silica, alumina, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, iron oxide, mixed oxides composed of those elements, and organically modified derivatives of each of these.

5. The method of claim 4, wherein the organically modified silicate includes carboxylate groups on the surface of the solid substrate material.

6. The method of claim 5, wherein the hyperbranched polymer is covalently bonded to an oxygen of the hydroxyl group on the surface of the solid substrate material.

7. The method of claim 1, wherein the hyperbranched polymer is an ethyleneamine hyperbranched polymer.

8. The method of claim 1, wherein the hyperbranched polymer includes units having the formula RwN—

CR2-CR2, wherein R is selected from H and a functional group, wherein w is 0, 1, or 2.

9. The method of claim 1, wherein the hyperbranched polymer includes units having the formula HwN—

CH2-CH2, wherein w is 0, 1, or 2.

10. The method of claim 4, wherein the hyperbranched polymer is covalently bonded via a silicon compound to one or more oxygen atoms on the surface of the solid substrate material, wherein the silicon compound has the formula Si(OCH3), wherein Si forms bonds to one, two, or three oxygen atoms on the surface of the pore.

11. The method of claim 5, wherein the solid substrate material is porous and wherein the pores extend below the outer surface of the solid substrate, and wherein a molecule having the formula —

(CRIR2)s-XHP is covalently bonded to the oxygen of a hydroxyl group on the inside surface of a pore, wherein s is 1 to 10, wherein each of RI and R2 are independently selected from the group consisting of;

H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where a substitution is from a group selected from the group consisting of;

F, CI, Br, I, N, P, S, and 0, wherein X is selected from the group consisting of;

N—

R, S, and P—

R, where N or P bonds to the HP, wherein R is selected from the group consisting of;

H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where the substitution is from a group selected from the group consisting of;

F, CI, Br, I, I, N, P, S, and 0, wherein if X is N—

R or P—

R, then R is selected from the group consisting of;

HP, H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where the substitution is from a group selected from the group consisting of;

F, CI, Br, I, N, P, S, and 0, and wherein HP is the hyperbranched polymer.

12. The method of claim 1, wherein the solid substrate material is porous and wherein the pores extend below the outer surface of the solid substrate, and wherein a molecule having the formula —

SiR4q(CRIR2)s-X—

HP is covalently bonded to one, two, or three oxygen atoms on the surface of a pore, wherein s is 1 to 10, wherein each of RI and R2 are selected from the group consisting of;

H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where a substitution is from a group selected from the group consisting of;

F, CI, Br, I, N, P, S, and 0, wherein X is selected from the group consisting of;

N—

R, S, and P—

R, where P bonds to the HP, wherein R is selected from the group consisting of;

H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where the substitution is from a group selected from the group consisting of;

F, CI, Br, I, N, P, S, and 0, wherein R4 is selected from the group consisting of;

an alkyl, a substituted alkyl, an alkenyl, a substituted alkenyl, a methyl, a substituted methyl, an alkoxyl, a substituted alkoxyl, a methoxy, a n-propoxy, an isopropoxy, a halogen, and N(R)2, wherein q is 1 or 2, and wherein HP is the hyperbranched polymer.

13. The method of claim 1, further comprising:

removing unreacted monomer from the solid substrate material.

14. The method of claim 13, wherein the step of removing unreacted monomer from the solid substrate material comprises flowing a gas across the surface of the solid substrate material to remove unreacted monomer.

15. The method of claim 1, wherein the structure of the solid substrate material is selected from the group consisting of:

a porous structure, a fiber, a capillary tube, a disk membrane, a tubular membrane, a sheet, and a monolith.

16. The method of claim 1, wherein the solid substrate material is an organic polymer.

17. The method of claim 1, wherein the solid substrate material has a longest dimension of about 500 nm to 500 μ

m.

18. The method of claim 1, wherein the solid substrate material has a dimension, perpendicular to the gas flow direction, of about 2 mm to 100 cm.

19. The method of claim 1, wherein the solid substrate material is porous and includes one or more oxygen atoms on the surfaces of the pores.