Cyclosiloxane-substituted polysiloxane compounds, compositions containing the compounds and methods of use thereof

• US 9,175,141 B2
• Filed: 08/04/2011
• Issued: 11/03/2015
• Est. Priority Date: 08/05/2010
• Status: Expired due to Fees

• Current Assignee: Biofilm Ip, LLC
• Original Assignee: Biofilm Ip, LLC
• Inventors: Wray, Daniel X., Halsdorff, Michael B., De Armond, Robert L.
• Primary Examiner(s): Hartley, Michael G
• Assistant Examiner(s): CABRAL, ROBERT S
• Application Number:
  US13/198,658
• Publication Number:
  US 20120064022A1
• Time in Patent Office: 1,552 Days
• US Class Current: 1/1
• CPC Class Codes: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C08L 83/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08L83/10 takes precedence

Abstract

Provided herein are cyclosiloxane-substituted polysiloxane compounds, compositions that include the polysiloxane compounds, and methods for preparation and use of the polysiloxane compounds. Provided are mechanical lubricant compositions, hydraulic fluid compositions, anti-foam compositions, water repellant agent compositions, release agent compositions, personal care compositions, cosmetic compositions, household care compositions and drug delivery compositions that include one or more of the cyclosiloxane-substituted polysiloxane compounds provided herein.

Claims

1. A polysiloxane of Formula I:

2. The polysiloxane of claim 1, wherein one or more R⁷ is a cyclosiloxane selected from among cycloheptasiloxane, cyclohexasiloxane, cyclopentasiloxane, or cyclotetrasiloxane that is substituted with one or more moieties selected from among halogen, hydroxyl, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkyl, C₁-C₆ heteroalkyl, C₃-C₁₀ aryl, C₃-C₁₀ heteroaryl and C₃-C₁₀ aryl substituted with halogen or C₁-C₆ haloalkyl.

3. The polysiloxane of claim 1, wherein:

R¹ is an optionally substituted C₁-C₁₀ alkyl; and

R² is an optionally substituted C₁-C₁₀ alkyl.

4. The polysiloxane of claim 1, wherein R³ is selected from among optionally substituted C₁-C₁₀ alkyl, optionally substituted C₃-C₂₀ cycloalkyl, an optionally substituted C₃-C₆ cycloalkyl, and an optionally substituted cyclosiloxane having three or more Si atoms.

5. The polysiloxane of claim 1, wherein the R⁴ in each subunit a independently is selected from among optionally substituted C₁-C₁₀ alkyl, optionally substituted C₁-C₂₀ haloalkyl, optionally substituted C₆-C₂₀ aryl, optionally substituted C₆-C₂₀ heteroaryl, and an optionally substituted cyclosiloxane selected from among cycloheptasiloxane, cyclohexasiloxane, cyclopentasiloxane, or cyclotetrasiloxane.

6. The polysiloxane of claim 1, wherein one or more R⁴ is trifluoropropyl or an optionally substituted phenyl.

7. The polysiloxane of claim 1, wherein R⁴ in each subunit a is an optionally substituted cycloheptasiloxane, cyclohexasiloxane, cyclopentasiloxane, or cyclotetrasiloxane.

8. The polysiloxane of claim 1, wherein the R⁴ in at least two subunits a is a cycloheptasiloxane, cyclohexasiloxane, cyclopentasiloxane, or cyclotetrasiloxane, in which at least one Si atom is substituted with a moiety selected from among alkyl, haloalkyl, heteroalkyl, cycloalkyl, optionally substituted aryl, heteroaryl, non-aromatic heterocycle, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halo, carbonyl, thiocarbonyl, O-carbamyl, N carbamyl, O thiocarbamyl, N thiocarbamyl, C amido, N amido, S-sulfonamido, N sulfonamido, azido, diazo, imino, formylamino, fluoro, iodo, oxo, cyano, cyanato, carboxy, C trihalomethanesulfonyl, O carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, and amino, and mono- and di-substituted amino groups.

9. The polysiloxane of claim 1, wherein the R⁴ in at least two subunits a is a cycloheptasiloxane, cyclohexasiloxane, cyclopentasiloxane, or cyclotetrasiloxane, in which at least one Si atom is substituted with a moiety selected from among halogen, hydroxyl, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkyl, C₁-C₆ heteroalkyl, C₃-C₁₀ aryl, C₃-C₁₀ heteroaryl and C₃-C₁₀ aryl substituted with halogen or C₁-C₆ haloalkyl.

10. The polysiloxane of claim 1, wherein the R⁵ in each subunit a independently is selected from among optionally substituted C₁-C₁₀ alkyl, optionally substituted C₁-C₂₀ haloalkyl, optionally substituted C₆-C₂₀ aryl, optionally substituted C₆-C₂₀ heteroaryl, and butylated aryloxypropyl.

11. The polysiloxane of claim 1, wherein at least one R⁵ is butylated aryloxypropyl or trifluoropropyl or phenyl.

12. The polysiloxane of claim 1, wherein the R⁶ in each subunit b independently is selected from among optionally substituted C₁-C₁₀ alkyl, optionally substituted C₁-C₂₀ haloalkyl, optionally substituted C₆-C₂₀ aryl, optionally substituted C₆-C₂₀ heteroaryl, and butylated aryloxypropyl.

13. The polysiloxane of claim 1, wherein at least one R⁶ is trifluoropropyl or an optionally substituted phenyl or butylated aryloxypropyl.

14. The polysiloxane of claim 1, wherein:

R⁸ is an optionally substituted C₁-C₁₀ alkyl; and

R⁹ is an optionally substituted C₁-C₁₀ alkyl.

15. The polysiloxane of claim 1, wherein R¹⁰ is selected from among optionally substituted C₁-C₁₀ alkyl, optionally substituted C₃-C₂₀ cycloalkyl, and an optionally substituted cyclosiloxane having three or more Si atoms.

16. The polysiloxane of claim 1, wherein a is 1-5.

17. The polysiloxane of claim 1, wherein b is 1-5.

18. The polysiloxane of claim 1, wherein q is 2-15.

19. The polysiloxane of claim 1, wherein w 0-5.

20. The polysiloxane of claim 1, wherein y is 0-5.

21. The polysiloxane of claim 1, wherein:

at least one of R³ or R¹⁰ is a cyclosiloxane;

or

R³ and R¹⁰ each independently is a cyclosiloxane.

22. The polysiloxane of claim 1, wherein at least one of R⁵ and R⁶ is an aryl substituted with an alkyl or halogen.

23. The polysiloxane of claim 1, wherein:

R⁵ and R⁶ are C_I-C⁶ alkyl;

R⁴ is an optionally substituted aryl; and

R⁷ is an optionally substituted cycloheptasiloxane, cyclohexasiloxane, cyclopentasiloxane, or cyclotetrasiloxane.

24. The polysiloxane of claim 1, wherein the polysiloxane has a molecular weight in the range from about 200 to over 500,000.

25. The polysiloxane of claim 1, wherein the polysiloxane is thermally stable at temperatures above 150°

C.

26. The polysiloxane of claim 1, wherein the polysiloxane has a viscosity of up to about 150,000 centipoise when measured at 25°

C. at a shear rate of 100 sec<sup>−

1</sup>.

27. A composition, comprising:

a polysiloxane of claim 1; and

a carrier.

28. The composition of claim 27, wherein the viscosity of the polysiloxane is from 100 to 100,000 centipoise when measured at 25°

C. at a shear rate of 100 sec<sup>−

1</sup>.

29. The composition of claim 27 that is a lubricant composition, further comprising a solid lubricant selected from among a graphite, graphite fluoride, a buckyball, molybdenum disulfide, boron nitride, tungsten disulfide, hollow fullerene-like nanoparticles, metal dichalcogenides and polytetrafluoroethylene (PTFE) or a combination thereof, wherein:

the viscosity of the polysiloxane is from 10 cP to 150,000 cP when measured at 25°

C. at a shear rate of 100 sec<sup>−

1</sup>; and

the polysiloxane is present at from about 0.1% to 50% by weight of the composition;

or

the polysiloxane is present at from about 50% to 99% by weight of the composition.

30. The composition of claim 27 that is a hydraulic fluid, comprising:

from about 91.9 to 99.8% by weight polysiloxane;

from about 0.005 to 0.1% by weight anti-oxidant; and

from about 0.01 to 1.0% by weight anti-foaming agent.

31. The composition of claim 27 that is a water repellent composition, wherein:

the polysiloxane is present at a concentration between about 50% to 100% by weight of the composition;

or

the polysiloxane is present at a concentration between about 0.5 to 50% by weight of the composition; and

the composition further comprises an additive selected from among waxes, tertiary fatty amines, metallic soaps, fungicides, bactericides, and fire-retardant materials and mixtures thereof.

32. The composition of claim 27 that is a release agent composition, wherein:

the polysiloxane is present at a concentration between about 50% to 100% by weight of the composition;

or

the polysiloxane is present at a concentration between about 0.5 to 50% by weight of the composition; and

the composition further comprises a thickening agent.

33. The composition of claim 27 that is a personal care or cosmetic composition, wherein:

the polysiloxane is present at a concentration between about 50% to 100% by weight of the composition;

or

the polysiloxane is present at a concentration between about 0.5 to 50% by weight of the composition; and

the composition further comprises an additive selected from among emollients, moisturizers, humectants, pigments, dyes, pearlescent compounds, nacreous pigments, bismuth oxychloride coated mica, titanium dioxide coated mica, colorants, fragrances, biocides, preservatives, alpha hydroxy acids, antioxidants, anti-microbial agents, anti-fungal agents, antiperspirant agents, exfoliants, hormones, enzymes, medicinal compounds, vitamins, salts, electrolytes, alcohols, polyols, polypropylene glycol, polyisobutene, polyoxyethylene, behenic acid, behenyl, sugar-alcohols, absorbing agents for ultraviolet radiation, botanical extracts, surfactants, silicone oils, organic oils, waxes, alkaline or acidic or buffering agents, film formers, thickening agents, hyaluronic acid, fumed silica, hydrated silica, talc, kaolin, starch, modified starch, mica, nylon, clay, bentonite, organo-modified clays and combinations thereof.

34. The composition of claim 33, wherein the personal care or cosmetic composition is formulated as a product selected from among deodorants, antiperspirants, insect repellants, anesthetics, skin conditioners, skin lotions, skin moisturizers, skin toners, skin sanitizers, skin cleansing compositions, skin soothing and lubricating compositions, sunscreen, anti-aging products, concealer products, soaps, foaming bath products, shower gels, cleansing products, shampoos, hair conditioners, hair styling gels, hair anti-dandruff compositions, hair growth promoter compositions, hair colorant compositions, hair bleaching agent compositions, hair anti-frizzing agent compositions, hair shining compositions, hair relaxer compositions, mousses, styling gels, hair sprays, hair dyes, hair waving products, hair straightening products, shaving product compositions, personal lubricant compositions, spermicidal gel compositions, manicure products, nail polish, nail polish remover, nail creams and lotions, cuticle softeners, color cosmetics, lipsticks, lip balms, foundations, face powders, eye liners, eye shadows, blushes, makeup, mascaras and color cosmetic removers.

35. The composition of claim 27, further comprising a fragrance or fragrance releasing compound or fragrant material or a combination thereof.

36. The household care composition of claim 35 that is formulated as a product selected from among laundry detergents and softeners, fabric sizing agents, dish and hard surface detergents, hard surface sanitizing agents, all purpose kitchen cleaner and disinfectants, toilet, tub and tile cleaning and disinfectant preparations, polishing compositions, waxes and polishing compositions for treating wood, furniture, automobiles or boats, pesticide preparations, static control preparations, air deodorants/fresheners, and rug and upholstery shampoos, cleaners and deodorizers.

37. The composition of claim 27 that is a drug delivery system for topical application of an active agent to the skin, further comprising one or more of a skin-penetration enhancer, accelerant, adjuvant and sorption promoter and combinations thereof.

38. The composition of claim 27 that is a personal lubricant composition, the composition further comprising a linear or cyclic silicone fluid or mixtures thereof.

39. A polysiloxane of Formula I: