Quaternary ammonium-functionalized-POSS compounds

• US 20100004202A1
• Filed: 02/11/2009
• Published: 01/07/2010
• Est. Priority Date: 02/15/2008
• Status: Abandoned Application

• Current Assignee: Ndsu-Research Foundation
• Original Assignee: Ndsu-Research Foundation
• Inventors: Majumdar, Partha, Chisholm, Bret Ja
• Application Number:
  US12/378,155
• Publication Number:
  US 20100004202A1
• Time in Patent Office: Days
• US Class Current: 514/63
• CPC Class Codes: A01N 55/00 Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing organo-phosphorus compounds A01N57/00
• CPC Class Codes: C07F 7/21 Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• CPC Class Codes: C08K 5/5419 containing at least one Si—C bond
• CPC Class Codes: C09D 5/14 Paints containing biocides, e.g. fungicides, insecticides or pesticides C09D5/16 takes precedence
• CPC Class Codes: C09D 7/63 organic

Abstract

A silsesquioxane cage structure has a general formula [R¹SiO_1.5]_n, wherein, n is an integer greater than or equal to 4; each R¹ is an amine-functional siloxy group, a quaternary ammonium-functional siloxy group, or a texturizing moiety. At least one R¹ group may optionally be a quaternary ammonium-functional siloxy group. Compositions may be prepared from polymers and the silsesquioxane compounds.

Claims

1. A compound comprising:

a silsesquioxane cage structure of a general formula [R¹SiO_1.5]_n, wherein,

n is an integer greater than or equal to 4;

each R¹ is independently an amine-functional siloxy group, a quaternary ammonium-functional siloxy group, a texturizing moiety or a cross-linkable group; and

at least about 25% of the R¹ groups are quaternary ammonium-functional siloxy groups, amine-functional siloxy groups, or a combination thereof.

2. The compound of claim 1, wherein the silsesquioxane cage structure includes compounds represented by the formula:

3. The compound of claim 1, wherein:

the amine-functional siloxy group is a group of formula —

OSiR²R³(CH₂)_xNR⁴R⁵;

R² and R³ are independently alkyl, cycloalkyl, aralkyl, or aryl;

R⁴ and R⁵ are independently H, alkyl, cycloalkyl, aralkyl, aryl, or R⁴ and R⁵, along with the N, form a heterocycloalkyl; and

x is an integer from 2 to 25.

4. The compound of claim 1, wherein:

the quaternary ammonium-functional siloxy group is a group of formula —

OSiR²R³(CH₂)_xN⁺R⁴R⁵R⁶;

R² and R³ are independently alkyl, cycloalkyl, aralkyl, or aryl;

R⁴ and R⁵ are independently H, alkyl, cycloalkyl, aralkyl, aryl, or R⁴ and R⁵, along with the N, form a heterocycloalkyl;

R⁶ is H, alkyl, cycloalkyl, or aralkyl; and

x is an integer from 2 to 25.

5. The compound of claim 4, wherein about 25% to 75% of the R¹ groups are quaternary ammonium-functional siloxy groups.

6. A method of producing the compound of claim 1 comprising:

reacting a silsesquioxane cage compound of formula [R²R³HSiOSiO_1.5]_n with a compound of formula H₂C═

CH(CH₂)_xNR⁴R⁵ and a vinyl functional texturizing compound to form an amine-functional silsesquioxane cage compound;

wherein x is an integer from 2 to 25;

n is an integer greater than or equal to 4;

R² and R³ are independently alkyl, cycloalkyl, aralkyl, or aryl; and

R⁴ and R⁵ are independently H, alkyl, cycloalkyl, aryl, or R⁴ and R⁵, along with the N atom form a heterocycloalkyl group;

wherein the silsesquioxane cage compound is a polyhedral oligomeric silsesquioxane (POSS).

7. A method of producing the compound of claim 1 comprising:

reacting a compound of formula H₂C═

CH(CH₂)_xNR⁴R⁵ with a polyhedral oligomeric silsesquioxane (POSS) of formula [R¹SiO_1.5]_n, where, each R¹ is independently a —

OSiHR²R³ group or a texturizing moiety to form an amine-functional silsesquioxane cage compound;

wherein,

x is an integer from 2 to 25;

n is an integer greater than or equal to 4;

R² and R³ are independently H, alkyl, cycloalkyl, aralkyl, or aryl;

R⁴ and R⁵ are independently H, alkyl, cycloalkyl, aryl, or R⁴ and R⁵, along with the N, form a heterocycloalkyl; and

at least one R¹ is a —

OSiHR²R³ group.

8. The method of claim 7, further comprising:

reacting the amine-functional silsesquioxane cage compound with a compound of formula R⁶X to form a quaternary ammonium-functional polyhedral oligomeric silsesquioxane;

wherein;

R⁶ is an alkyl, cycloalkyl or aralkyl group; and

X is a halogen or an R⁶SO₄—

group.

9. A biocidal composition comprising polymeric material and the compound of claim 1.

10. The biocidal composition of claim 9, wherein the polymer material comprises a thermoplastic polymer, an elastomeric polymer, or a blend thereof.

11. The biocidal composition of claim 9, wherein the biocidal composition is a coating on a substrate surface.

12. The biocidal coating of claim 11, wherein the coating comprises:

at least about 75 wt. % polydialkyl siloxane; and

about 5 to 25 wt. % of the compound of claim 3;

wherein the quaternary ammonium-functional siloxy groups are represented by the formula

—

OSiR²R³(CH₂)_xN⁺R⁴R⁵R⁶; and

R⁶ is C₁₀-C₁₈ n-alkyl.

13. The biocidal coating of claim 12, wherein about 25% to 75% of the R¹ groups are quaternary ammonium-functional siloxy groups.

14. The biocidal coating of claim 11 wherein the coating is a cross-linked polysiloxane coating.

15. The biocidal coating of claim 11 comprising the silsesquioxane cage structure wherein n is 8.

16. The biocidal coating of claim 12, wherein R², R³, R⁴, and R⁵ are methyl;

x is an integer from 2 to 4; and

quaternary ammonium-functional siloxy groups include groups wherein R⁶ is C₁₂ n-alkyl.

17. The biocidal coating of claim 12, wherein R², R³, R⁴, and R⁵ are methyl;

x is an integer from 2 to 4; and

quaternary ammonium-functional siloxy groups include groups wherein R⁶ is C₁₆ n-alkyl.

18. The biocidal coating of claim 12, wherein R², R³, R⁴, and R⁵ are methyl;

x is an integer from 2 to 4; and

quaternary ammonium-functional siloxy groups include groups wherein R⁶ is C₁₈ n-alkyl.

19. A method of producing a biocidal coating, comprising:

reacting a mixture comprising;

(A) a tertiaryamino-functional polyhedral oligomeric silsesquioxane and/or an amino-functional polydimethylsiloxane; and

(B) a halo-functional polyhedral oligomeric silsesquioxane and/or a halo-functional polydimethylsiloxane, wherein the halide is Cl, Br, and/or I; and

wherein the reaction mixture includes at least one of the tertiaryamino-functional polyhedral oligomeric silsesquioxane and the haloalkyl-functional polyhedral oligomeric silsesquioxane.

20. A biocidal coating prepared by a method comprising:

reacting a mixture comprising;

(A) a tertiaryamino-functional polyhedral oligomeric silsesquioxane and/or an amino-functional polydimethylsiloxane; and

(B) a haloalkyl-functional polyhedral oligomeric silsesquioxane and/or a halo-functional polydimethylsiloxane, wherein the halide is Cl, Br, and/or I; and

wherein the reaction mixture comprises at least one of the tertiaryamino-functional polyhedral oligomeric silsesquioxane and the haloalkyl-functional polyhedral oligomeric silsesquioxane.