Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
  • C09K3/185—Thawing materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

• the present invention relates to a process for coating a water-impermeable surface with a silicone composition to facilitate the removal of frozen water therefrom.
• frozen water such as ice, snow, sleet and frost
• human-made structures that are exposed to weather, such as buildings, ships, aircraft, trailers, automobiles, cables, antennae, bridges, wires, signs, storage tanks and traffic signals
• weather such as buildings, ships, aircraft, trailers, automobiles, cables, antennae, bridges, wires, signs, storage tanks and traffic signals
• freezing water onto a substrate is also diliberately caused by humans, such as in the formation of ice pieces, such as blocks, cakes and cylinders. Its removal from the substrate in these instances is necessitated by convenience and/or economic considerations.
• the present invention relates to a method for treating a water-impermeable surface to facilitate the release of frozen water therefrom, said method comprising applying to said water-impermeable surface a coating composition obtained by mixing components consisting essentially of (A) 15 to 70 parts by weight of a carboxy-functional siloxane fluid having the formula
• x has an average value of from 25 to 400
• ⁇ has an average value of from 0 to 25, there being an average of at least two carboxy-functional radicals per- molecule of said siloxane fluid
• B 0.1 to 5 parts by weight of a titanate having the formula Ti(OR")4 wherein each R" is an aliphatic radical or a hydroxylated aliphatic radical having 1 to 12 carbon atoms and (C) 25 to 80 parts by weight of a volatile diluent, the total of (A) + (B) + (C) being 100 parts by weight, and thereafter drying the applied coating composition.
• One of the components that is essential for preparing the above compositions is a carboxy-functional siloxane fluid of the general formula
• R (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] x [(CH 3 )RSiO] y Si(CH 3 ) 2 R'
• R can be any monovalent radical containing a -COOH group and which is attached to the silicon atom by a silicon-to-carbon (Si-C) bond. So far as is known at this time, these two characteristics are the only essential ones for this component.
• R is a radical having the formula HOOC-Q- wherein Q is a divalent linking group attached to the silicon atom by an Si-C bond and is composed of carbon and hydrogen atoms, or carbon, hydrogen and sulfur atoms, there being from 2 to 10 carbon atoms in Q, and any sulfur atoms present are in the form of thioether linkages.
• R radicals include the HOOCCH 2 CH 2 -, HOOCCH(CH 3 )CH 2 -, HOOC(CH 2 ) 6 , HOOC(CH 2 ) 18 -, HOOCCH 2 SCH 2 CH 2 -, HOOCCH 2 OCH 2 CH 2 - and HOOC-C 6 H 4 -S-C 6 H 4 -.
• the number of dimethylsiloxane units in the carboxy-functional siloxane is defined by x in the above formula and can range from 25 to 400 , but preferably ranges from 75 to 125.
• the number of (CH 3 )RSiO units is defined by y in the above formula and can range from 0 to 25, and preferably ranges from 0 to 10.
• the carboxy-functional fluid may be endblocked with trimethylsiloxane units (i.e. R' is a methyl radical) and/or carboxy-functional dimethylsiloxane units (i.e. R' is a carboxy-functional radical).
• the fluid is endblocked with trimethylsiloxane units and ⁇ ranges from 2 to 10. In any case there must be an average of at least two carboxy-functional radicals per molecule of the siloxane fluid.
• the carboxy-functional radicals may or may not all be identical; conveniently they are.
• the viscosity of the carboxy-functional siloxane is not critical and any such fluid siloxane can be employed. Obviously, the more viscous fluids can be more difficult to apply to a substrate, but this can be compensated for, to a large degree, by the amount of volatile diluent that is used.
• the R" radical can be any aliphatic hydrocarbon radical or any hydroxylated aliphatic hydrocarbon radical containing from 1 to 12 carbon atoms.
• R" can be, for example, a methyl, ethyl, isopropyl, butyl, 2-ethylhexyl, decyl, dodecyl, octylene glycolyl, ethylene glycolyl or hexylene glycolyl radical.
• the R" groups can be the same or mixed. Tetraisopropyl titanate is preferred.
• a final essential component for preparing the above-described coating compositions is a volatile diluent.
• volatile it is meant that the diluent evaporates sufficiently rapidly, under the particular drying conditions that are used in the method of this invention, that a non-lumpy coating is obtained on the water-impermeable surface.
• diluent it is meant a material that serves to disperse the carboxy-functional siloxane fluid in a homogeneous manner, such as in suspension, and preferably, in solution.
• volatile diluents that are suitable for use in the method of this invention include benzene, toluene, xylene, naphtha mineral spirits, petroleum ethers, pentane, hexane, heptane, cyclohexane, perchloroethylene, trichloroethane and methylene chloride.
• the volatile diluent has little or no affinity for water.
• Hexane is a particularly effective diluent to use when the composition is applied and dried at temperatures ranging from 10° to 30°C.
• a more- or less-volatile diluent may be desired.
• More than one volatile diluent may be used if desired.
• the coating composition that is used in the method of this invention may contain non-essential components provided its premium release characteristics toward frozen water is not significantly decreased.
• Non-essential components encompass colorants, stabilizers, propellents and other adjuvants well-known in the coatings art.
• the volatile diluent accounts for from 25 to 80 parts
• the siloxane fluid accounts for from 15 to 70 parts
• the titanate accounts for from 0.1 to 5 parts, preferably from 0.25 to 0.75 parts, by weight.
• the gel time, and hence the pot life, of a curable siloxane composition whose curing reaction is catalyzed by a titanate catalyst is decreased as the concentration of titanate is increased.
• the proper amount of any particular titanate (B) that is mixed with any particular carboxy-functional siloxane fluid (A) can be determined by simple experimentation so as to avoid undesirable gelation in the coating composition.
• the best method for preparing the compositions that are used in the method of this invention is to first mix the titanate in a portion of the volatile diluent and the carboxy-functional siloxane in the balance of the volatile diluent and then mix the two solutions and any other ingredients.
• Other orders of mixing can be used but tend to cause the formation of undesirable gels before the coating composition can be applied to a substrate if they involve mixing undiluted titanate with undiluted carboxy-functional siloxane fluid.
• compositions in the process of this invention can be accomplished in a relatively simple and straightforward manner.
• the process involves applying the composition to the water-impermeable surface and then drying the applied composition. In this manner it is believed that the surface is altered in some manner, such as by the deposition of a film thereon, whereby the release of the frozen water therefrom is facilitated.
• the compositions can be applied to the surface by any manner convenient to the user such as by spraying, brushing, dipping, flooding or wiping the composition thereon.
• drying can be accomplished in any convenient manner as by simple air-drying (e.g. standing), by blowing air or other dry gas over the surface, or by heating to speed up the drying process.
• the amount of the coating composition that is applied to the surface is not critical except in so far as enough must be applied to achieve the degree of improved release of frozen water from the surface that is desired. Obviously there will be a maximum amount which can be applied beyond which no additional benefit can be seen and to use more would be wasteful.
• the method of this invention is useful for treating any water-impermeable substrate, such as metallic, painted, rubber, glass, porcelain and plastic-coated surfaces; however, it is most useful for treating surfaces that are wetted by water and particularly metallic surfaces such as aluminum, copper and ferrous surfaces, such as iron, steel and stainless steel.
• An ice-releasing coating composition was prepared by mixing 0.15 grams of tetraisopropyl titanate with 40 grams of hexane and mixing with the resulting solution 20 grams of a carboxy-functional siloxane fluid having the formula
• a stainless steel spatula was immersed into the coating composition, withdrawn and allowed to dry at room temperature. Water droplets were placed on the thus-treated spatula and on an untreated stainless steel spatula and the droplet-bearing spatulas were placed in a freezer at -20°F (-29°C) to freeze the droplets of water. The frozen droplets were easily slid from the spatula that had been treated by the process of this invention but not from the untreated spatula.
• An ice-releasing coating composition was prepared by mixing 112.5 grams of tetraisopropyl titanate with 3750 grams of hexane, to form a first solution, and mixing 7500 grams of the carboxy-functional siloxane fluid disclosed in Example 1 with 3750 grams of hexane to form a second solution and thereafter mixing the two solutions.
• Example 3 Approximately three weeks after being coated the four panels experienced a snowstorm having both wet and dry snow. The panel that had been coated four times remained ice- and snow-free during the snowstorm, but experienced a slight accumulation of snow during another snowstorm 11 days later. The remaining three panels having lesser amounts of coating composition did not remain free of ice and/or snow.
• Example 3 The panel that had been coated four times remained ice- and snow-free during the snowstorm, but experienced a slight accumulation of snow during another snowstorm 11 days later. The remaining three panels having lesser amounts of coating composition did not remain free of ice and/or snow.
• Aluminum panels, 0.25 inches thick and approximately 6 inches long and 2.5 inches wide were scoured with cleanser and water until they were uniformly wetted with water and were then air-dried.
• One panel was rubbed with a paper towel saturated with the coating composition of Example 2.
• Another panel was rubbed with a paper towel saturated with the neat carboxy-functional siloxane fluid described in Example 1.
• Another panel was rubbed with a paper towel saturated with a prior art ice-releasing composition obtained by mixing 20.8 parts of isopropyl alcohol, 20 parts of hydroxyl-endblocked polydimethylsiloxane having a viscosity in the range of 35 to 50 centistokes at 25°C, 1.6 parts of (CH3O) 2 CH 3 Si(CH 2 ) 3 NH(CH 2 ) 2 NH 2 and 1.2 parts of acetic acid.
• the three treated panels were immobilized in a cold box at -13°C and a 0.25 inch thick circular stainless steel washer having an attached wire lanyard and a circular hole of 1 square inch area was placed on the treated surface of each panel.
• a 0.25 inch thick circular stainless steel washer having an attached wire lanyard and a circular hole of 1 square inch area was placed on the treated surface of each panel.
• the panels and washers were thoroughly chilled water was poured into each cylinder defined by the washer and the treated panel. After the water had froze the force necessary to pull the ice cylinder from the treated panels was measured by leading the wire lanyard in a direction parallel to the surface of the panel, through a small hole in the wall of the cold box to a spring balance located outside of the cold box and pulling on the spring balance. Release force was measured in grams and was converted to'newtons for this disclosure by multiplying by 0.009806650 and rounding off.
• the panel that had been treated by the process of this invention released ice under a force of 300 ⁇ 100 grams (2.9 ⁇ 1.0 newtons).
• the panel that had been treated with the neat (i.e. solvent-free and titanate-free) carboxy-functional siloxane fluid release ice under a force of 900 grams (8.8 newtons).
• the panel that had been treated with the prior art ice-releasing composition released ice under a force of about 750 grams (7.4 newtons).
• a clean untreated panel releases ice under a force of approximately 115 pounds (513 newtons).
• the superior ice-releasing behavior of an aluminum surface that has been treated by the method of this invention is evident, being more than 2.5 times better than the prior art performance.
• volatile diluents other than hexane, which are known to be useful in connection with carboxy-functional silicone fluids would also be useful in the present invention.
• Such alternative volatile diluents would include those listed above as specific examples of useful volatile diluents.
• titanates of the general formula Ti(OR") 4 would be useful where R" is a hydroxylated aliphatic hydrocarbon radical having from 1 to 12 inclusive carbon atoms. Such titanates are usually interchangeable with similar results normally achieved in the field of silicone chemistry.
• any of the carboxyfunctional silicones described above would be expected to give similar results when substituted for the fluid of Example 1.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Polymers & Plastics (AREA)
• Combustion & Propulsion (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

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• 1979
  • 1979-10-31 US US06/089,438 patent/US4271215A/en not_active Expired - Lifetime
• 1980
  • 1980-09-08 JP JP55502452A patent/JPS6410551B2/ja not_active Expired
  • 1980-09-08 WO PCT/US1980/001158 patent/WO1981001256A1/en unknown
  • 1980-09-10 CA CA000360011A patent/CA1151477A/en not_active Expired
  • 1980-09-26 EP EP80303394A patent/EP0028880B1/en not_active Expired
  • 1980-09-26 DE DE8080303394T patent/DE3063522D1/de not_active Expired
• 1981
  • 1981-06-30 DK DK290081A patent/DK290081A/da not_active Application Discontinuation

Patent Citations (8)

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