Methods for using water-stabilized organosilanes

• US 6,632,805 B1
• Filed: 05/07/1996
• Issued: 10/14/2003
• Est. Priority Date: 05/07/1996
• Status: Expired due to Term

• Current Assignee: Emory University
• Original Assignee: Emory University
• Inventors: Allred, Gary D., Liebeskind, Lanny S.
• Primary Examiner(s): Pak, John
• Application Number:
  US08/646,160
• Time in Patent Office: 2,716 Days
• Field of Search: 840/5, 840/6, 852/4, 514/63, 514/642, 514/643, 514/669, 514/738, 514/769, 514/770, 514/970, 514/971, 504/100, 504/114, 424/401, 424/402, 424/411, 424/414, 424/422, 426/278, 426/321, 426/323, 426/324, 426/330, 426/335, 426/532, 426/665, 427/2.1, 427/2.11, 427/2.24, 427/2.29, 427/2.3, 427/2.31, 427/230, 427/382, 528/25, 528/27, 528/28, 528/29, 524/386-387, 524/389, 106/15.05, 106/18.32, 106/18.35, 106/287.11, 106/287.12, 106/287.13, 106/287.14, 106/287.15, 106/287.16
• 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: A23L 3/00 Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs preserving foods or foodstuffs in association with packaging B65B55/00
• CPC Class Codes: A23L 3/3463 Organic compounds; Microorganisms; Enzymes
• CPC Class Codes: A23L 3/349 with singly-bound oxygen
• CPC Class Codes: A23L 3/3526 Organic compounds containing nitrogen
• CPC Class Codes: A23L 3/3544 Organic compounds containing hetero rings
• CPC Class Codes: A23L 5/42 Addition of dyes or pigments, e.g. in combination with optical brighteners
• CPC Class Codes: A61L 2/18 Liquid substances or solutions comprising solids or dissolved gases
• CPC Class Codes: A61L 2300/216 with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
• CPC Class Codes: A61L 2300/404 Biocides, antimicrobial agents, antiseptic agents
• CPC Class Codes: A61L 2300/606 Coatings
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence
• CPC Class Codes: C07F 7/1804 Compounds having Si-O-C linkages Si-O-acyl linkages C07F7/1896
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C12H 1/00 Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages simulating ageing by flavouring C12G3/06
• CPC Class Codes: D06M 13/513 with at least one carbon-silicon bond
• CPC Class Codes: D06M 15/643 containing silicon in the main chain
• CPC Class Codes: D06M 16/00 Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
• CPC Class Codes: D06M 23/005 Applying monomolecular films on textile products like fibres, threads or fabrics
• CPC Class Codes: D06P 1/5292 : containing Si-atoms
• CPC Class Codes: D06P 1/62 : using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
• CPC Class Codes: D06P 1/64 : using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups

Abstract

A method of dyeing and treating a substrate using a water-stabilized organosilane. A method of antimicrobially treating a food article. A method of antimicrobially coating a fluid container. A method of antimicrobially coating a latex medical article.

Claims

1. A method of antimicrobially treating a food article, comprising contacting the food article with an effective amount of a water stable composition comprising water and a product that is formed by reacting in water:

a) an organosilane of the formula R_nSiX<sub>4−

n</sub> where n is an integer of from 0 to 3;

each R is, independently, a nonhydrolizable organic group; and

each X is, independently, a hydrolyzable group, with

b) a polyol containing at least three hydroxy groups, wherein all of the hydroxy groups are separated by at least three intervening atoms,

wherein the polyol is not hydroxyethyl cellulose,

wherein the product is a monomer, oligomer, or a combination thereof,

for a period of time sufficient to antimicrobially treat the food article.

2. A method of antimicrobially coating a fluid container used for containing a human or animal consumable product, comprising contacting the container with an effective amount of a water stable composition comprising water and a product that is formed by reacting in water:

a) an organosilane of the formula R_nSiX<sub>4−

n</sub> where n is an integer of from 0 to 3;

each R is, independently, a nonhydrolizable organic group; and

each X is, independently, a hydrolyzable group, with

b) a polyol containing at least three hydroxy groups, wherein all of the hydroxy groups are separated by at least three intervening atoms,

wherein the polyol is not hydroxyethyl cellulose,

wherein the product is a monomer, oligomer, or a combination thereof,

for a period of time sufficient to antimicrobially coat the container.

3. A method of antimicrobially coating a latex medical article for use in a human or animal medical procedure, comprising contacting the article with an effective amount of a water stable composition comprising water and a product that is formed by reacting in water:

a) an organosilane of the formula R_nSiX<sub>4−

n</sub> where n is an integer of from 0 to 3;

each R is, independently, a nonhydrolizable organic group; and

each X is, independently, a hydrolyzable group, with

b) a polyol containing at least three hydroxy groups, wherein all of the hydroxy groups are separated by at least three intervening atoms,

wherein the polyol is not hydroxyethyl cellulose,

wherein the product is a monomer, oligomer, or a combination thereof,

for a period of time sufficient to antimicrobially coat the article.

4. The method of claim 3, wherein the article is a surgical glove.

5. A method of antimicrobially enhancing a product of rubbing alcohol, a flower preservative, or a waterproofing solution, comprising admixing with the product an effective amount of a water stable composition comprising water and a product that is formed by reacting in water:

a) an organosilane of the formula R_nSiX<sub>4−

n</sub> where n is an integer of from 0 to 3;

each R is, independently, a nonhydrolizable organic group; and

each X is, independently, a hydrolyzable group, with

b) a polyol containing at least three hydroxy groups, wherein all of the hydroxy groups are separated by at least three intervening atoms,

wherein the polyol is not hydroxyethyl cellulose,

wherein the product is a monomer, oligomer, or a combination thereof,

for a period of time sufficient to antimicrobially enhance the product.

6. A method of antimicrobially treating a substrate selected from the group consisting of a concrete pipe, a tooth brush, a comb, a hair brush, a denture, an orthodontic retainer, a spa or pool filter, an air filter, an HVAC air system, a cabin air system, a marble article, a statue, an exposed work of art, an HDP plastic cover, a stucco finish, blended cotton, a bio-film, a bio-adhesive, a single ply roofing, a roofing shingle, and a fiberglass reinforcement product, comprising contacting the substrate with an effective amount of a water stable composition comprising water and a product that is formed by reacting in water:

a) an organosilane of the formula R_nSiX<sub>4−

n</sub> where n is an integer of from 0 to 3;

each R is, independently, a nonhydrolizable organic group; and

each X is, independently, a hydrolyzable group, with

b) a polyol containing at least three hydroxy groups, wherein all of the hydroxy groups are separated by at least three intervening atoms,

wherein the polyol is not hydroxyethyl cellulose,

wherein the product is a monomer, oligomer, or a combination thereof,

for a period of time sufficient to antimicrobially treat the substrate.

7. The method of claim 6, wherein n is an integer from 0 to 2;

each R is, independently, alkyl, alkyl alcohol, or aromatic;

each X is, independently, hydroxy, alkoxy, halogen, acetyl, acetoxy, acyl, a hydroxylated solid or liquid polymeric moiety, polyether or polyalkylether; and

wherein the polyol is of the formula I;

8. The method of claim 7, wherein V⁻

and Q⁻

are halide, sulfate, tosylate, carboxylate, polycarboxylate, alkyl, arylsulfonate, phosphate, phosphonate, borate, or boronate.

9. The method of claim 7, wherein W is alkyl of from 1 to 22 carbon atoms.

10. The method of claim 7, wherein W is alkyl of from 1 to 10 carbon atoms.

11. The method of claim 7, wherein W is alkyl of from 1 to 3 carbon atoms.

12. The method of claim 6, wherein the organosilane is (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Br⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(C₁₀H₂₁)₂CH₃Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(C₁₀H₂₁)₂CH₃Br⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₃Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₈H₁₇Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₀H₂₁Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₂H₂₅Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₄H₂₉Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₆H₃₃Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₂₀H₄₁Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(C₄H₉)₃Cl⁻

, (CH₃O)₃Si(CH₂)₃N⁺(C₂H₅)₃Cl⁻

, (CH₃CH₂O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₂₇Cl⁻

, (CH₃O)₃Si(CH₂)₃NHC(O)(CF₂)₆CF₃, (CH₃O)₃Si(CH₂)₃NHC(O)(CF₂)₈CF₃, (CH₃O)₃Si(CH₂)₃NHC(O)(CF₂)₁₀CF₃, (CH₃O)₃Si(CH₂)₃NHC(O)(CF₂)₁₂CF₃, (CH₃O)₃Si(CH₂)₃NHC(O)(CF₂)₁₄CF₃, (CH₃O)₃Si(CH₂)₃NHC(O)(CF₂)₁₆CF₃, (CH₃O)₃Si(CH₂)₃NHSO₂(CF₂)₇CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CH₂)₆CH₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CH₂)₈CH₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CH₂)₁₀CH₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CH₂)₁₂CH₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CH₂)₁₄CH₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CH₂)₁₆CH₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₆CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₈CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₁₀CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₁₂CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₁₄CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₁₆CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHSO₂(CF₂)₇CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHSO₂(CF₂)₉CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHSO₂(CF₂)₁₁CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHSO₂(CF₂)₁₃CF₃, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHSO₂(CF₂)₁₅CF₃, or (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHSO₂(CF₂)₁₆CF₃.

13. The method of claim 6, wherein the organosilane is NH₂(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, NH₂(CH₂)₃Si(OCH₃)₃, NH₂(CH₂)₃Si(OCH₂CH₃)₃, Cl(CH₂)₃Si(OCH₃)₃, Cl(CH₂)₃Si(OCH₂CH₃)₃, Cl(CH₂)₃SiCl₃, CH₃CH₂C(O)O—

(CH₂)₃Si(OCH₃)₃, CH₃CH₂C(O)O—

(CH₂)₃Si(OCH₂CH₃)₃, H₂C═

C(CH₃)C(O)O—

(CH₂)₃Si(OCH₃)₃, H₂C═

C(CH₃)C(O)O—

(CH₂)₃Si(OCH₂CH₃)₃, CH₃SiHCl₂, NaO(CH₃O)P(O)(CH₂)₃Si(OH)₃, SiHCl₃, H₂C═

CHSi(OCOCH₃)₃, H₂C═

CHSi(OCH₃)₃, H₂C═

CHSi(OCH₂CH₃)₃, H₂C═

CHSiCl₃, (CH₃)₂SiCl₂, (CH₃)₂Si(OCH₃)₂, (C₆H₅)₂SiCl₂, (C₂H₅)SiCl₃, (C₂H₅)Si(OCH₃)₃, (C₂H₅)Si(OCH₂CH₃)₃, isobutyltrimethoxysilane, n-octyltriethoxysilane, CH₃(C₆H₅)SiCl₂, CH₃SiCl₃, CH₃Si(OCH₃)₃, C₆H₅SiCl₃, C₆H₅Si(OCH₃)₃, C₃H₇SiCl₃, C₃H₇Si(OCH₃)₃, SiCl₄, ClCH₂C₆H₄CH₂CH₂SiCl₃, ClCH₂C₆H₄CH₂CH₂Si(OCH₃)₃, ClCH₂C₆H₄CH₂CH₂Si(OCH₂CH₃)₃, (decyl)(trichloro)silane, (dichloro)(methyl)(4-methylphenethyl)silane, (diethoxy)(methyl)(phenyl)silane, {3-(diethylamino)propyl}(trimethoxy)silane, {3-(dimethoxy)(methyl)silyl}-1-propanethiol, (dimethoxy)(methyl)(vinyl)silane, 3-{tris(trimethylsilyloxy)silyl}propyl methacrylate, (trichloro){4-(chloromethyl)phenyl}silane, (methyl){bis(trimethylsilyloxy)}(vinyl)silane, (methyl)(tripropoxy)silane, or (trichloro)(cyclopentyl)silane.

14. The method of claim 6, wherein the polyol is a compound having the formula VII:

15. The method of claim 14, wherein g is an integer of from 0 to 3;

R₁₂ is (CH₂)_gR₁₄, lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R₁₅)(R₁₆), N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N⁺(CH₃)₂(CH₂)₃SO₃⁻

, N⁺(CH₃)₃T⁻

, or N⁺(R₁₇)(R₁₈)(R₁₉)T⁻

;

R₁₃ is H, OH, (CH₂)_sR₁₄, (CH₂)OPO₃H₂, or (CH₂)PO₃H₂, lower alkyl of from 1 to 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, and

each R₁₄ is, independently, OH or {—

CH₂C(CH₂OH)₂CH₂O}_j—

H where j is an integer of from 0 to 5.

16. The method of claim 14, wherein R₁₂ is (CH₂)_gR₁₄, lower alkyl of from 1 to about 4 carbon atoms, or lower alkoxy of from 1 to about 4 carbon atoms.

17. The method of claim 14, wherein R₁₂ is N(R₁₅)(R₁₆), N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N⁺(CH₃)₂(CH₂)₃SO₃⁻

, N⁺(CH₃)₃T⁻

, or N⁺(R₁₇)(R₁₈)(R₁₉)T⁻

.

18. The method of claim 14, wherein g is an integer of from 0 to 3;

R₁₂ is (CH₂)_g14, lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R₁₅)(R₁₆), N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N⁺(CH₃)₂(CH₂)₃SO₃⁻

, N⁺(CH₃)₃T⁻

, or N⁺(R₁₇)(R₁₈)(R₁₉)T⁻

; and

each R₁₄ is OH.

19. The method of claim 14, wherein g is an integer of from 0 to 3;

R₁₂ is (CH₂)_gR₁₄, lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R₁₅)(R₁₆), N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N(H)(CH₂)₃OSO₃H, N⁺(CH₃)₂(CH₂)₃SO₃⁻

, N⁺(CH₃)₃T⁻

, or N⁺(R₁₇)(R₁₈)(R₁₉)T⁻

; and

each R₁₄ is, independently, {—

CH₂C(CH₂OH)₂CH₂O}_j—

H where j is an integer of from 0 to 5.

20. The method of claim 6, wherein the polyol is aryl substituted with from 2 to 6 moieties of —

(OCH₂)C(CH₂OH)₃.

21. The method of claim 6, wherein the polyol is pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, tris(hydroxymethyl)ethane, tris(hydroxymethyl)propane, tris(hydroxymethyl)nitromethane, tris(hydroxymethyl)aminomethane, tris(hydroxymethyl)methane trimethyl ammonium iodide, or tetrakis(hydroxymethyl)phosphonium chloride.

22. The method of claim 6, wherein the organosilane is of the formula II, III, IV, or V:

23. The method of claim 22, wherein each of Y and V is, independently, halide, sulfate, tosylate, carboxylate, polycarboxylate, alkyl, arylsulfonate, phosphate, phosphonate, borate, or boronate.

24. The method of claim 6, wherein the organosilane is 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, 3-(trimethoxysilyl)propylmethyldi(decyl) ammonium chloride, 3-chloropropyltrimethylsilane, 3-chloropropyltrimethoxysilane, octadecyltrimethoxysilane, or perfluorooctyltriethoxysilane and the polyol is pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, tris(hydroxymethyl)ethane, tris(hydroxymethyl)propane, tris(hydroxymethyl)nitromethane, tris(hydroxymethyl)aminomethane, or tris(hydroxymethyl)methanetrimethyl ammonium iodide.

25. The method of claim 6, wherein the organosilane is 3-(trihydroxysilyl)propyldimethyloctadecyl ammonium chloride and the polyol is pentaerythritol.

26. The method of claim 6, wherein the polyol is pentaerythritol.

27. The method of claim 6, wherein the product is monomeric.

28. The method of claim 6, wherein the product is oligomeric.

29. The method of claim 6, wherein the products of the composition are substantially monomeric.

30. The method of claim 6, wherein the products of the composition are substantially oligomeric.

31. The method of claim 6, wherein the polyol has the structure XX, XXV, or XXX:

32. The method of claim 6, wherein the polyol has the structure XXXV or XL:

 

(HOCH₂)₃CN(R₁₄)(R₁₅) 

 

(XXXV)

or

33. The method of claim 6, wherein the organosilane is 3-(trimethoxysilyl)propylmethyldi(decyl) ammonium chloride and the polyol is pentaerythritol.