Process for the Production of Partially Polymerized Antimicrobial Silanol Quaternary Ammonium Compounds

• US 20170071198A1
• Filed: 09/14/2015
• Published: 03/16/2017
• Est. Priority Date: 09/14/2015
• Status: Active Grant

• Current Assignee: Novalent Limited
• Original Assignee: Indusco, Ltd.
• Inventors: Neigel, Dennis Victor
• Granted Patent: US 10,010,080 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• 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 alkoxysilyl quaternary ammonium compounds and their trisilanol, polysiloxanol and water soluble polysiloxane derivatives thereof (SQACs). 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 loosing 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) to the point where substantially all the residual excess chlorosilanol monomer has polymerized to form a copolymer with the SQAC, then to retard or stop the aqueous solution from further polymerization (further viscosity increases and/or precipitation) by:

a) preparing a mixture of anhydrous, concentrated SQAC with one or more renewable, naturally derived, antimicrobial, phytochemical essential oils or extracts, then diluting this mixture to greater than 5% active SQAC with demineralized water thus producing a crystal clear, stable microemulsion, that is then partially polymerized to the point where substantially all the residual excess chlorosilanol monomer has polymerized to form a copolymer with the SQAC. This 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.

b) preparing a mixture of anhydrous, concentrated SQAC with one or more renewable, naturally derived, antimicrobial, phytochemical essential oils or extracts, then diluting this mixture to the desired aqueous concentration with demineralized water thus producing a crystal clear, stable microemulsion, that is then partially polymerized to the point where substantially all the residual excess chlorosilanol monomer has polymerized to form a copolymer with the SQAC. This stabilized, partially polymerized microemulsion is either used as is in application or further diluted with an unstabilized partially polymerized solution to stop or retard further polymerization.

c) preparing a mixture of decyl glucoside, or any other suitable surfactant capable of microemulsifing one or more renewable, naturally derived, antimicrobial, phytochemical essential oils or extracts, then diluting this mixture to the desired aqueous concentration with demineralized water thus producing a crystal clear, stable microemulsion, and adding this microemulsion to stabilize an SQAC solution that has been partially polymerized to the point where substantially all the residual excess chlorosilanol monomer has polymerized to form a copolymer with the SQAC.

2. A process of claim 1 where the preferred SQAC used to form stable microemulsions is selected from the following monomers:

SQAC #1 3-(trimethoxysilyl) propyl-N-octadecyl-N,N-dimethyl ammonium chloride

SQAC #2 3-(trimethoxysilyl) propyl-N-tetradecyl-N,N-dimethyl ammonium chloride

SQAC #3 3-(triethoxysilyl) propyl-N-octadecyl-N,N-dimethyl ammonium chloride

SQAC #4 3-(trimethoxysilyl) propyl-N-didecyl-N,N-dimethylammonium chloride

and the trisilanol, polysiloxanol and water soluble polysiloxane derivatives thereof.

3. A process of claim 1 where the essential oil or extract used to form stable microemulsions is selected from the following non-all inclusive list:

Jasonia candicans (sesquiterpenes, lactones);

Polygonum flaccidum (flavone and alpha santalene derivatives);

Acalypha wikesiana (extracts);

Pavetta owariensis (procyanidins);

Plectranthus hereroensis (diterpenoids, diterpenes);

Moss (Dicranin extract);

Cannabis sativa (extract);

Gloiosiphonia spp. (gloiosiphones);

Laminaceae spp. (extract);

Securidaca spp. (extract);

Veronia spp. (extract);

Hyptis umbrose (umbrosone);

Asclepias syriaca (milkweed extract);

Tagetes tenuifolia (thiophene);

Calophyllum inophylloide (flavonoids);

Tanacetum densum (sesquiterpene lactones, triterpenoids);

Neorautanenia mitis (extract);

Premna schimper (diterpene);

Premna oligotricha (sesquiterpenes);

Premna oligotricha (diterpenes);

Jasonia candicans (essential oils);

Visnea mocanera (beta-sitosterol, triterpenic betulinic acid, ursolic acid, plantanic acid);

Asteraceae spp. (terthiophenes and polyynes);

Petalostemum purpureum (extract);

Camelia sinensis (catechin);

Helichrysum picardii (flavonoids);

Helichrysum italicum (flavonoids);

Corydalis pallida (protoberberine alkloids);

Shiraia bambusicola (perylenequinones);

Fraxinum omus (hydroxycoumarins);

Podocarpus nagi (totarol and nortiterpene dilactones);

Heterotheca inuloides (sesquiterpenoids);

Pelargonium spp. (essential oils);

Piper sarmentosum (phenylpropanoids);

Allium spp. (extract);

Juniperus procera (diterpenes);

Achillea conferta (flavonoids, flavones, sesquiterpenoid lactones);

Magnolia virginiana (lignans, neolignans);

Eucalyptus euglobal (euglobal);

Armillaria mellea (armillaric acid);

Dracena mannii (spirostanol saponin);

Piper aduncum (chromenes, prenylated benzoic acid);

Rhamnaceae spp. (cyclopeptide alkaloids);

Buddleja globosa (verbascoside);

Cephalocereus senilis (phytoalexin aurone);

Salvia albocaerulea (diterpene);

Gomphrena martiana and Gomphrena boliviana (extracts);

Paepalanthus spp. (vioxanthin);

Helichrysum stoechas and Helichrysum crispum (extracts);

Achillea ptarmica (trans-pinocarveyl hydroperoxides);

Dehaasia incrassata (alkaloids);

Asteraceae spp. (extracts);

Arctotis auriculate (extracts);

Eriocephalus africanus (extracts);

Felicia erigeroides (extracts);

Hemerocallis fulva (phytosterols, fatty acid esters);

Psoralea juncea (plicatin B);

Pluchea symphytifolia (caffeic acid esters);

Tovomitopsis psychotrifolia (Vitamin E derivative), Celosia argentea (triterpenoid saponins and flavonoids);

Azadirachta indica (tetranortriterpenoid, mahmoodin, protolimonoids, naheedin);

Moraceae spp. (coumarins);

Hypericum erectum (phloroglucinol derivatives);

Podospora appendiculate (Appenolides A, B, &

C, furanones);

Artemisia princeps var. orientalis, Artemisia capillaris, Artemisia mexicana and Artemisia scoparia (extract);

Paddy malt (mash extract);

Kigelia pinnata (extract);

Acalypha wilkesiana (extract);

seaweeds, seagrass and lemongrass (essential oils);

Borrieria latifolia, Borreria setidens, Hedyotis diffusa), Hedyotis nudicaulis, Morinda elliptica, Morinda umbellata, Sida rhombifolia, and Vitex ovata (extracts);

Tabebuia impetiginosa, Achyrocline spp., Larrea divaricata, Rosa borboniana, Punica granatum, Psidium guineense, Lithrea ternifolia (extracts);

Lepechinia caulescens, Lepidium virginicum and Tanacetum parthenium (extracts);

Talaromyces flavus (extracts);

Daucus carota (extract);

Flabellia petiolata, Caulerpa prolifera, Halimeda tuna, Corallina elongata, Lithophyllum lichenoides, Phyllophora crispa, Cystoseira spp., Halopteris spp., Codium spp., Valonia utricularis, Posidonia oceanica, Zostera noltil and Cymodocea nodosa (extracts);

Centauraea orientalis, Diospyros khaki, Sida hermaphrodita, Forsythia intermedia, Scutellaria polydon, Eugenia malaccensis and Eugenia jambolana (extracts);

Fritillaria L. spp. (ebeinone, steroidal alkaloids);

Kigelia pinnata, Peperomia pellucida, Populus nigra, Populus balsamifera and Populus deltoides (extracts);

Melaleuca alternifolia (essential oil);

Elfvingia applanata (naringenin);

Ficus sycomorus, grapefruit seed, Garlic, Allicin, Peat, Strophanthus hispidus, Secamone afzeli, Mitracarpus scaberi, Entada abyssinjca, Terminalia spinosa, Harrisonia abyssinica, Ximinea caffra, Azadirachta indica, Spilanthes mauritiana, Terminalia spinosa (extracts);

Cyanobacteria (ambigols A and B, tjipanazole);

coffee (extract);

Sporochnus pedunculatus, Dalbergia melanozylon, Celastrus scandens, Juglans nigra, Kalmia latifolia, Pelargonium xhortorum, Rhus glabra and Lindera benzoin (extracts);

Striga densiflora, Striga orobanchioides, Striga lutea, Pistacia lentiscus L., Mitracarpus villosus, Bixa orellana, Bridelia ferruginea, Alpinia katsumadai, Alpinia officinarum, Artemisia capillaris, Casia obtusifolia, Dendrobium moniliforme, Epimedium grandiflorum, Glycyrrhiza glabra, Lithosperum erythrorhizon, Magnolia obovata, Morus bonbycis, Natopterygii incisium, Polygonum multiflorum, Prunus mume, Rheum palmatum, Ricinus communis, Sophora flavescens, Swertia japonica, black pepper, rosemary, red pepper, Isopyrum thalictroides, Calotropis procera, Chrysanthemum spp., Holarrhena antidysenterica, Lunularia crusiata, Dumertiera hirsuta, Exormotheca tuberifera, and liverwort (extracts);

Filipendula ulmaria, Salix glauca, Usnea filipendula, Clkadina arbuscula (salicylic compounds);

Tanacetum parthenium, Thymus capitatus, and Elfingia applanata (extracts);

Fraxinus ornus (hydroxycoumarins, esculin, esculetin, fraxin, and fraxetin);

Zizyphus nummularia, LONGO VITAL, Pelargonium spp., Scaevola sericea, Psychotria hawaiiensis, Pipturus albidis, Aleurites moluccana, Solanum niger, Piper methysticum, Barringtonia asiatica, Adansonia digitata, Harungana madagascariensis, Jacaranda mimosaefolia, Erythroxylum catauba, Bidens pilosa, Lemna minor, Potamogeton spp., Nasturtium officinale, Apium nodiflorum, Agaricus subrutilescens, Amanita virosa, Amanita pantherina, Lycoperdon perlatum, Psidium guajava, Averrhoa carambola, musa sapientum, Carica papaya, Passiflora edulis, Lansium domesticum and Baccaurea motleyana (extracts);

horse radish, celandine grass, bur marigold and yarrow grass (extracts);

Abuta grandifola, Cyperus articulatus, Gnaphalium spicatum, Pothomorphe peltata, Ficus sycomorus, Ficus Benjamina, Ficus bengalensis, Ficus religiosa, Alchornea cordifolia, Bridelia feruginea, Eucalyptus citriodora, Hymenocardia acida, Maprounea africana, Monachora arbuscula, Tedania ignis, Arenosclera spp., Amphimedon viridis, Polymastia janeirensis, Aplysina fulva, Pseudaxinella lunaecharta, Nelumbium speciosum and Mycale arenosa (extracts);

cloves (eugenol acetate and iso-eugenol);

Chrysthanemum boreale (sesquiterpenoid lactones);

Eucalyptus globolus, Punica granatum, Bocconia arborea, Syzygium brazzavillense, Syzygium guineense, Carthamus tinctorius), Ginkgo biloba, Mosla chinensis, Salvia officinalis, and Cinnamomum cassia (extracts);

Cryptolepis sanguinolenta (alkaloids, cryptolepine);

Chelidonium majus (alkaloids, berberine, coptisine);

Vitex agnus-castus (extract);

Cladonia substellata (usnic acid);

Fuligo septica, Tubifera microsperma (extract);

Mundulea monantha, Tephrosia linearis (flavonoids);

Lpomoea fistulosa (extract);

Pimenta dioica (essential oils);

Ratibida latipalearis, Teloxys graveolens, Dodonaea viscosa, Hypericum calycinum, Hyptis albida, Hyptis pectinata, Hyptis suaveolens and Hyptis verticillata (extracts);

Asteriscus graveolones (bisabolone hydroperoxides);

Derris scandens, Alnus rubra, Araliaceae family (extracts);

Vinca rosea, Australian tea tree oil, peppermint oil, sage oil, thyme oil, thymol, grapefruit oil, lemon oil, lime oil, orange oil, tangerine oil, cedarwood oil, pine oil and d-limonene, eugenol and Thuja orientalis (extracts);

Anacardium occidentale (phenolic lipids);

Oidiodendron tenuissimum (extract);

Acacia nilotica and Acacia farnesiana (polyphenol, tannin);

Teminalia alata and Mallotus phillipinensis (extracts);

Piectranthus grandidentatus (abientane diterpenoids);

Pumica granatum and Datura metel (extracts);

tea, Agave lecheguilla, Chamaesyce hirta, Baccharis glutinosa and Larrea tridentata (extracts);

Camelia sinensis and Euphorbia hirta (theaflavin, polyphenon

     60);

Tabernaemontana pandacaqui, Yucca shidigera, Hemistepa lyrata, Yougia japonica, Prunella vulgaris, Lamium amplexicaule, Juniperus chinensis, Ixeris dentata, Gnaphalium affine, Chelidonium majus, Spirea prunifolia, Erythronium japonicum, Taxus wallichiana, Ganoderma lucidum Drava nemorosa, Youngia capillaris, Equisetum arvense, Australiam Lavender, Black Seed, Catuaba casca, Cineole, Damiana, Dicranum scoparium, Eucalptus oil, Ginger, and Grape seed (extracts);

Neem seed, bark, and leaf extract;

Neem oil;

New Zealand Manuka extract;

Nicotiana tabacum extract;

olive leaf extract;

a-pinene and b-pinene extracts;

Rhubarb root extract;

Syringa vulgaris extract.

4. A process of claim 1 where the preferred essential oil or extract used to form stable microemulsions is selected from the following:

tea tree, peppermint, thyme, grapefruit, lemon, lime, orange, tangerine, cedarwood and pine, and orange peel extract d-limonene.

5. A process of claim 1 where the concentrated SQAC (68 to 72% in methanol) or the surfactant and the essential oil or extract are premixed to form a clear solution before adding demineralized water to form the microemulsion without the need for high intensity mixing.

6. A process of claim 1 where 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.

7. A process of claim 1 where 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.

8. A process of claim 1 where substantially no toxic chlorosilanol monomer remains in a partially polymerized solution of SQAC.

9. A process of claim 1 where the chlorosilanol is chloropropyltrimethoxysilane or chloropropyltriethoxysilane.

10. A process of claim 1 where the essential oil stabilized SQAC microemulsion contains from 3% to 40% essential oil based on active weight of anhydrous SQAC.

11. A process of claim 1 where 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.

12. A process of claim 1 where the resultant blend of the partially polymerized SQAC solution and the essential oil stabilized microemulsion form a water stable mixture that remains crystal clear, without separation (ringing), precipitation or further significant viscosity gain.

13. A process of claim 1 where the concentration of active SQAC in water during the partial polymerizations is greater than 5% to 12%.

14. A process of claim 1 where the temperature during the partial polymerization process is 100 to 100C, preferably 25C to 35C.

15. A process of claim 1 where the pH of the SQAC solution during the partial polymerization is pH 2 to pH 8 and preferably pH 3 to pH 7 and the pH is adjusted with solutions of hydrochloric acid or sodium hydroxide.

16. A process of claim 1 where the resultant essential oil stabilized, partially polymerized, crystal clear SQAC microemulsion is diluted to 0.01% to 5.0% active SQAC, contains substantially no monomeric chlorosilanol, 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.

17. A process of claim 1 where 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 (persistent), chemically bonded, antimicrobial barrier that lasts through many washes and provides up to 3 days of reduction or elimination of bacteria, viruses and fungi.

18. A process of claim 1 where 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 (persistent) chemically bonded antimicrobial barrier yet doesn'"'"'t interfere with the benefits of the base product design or its ability to foam, if designed as a foaming product.