US 20120196832A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0196832 A1 LURA (43) Pub. Date: Aug. 2, 2012 (54) SUBSTITUTED POLYALKOXYSILOXANE Publication Classification COMPOSITIONS AND METHODS OF USE (51) Int. Cl. A6II 3/695 (2006.01) (75) Inventor: LEONARD WILLIAM LURIA, AOIN 55/10 (2006.01) Tampa, FL (US) AOIP I/00 (2006.01) A6IP 7/10 (2006.01) (73) Assignee: ONE UNLIMITED, INC., Tampa, A6IP 7/02 (2006.01) FL (US) C07F 7/02 (2006.01) A6IP 700 (2006.01) (21) Appl. No.: 13/446,064 (52) U.S. Cl. ........................................... 514/63:556/449 (57) ABSTRACT (22) Filed: Apr. 13, 2012 Linear polydialkoxysiloxanes with 2-8 polymeric units have been reacted with alcohols by a transetherification reaction to Related U.S. Application Data provide hydrophilic and water soluble silicone products. The glycerol Substituted siloxanes in particular are effective in (63) Continuation-in-part of application No. 12/701,312, topically treating skin lesions such as radiation burns. Com filed on Feb. 5, 2010, now Pat. No. 8,158,740, which is positions including the Substituted polydialkoxysiloxane a continuation-in-part of application No. 1 1/542,996, products inhibit biofilm formation when used as coatings on filed on Oct. 4, 2006, now Pat. No. 7,687,592. hard Surfaces. Patent Application Publication Aug. 2, 2012 Sheet 1 of 2 US 2012/0196832 A1 pêssê.ippeeeueApog 92 +-0/ 06 08 09 09 O#7 09 OZ 0|| 0 ÁeG/XZu ÁeG/XI.S p?d?QUuÐUue}}[,] }ueue Aodu% Patent Application Publication Aug. 2, 2012 Sheet 2 of 2 US 2012/0196832 A1 Fish Tank % Dilution of ALLENCONE FIG 2 US 2012/0196.832 A1 Aug. 2, 2012 SUBSTITUTED POLYALKOXYSILOXANE characterized and monitored by light scattering. Despite the COMPOSITIONS AND METHODS OF USE inherent instability of most emulsions, many cosmetic prod ucts have been Successfully based on emulsification. Exten sive experimentation in selecting the optimal Surfactant and 0001. This is a continuation-in-part of co-pending U.S. in confirming the emulsion stability of the product over an patent application Ser. No. 12/701,312, filed Feb. 5, 2010, appropriate time period is usually necessary. now U.S. Pat. No. 8,158,740, which is a continuation-in-part 0013 Efforts have also been made to develop hydrophobic of U.S. patent application Ser. No. 1 1/542,996, filed Oct. 4, silicones; for example, a reaction between alcohols and 2006, now U.S. Pat. No. 7,687,592, the disclosures of which alkoxysiloxanes is typically used to introduce hydrophobic are hereby incorporated by reference in their entirety, includ properties. Wood contains hydroxyl groups and, in the form ing all figures, tables and amino acid or nucleic acid of a finely divided flour, has been reacted with oligoethoxysi Sequences. loxanes to produce a solid material with low water affinity and compatibility with hydrocarbon polymers. BACKGROUND OF THE INVENTION 0014 Personal care products rely heavily on the use of 0002 1. Field of the Invention silicones with at least half of the U.S. market for silicones 0003. The invention relates to the preparation and use of used in antiperspirants and deodorants. Cosmetics tradition modified polydialkoxysiloxanes as protective barriers and as ally use formulations that include octamethylcyclotetrasilox treatments for skin damage. ane, also known as D4, in topical skin creams because of its 0004 2. Description of Background Art lack of toxicity and low cost. A related compound, D5 or 0005 Silicone fluids having remarkable versatility and decamethylcyclopentasiloxane has to Some extent replaced new uses are continually being developed and sought. The use of D4, which recently has raised concerns related to name “silicone' denotes a polymer with the formula shown in bioaccumulation, particularly in marine environments. I: Despite these concerns, the general consensus among manu facturers and Suppliers appears to be that the cyclic silicones are safe. In a recent study, the Canadian government deter mined that siloxane D5 is safe for use in personal care prod (R, SiO4 - n), I ucts such as topical skin creams, antiperspirants and hair products. These siloxanes are used in amounts varying from 0.01% in skin cleansers to up to 0.65% in hair conditioners 0006 where n is between 0 and 3 m is 2 or larger and R is and hair grooming products. The market in 2009 for cyclic typically alkyl. The term “silicone' arose from the work of methylsiloxanes was 104 million pounds (Chem & Engineer early investigators who erroneously assumed that oxygen was ing News, vol. 89, No. 18, May 2, 2011). bound to silicone by a double bond similar to that in ketones. 0007. The simplest silicones are polydimethyl siloxanes SUMMARY OF THE INVENTION having the structure: 0015 The invention concerns the use of linear polyalkoxy CH3 Si-O-Si-O-Si-CH II siloxanes which have been chemically modified by a 0008. The repeating unit of the polymer, Si-O. , the transetherification reaction with alcohols to produce poly dimethylsiloxane unit, in the dimethoxysiloxane unit shown meric silicon products with hydrophilic side groups on a in II above is referred to as the D unit so that the structure silicone backbone. The starting material is a linear dialkoxy above is often referred to as MDM. Structure II is shown as siloxane typically having 2-15 polymer units. Polydiethoxy linear, although silicones can have branched points referred to or polydimethoxy silicones are reacted with a primary or as T and Q groups. Branch points form a network and intro secondary alcohol through a transetherification exchange. duce rigidity into the structure. Compositions comprising silicone products with hydrophilic 0009. The methyl group in I can be substituted by other Substitutions show Surprising therapeutic effectiveness in groups, most commonly phenyl, vinyl and hydrogen. The treatment of burns, skin infections and disease produced Substitutions, branching and molecular weight of the silicone lesions. Reaction of diethoxy or dimethoxy polysiloxanes polymers determine properties and use. with alcohols using the described transetherification reaction 0010 Low molecular weight siloxanes are used as mono produces novel polysiloxane compositions which can be cus mers and terminators in the polymerization of higher molecu tomized for specific applications. lar weight silicones. 0016. The reaction with alkoxy groups requires a free 0011. In order to provide water soluble silicones, several alcohol group. The reaction is reversible and in a closed methods to chemically modify the silicone structure in order system would reach equilibrium with all species present at to circumvent the need for emulsification have been tested. concentrations not significantly different from each other. Some commercially available compounds include dimethi When methoxy and ethoxy silicones are substituted with cone polyols (SILTECH), cyclomethicones (CLEARDO) alcohols having larger or hindered groups the equilibrium and polyesters (ZENITECH). may be forced to completion by removing methanol or etha 0012 Liquid silicone polymers, such as polydimethoxysi nol as the more Volatile products. loxane and polydiethoxysiloxane, have a very low solubility 0017. The reaction may be carried out on a practical scale in water or aqueous solutions. In order to accommodate this by mixing a polydialkoxysiloxane with the alcohol to be property, slightly soluble siloxane compounds can be emul coupled and heating to about 200°F. for 20 hr or more. After sified with Surfactants to form aqueous emulsions, which are cooling to room temperature, a water Soluble portion can be stable for long periods up to several months. Such emulsions obtained by mixing with water and recovering water soluble consist of a Suspension of very Small droplets of liquid sili product by centrifugation, decantation or filtration. The prod cone that may be visible microscopically, but are more easily uct is a heterogeneous composition of predominately linear US 2012/0196.832 A1 Aug. 2, 2012 Substituted polydialkoxysiloxane polymers. The polymers promote skinhealing and regeneration when topically admin have 8-15 units and are substituted with the alcohol to varying istered to areas in the ear canal in treatment of chronically degrees along the silicone backbone. The number of polymer draining ear. units will depend on the starting material which is usually a 0024. A particularly important medical treatment applica dialkoxy siloxane with 8-15 polymer units. If separation of tion is the healing effect of some of the hydrophilic substi the products is desired, they can be fractionated by high tuted polydialkoxysiloxanes on radiation burn injuries. Skin performance liquid chromatography (HPLC) or used without irritation and burning is common in cases where patients fractionation in cosmetic or therapeutic preparations. The undergo radiation treatment associated with certain cancers. major products appear to result from replacement of about Topical application of glycerol Substituted polydialkoxysi 30-70% of the alkoxy groups on the siloxane backbone with lane compositions relieves pain and accelerates healing com a selected alcohol. pared to treatment with commonly used burn or cortisone 0018 Silicones substituted with glycerol or BRONOPOL ointments. The glycerol polysiloxanes can be used in combi or combinations of the two are typically at least 5% water nation with topical antibacterials; for example, when applied soluble and when applied in aqueous Solution to the skin leave with Nu-3 (butyl-phosphate-5'-thymidine-3'-phosphate), to a very thin adherent coating. The film is nonwettable and treat burn wound infections from Pseudomonas aeruginosa, provides an exceptionally smooth texture which is retained there was only a slight decrease in antibacterial effectiveness through repeated exposures to water. The water solubility of of Nu-3. Nubiotics are a new class of antibiotic agents with Such modified silicones might Suggest that topical prepara broad spectrum activity. tions applied to skin are readily removed by washing but Surprisingly it appears that hydrophobic interactions between Definitions and Terms the polysiloxane and the skin impart strong adherence.