Process for the production of partially polymerized antimicrobial silanol quaternary ammonium compounds

• US 10,010,080 B2
• Filed: 09/14/2015
• Issued: 07/03/2018
• Est. Priority Date: 09/14/2015
• Status: Active Grant

• Current Assignee: Novalent Limited
• Original Assignee: Indusco, Ltd.
• Inventors: Neigel, Dennis Victor
• Primary Examiner(s): Zhang, Yanzhi
• Application Number:
  US14/852,874
• Publication Number:
  US 20170071198A1
• Time in Patent Office: 1,023 Days
• Field of Search: 424426, 514 63
• CPC Class Codes: A01N 25/04 Dispersions, emulsions, suspoemulsions, suspension concentrates or gels foams A01N25/16
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A01N 33/12 Quaternary ammonium compounds
• 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: A01N 65/00 Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof containing compounds of determined constitution A01N27/00 - A01N59/00
• CPC Class Codes: A01N 65/36 Rutaceae [Rue family], e.g. lime, orange, lemon, corktree or pricklyash

Abstract

This invention is a process for the manufacture of water stable, partially polymerized antimicrobial silanol quaternary ammonium compounds (SQACs) and their trisilanol, polysiloxanol and water soluble polysiloxane derivatives thereof. Partial polymerization is accomplished by allowing the aqueous SQAC product solution to polymerize at conditions that will substantially convert all the chlorosilanol monomer to a copolymer of the SQAC, thus reducing the toxicity of the solution greatly. A stabilizing agent is added either before or after the partial polymerization. The stabilizing agent is selected from a list of antimicrobial, naturally occurring, renewable phytochemical essential oils and extracts that easily form crystal clear microemulsions when water is added to the concentrated SQAC/essential oil mixture. These non-foaming oil in water microemulsions have excellent long term storage stability, are freeze/thaw stable, remain very low in viscosity and do not phase separate or precipitate for many months. Many of the essential oils found to be useful in this process are non-toxic food additives and have pleasant scents, have low flammability yet are volatile enough to evaporate upon cure down of the SQAC, thereby resulting in a higher concentration of SQAC in the cured, antimicrobial film. Economically shippable concentrations of the low toxicity, partially polymerized, stabilized SQACs can be further diluted with water to application concentrations without losing any of their stabilizing properties and remain storage stable at these lower concentrations indefinitely. In particular, the invention relates to the use of such aqueous dilutions cured as durable antimicrobial coatings on both manufactured and natural substrates and for human or animal skin that covalently bond to the skin, remain active through many washings and reduce or eliminate bacteria, viruses and fungi for days.

Claims

1. A process to partially polymerize aqueous solutions of silanol quaternary ammonium compounds (SQACs) whereby substantially all the residual excess chlorosilanol monomer has polymerized to form a copolymer with the SQAC, and retard or stop the aqueous solution from further polymerization, further viscosity increases, and/or precipitation, the process comprising:

preparing a mixture of anhydrous, concentrated SQAC (68 to 72% in methanol) with one or more renewable, naturally derived, antimicrobial, phytochemical essential oil or extract, then diluting the mixture to between 5%-12% of active SQAC with demineralized water to produce a crystal clear, stable microemulsion, that is then partially polymerized to a point whereby the residual excess chlorosilanol monomer has polymerized to form a copolymer with the SQAC, the stabilized, partially polymerized microemulsion is then further diluted to 5% or less active SQAC with demineralized water to form a water stable, crystal clear microemulsion with a stable viscosity and clarity for greater than 6 months.

2. The process of claim 1, wherein the SQAC to form stable microemulsions is defined as 3-(trimethoxysilyl) propyl-N-octadecyl-N,N-dimethyl ammonium chloride and their trisilanol, polysiloxanol and water soluble polysiloxane derivatives.

3. The process of claim 1, wherein the essential oil or extract used to form the stable microemulsions is selected from the group consisting of grapefruit, lemon, lime, orange, tangerine, and orange peel.

4. The process of claim 1, wherein a partially polymerized aqueous solution of SQAC is generated by raising the concentration, the pH and/or the temperature to facilitate an increase in the rate of polymerization.

5. The process of claim 1, wherein a partially polymerized aqueous solution of SQAC is stopped or retarded by lowering the concentration by dilution with water, lowering the pH and/or the temperature prior to or after adding the essential oil stabilized microemulsion.

6. The process of claim 1, wherein the chlorosilanol is chloropropyltrimethoxysilane or chloropropyltriethoxysilane.

7. The process of claim 1, wherein the essential oil stabilized SQAC microemulsion contains from 3% to 40% essential oil based on active weight of anhydrous SQAC.

8. The process of claim 1, wherein the amount of essential oil stabilized, partially polymerized microemulsion added to the partially polymerized unstabilized SQAC solution is from 0.001% to 200% of the weight of the partially polymerized unstabilized solution.

9. The process of claim 1, wherein the mixture of the partially polymerized SQAC solution and the essential oil stabilized microemulsion form a water stable mixture that remains crystal clear, without separation, precipitation or further significant viscosity gain.

10. The process of claim 1, wherein the temperature during the partial polymerization process is 10°

C. to 100°

C.

11. A process of claim 10 where the temperature during the partial polymerization process is 25°

C. to 35°

C.

12. The process of claim 1, wherein the pH of the SQAC solution during the partial polymerization is pH 2 to pH 8 and the pH is adjusted with solutions of hydrochloric acid or sodium hydroxide.

13. A process of claim 12 where the pH of the SQAC solution during the partial polymerization is between pH 3 to pH 7 and the pH is adjusted with solutions of hydrochloric acid or sodium hydroxide.

14. The process of claim 1, wherein the resultant essential oil stabilized, partially polymerized, crystal clear SQAC microemulsion is diluted to 0.01% to 5.0% active SQAC, and used to treat building and construction materials, textiles and manufactured items to provide a durable, non-leaching chemically bonded antimicrobial barrier on the substrate treated.

15. The process of claim 1, wherein the resultant stabilized, partially polymerized SQAC microemulsion is used as an additive to shampoos, liquid soaps and hand sanitizers, both foaming and gel, to treat animal and human hair, nails and skin, providing a durable, chemically bonded, antimicrobial barrier that lasts through many washes and provides up to 3 days of reduction or elimination of bacteria, viruses and fungi.

16. The process of claim 1, wherein the resultant stabilized, partially polymerized microemulsion is added to benzalkonium chloride based hand sanitizers and soaps without causing a noticeable increase in solution turbidity and provides a durable chemically bonded antimicrobial barrier without interfering with the benefits of the benzalkonium chloride based hand sanitizer and soap design or its ability to foam.