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WO2016090468A1 - Compositions de revêtement, procédé de préparation associé et utilisation associée - Google Patents

Compositions de revêtement, procédé de préparation associé et utilisation associée Download PDF

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Publication number
WO2016090468A1
WO2016090468A1 PCT/CA2015/051260 CA2015051260W WO2016090468A1 WO 2016090468 A1 WO2016090468 A1 WO 2016090468A1 CA 2015051260 W CA2015051260 W CA 2015051260W WO 2016090468 A1 WO2016090468 A1 WO 2016090468A1
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Prior art keywords
coating composition
silicone resin
methoxy
functional
functional silicone
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English (en)
Inventor
Michel Couturier
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Bio-Innox Anticorrosion Inc
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Bio-Innox Anticorrosion Inc
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    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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

  • Ice accretion on various structures and vehicles exposed to the Nordic elements is problematic and can lead to catastrophic failures.
  • windmill blades will often build-up ice that results in a lower efficiency energy output.
  • some windmill manufacturers have designed active de-icing systems where electricity generated heat is deployed within the blades. In this context, the energy required for this de-icing procedure is compounded by the loss of energy of the non-operational windmill.
  • a room temperature curable coating under the trademark Wearlon a water- based amide type epoxy, comprised of a fatty acid derived polyethylenepolyamine, a bisphenol- A derived epoxy resin, a linear end functional polydiorganosiloxane and a surfactant is not as efficient at shedding ice as addition cured silicone resins.
  • certain matrices containing 20% of a liquid freezing point depressant magnesium chloride, propylene glycol 1 : 1 have been reported, however by virtue of its leachable nature in the mode of action, the freezing point depressant is sacrificial.
  • the curing of certain coatings is dependant on the water from atmospheric moisture, and the level of humidity determines the curing rate, which may cause drawbacks in an open environment.
  • a coating composition comprising: i) an epoxy resin;
  • a method for preparing the coating composition as described herein comprising crosslinking an epoxy resin with an amino-functional silicone resin and a methoxy-functional silicone resin in the presence of an end functional polydimethylsiloxane.
  • articles surface-coated with composition as defined herein to substantially reduce or eliminate ice accretion on said surface.
  • a method for reducing ice-adhesion to a substrate comprising preparing the ice coating composition as described herein, and applying said coating composition to said substrate prior to the curing of said composition.
  • a coating composition resulting from a blend comprising a), b) and c) wherein:
  • a) is a blend of i) an epoxy resin and iv) and an end functional polydimethylsiloxane
  • b) is a blend of ii) an amino-functional silicone resin and iii) a methoxy-functional silicone resin; c) is at least one catalyst.
  • an ice shedding coating composition resulting from a blend comprising a), b) and c) wherein: a) is a blend of i) an epoxy resin and iv) and an end functional polydimethylsiloxane; b) is a blend of ii) an amino-functional silicone resin and iii) a methoxy-functional silicone resin; c) is at least one catalyst and optionally additional agents.
  • a coating composition resulting from a blend comprising a), b) and c) wherein:
  • a) is a blend of i) an epoxy resin and iv) and an end functional polydimethylsiloxane
  • b) is a blend of ii) an amino-functional silicone resin and iii) a methoxy-functional silicone resin; c) is at least one catalyst in a), b) or both.
  • a coating composition resulting from a blend comprising a), b) and c) wherein:
  • a) is a blend of i) an epoxy resin and iv) and an end functional polydimethylsiloxane
  • b) is a blend of ii) an amino-functional silicone resin and iii) a methoxy-functional silicone resin; c) is at least one catalyst in a), b) or both and optionally additional agents.
  • a coating composition resulting from a blend comprising a), b), c) and optionally d) wherein:
  • a) is a blend of i) an epoxy resin and iv) and an end functional polydimethylsiloxane
  • b) is a blend of ii) an amino-functional silicone resin and iii) a methoxy-functional silicone resin; c) is at least one catalyst in a), b) or both;
  • HALS hindered amine light stabilizer
  • a coating composition resulting from a blend comprising a) and b) wherein:
  • a) is a blend of i) an epoxy resin, iv) an end functional polydimethylsiloxane and optionally a titanium catalyst;
  • b) is a blend of ii) an amino-functional silicone resin, iii) a methoxy-functional silicone resin and optionally an organotin catalyst.
  • a coating composition resulting from a blend comprising a) and b) wherein:
  • a) is a blend of i) an epoxy resin, iv) an end functional polydimethylsiloxane and a titanium catalyst;
  • b) is a blend of ii) an amino-functional silicone resin, iii) a methoxy -functional silicone resin and an organotin catalyst ;
  • a coating composition comprising:
  • a) is a blend of i) an epoxy resin and iv) an end functional polydimethylsiloxane; b) is a blend of ii) an amino-functional silicone resin and iii) a methoxy-functional silicone resin; c) at least one catalyst;
  • composition optionally comprising d) an hindered amine light stabilizer.
  • a coating composition comprising:
  • a) is a blend of i) an epoxy resin iv) an end functional polydimethylsiloxane and a titanium catalyst; b) is a blend of ii) an amino-functional silicone resin, iii) a methoxy-functional silicone resin and an organotin catalyst;
  • composition optionally comprising d) and optionally additional agents.
  • a coating composition comprising:
  • a) is a blend of i) an epoxy resin iv) an end functional polydimethylsiloxane and a titanium catalyst; b) is a blend of ii) an amino-functional silicone resin, iii) a methoxy-functional silicone resin and an organotin catalyst;
  • composition optionally comprising d) an hindered amine light stabilizer.
  • a method for preparing a coating composition comprising:
  • a method for preparing a coating composition comprising:
  • a method for preparing a coating composition comprising:
  • a method for preparing a coating composition comprising:
  • said catalyst of any blend of i) and iv) described herein is a titanium catalyst and said catalyst of any blend of ii) and iii) described herein is an organotin catalyst. In one embodiment, said catalyst of any blend of i) and iv) described herein is diisopropoxy titanium bis(acetylacetonate).
  • said catalyst of any blend of ii) and iii) described herein is dibutyltin dilaurate.
  • said catalyst of any blend of i) and iv) described herein is diisopropoxy titanium bis(acetylacetonate) and said catalyst of any blend of ii) and iii) described herein is dibutyltin dilaurate.
  • said catalyst of any blend of i), ii), iii) and iv) and optionally any additional agent is diisopropoxy titanium bis(acetylacetonate).
  • the coating composition herein may be characterized as an ice shedding coating composition.
  • the present disclosure provides new epoxy-polysiloxane polymer coating compositions that render surfaces on which they are applied to slippery such that ice accretion and accumulation is diminished.
  • the coatings of the present disclosure are of the thermoset plastic type.
  • Thermoset plastics contain polymers that cross-link together during the curing process to form an irreversible chemical bond.
  • Suitable epoxy resins useful in forming coating embodiments of the present disclosure may include non-aromatic epoxy resins comprising more than one epoxy group per molecule as glycidyl ethers.
  • the non-aromatic epoxide resin has two 1,2 epoxide group per molecule.
  • the epoxide has an epoxide equivalent weight of 100 to 5,000.
  • a preferred epoxy resins includes hydrogenated bisphenol A-type epoxy resin such as Eponex 1510 and 1513 from Hexion, Epalloy 5000 and 5001 from Emerald Performance Materials, YDH 3000 from Epotec and Denacol EX-252 from ChemteX.
  • the epoxide equivalent weight of preferred resins is in the range of from about 100 to 2000. Typically, the epoxide equivalent weight is 100 to about 500. According to various embodiments, the icephobic coating composition may comprise 15% to 50% by weight of the epoxide resin, relative to the total weight of the solids of the composition and in other embodiments from 20% to 30% by weight of epoxy resin. According to one embodiment the coating composition may comprise about 25% by weight of epoxide resin.
  • the epoxy resin may further comprise epoxy functional reactive modifiers such as TTA21 from Phibro and CER 4221 from Achiwell, Epodyl 757 from Air Products, Heloxy 107 from Hexion, Erisys GE-22 from Emerald Performance Materials.
  • Epoxy functional reactive modifiers propylene glycol diepoxide resins such as D.E.R 732 from Dow and triglycidyl ether of castor oil such as Erisys GE-35 from Emerald Performance Materials may be used in the formulation of an icephobic coating.
  • Epoxypropoxypropyl terminated polydimethylsiloxanes (DMS-09 and 11), (epoxypropoxypropylmethylsiloxane) - (dimethylsiloxane) Copolymers (EMS-622), (epoxypropoxypropyl)dimethoxysilyl terminated polydimethylsiloxanes (DMS-EX21), (epoxycyclohexylethylmethylsiloxane) - dimethylsiloxane copolymers (ECMS-series), all from Gelest, are examples of epoxy functional polydimethylsiloxanes that may be comprised in the coating formulation.
  • a polysiloxane is a silicon containing compound containing repeating (Si-O) units.
  • a silane is a silicon-containing compound, which does not contain repeating (Si-O) units.
  • Silicone resins are polymers containing siloxane units independently selected from (R3S1O1/2), (R 2 Si0 2 / 2 ), (RSi0 3 / 2 ), or (Si0 4/2 ) siloxy units, where R may be any monovalent organic group.
  • the siloxy units are commonly referred to as M, D, T, and Q units respectively. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures.
  • a silicone resin contains at least one T unit and/or at least one Q unit.
  • a silicone resin contains two or more T units and/or Q units.
  • the R groups are Methyl in (1), the R groups are Methyl and Phenyl, or Methyl and 3-Aminopropyl in (2), the R group is Phenyl or 3-Aminopropyl in (3) with an high amine content of about 250 g/NH and less than 2% of methoxy radicals.
  • the icephobic coating composition may comprise 20% to 60% by weight of the amine-functional silicone resin, relative to the total weight of the solids of the composition and in other embodiments from 25% to 50% by weight of amine-functional silicone resin.
  • the coating composition may comprise about 40% by weight of amine-functional silicone resin. Examples of such resin include DC 3055 from Dow Corning, and Silres HP 2000 from Wacker.
  • the R' groups are Methoxy, Methyl and Phenyl, with a methoxy content of about 15% and a molecular weight in the range of from about 1200 to about 1900;
  • the coating composition may comprise 15% to 50% by weight of the methoxy-functional silicone resin, relative to the total weight of the solids of the composition, and in other embodiments from 20% to 30% by weight of methoxy-functional silicone resin. According to one embodiment the coating composition may comprise about 25% by weight of methoxy-functional silicone resin.
  • Preferred methoxy-functional silicone resins include, Silres IC 232, Silres SY 231, Silres IC 368, Silres IC 678 all from Wacker, and DC 3037, DC 3074 from Dow Corning. Hydroxyl-functional silicone resins such as Silres SY 300 and Silres IC 836 may be used as replacement of methoxy- functional silicone resins.
  • the coating composition comprises end-functional polydimethylsiloxanes having the formula:
  • R 5 is an alkyl up to four carbon atoms, a hydroxyl group, a 3-aminopropyl, a 3- hydroxypropyl or a 3-(hydroxyethoxy)propyl;
  • P6 is a hydroxyl group, a 3-aminopropyl, a 3- hydroxypropyl or a 3 -(hydroxy ethoxy)propyl and where n is selected so that the molecular weight for the polysiloxane is 400 to 110,000.
  • Preferred end functional polysiloxanes includes mono and/or bis silanol-terminated polydimethylsiloxanes (i,e. one of R5 or R6 is -OH or both of R5 and R6 are -OH) with a viscosity of about 1000 cSt.
  • the viscosity of the end functional polydimethylsiloxane is about 15 cPs to 50,000 cPs, and in other embodiments from 100 cPs to 10000 cPs. According to one embodiment, the viscosity of the end functional polydimethylsiloxane is about 1000 cPs.
  • the coating composition may comprise 1% to 20% by weight of the end functional polydimethylsiloxane, relative to the total weight of the solids of the composition, and in other embodiments from 5% to 15% by weight of end functional polydimethylsiloxane. According to one embodiment the coating composition may comprise about 8%) by weight of end functional polydimethylsiloxane.
  • silanol-terminated polydimethylsiloxane examples include DMS-S, PDS and FMS series from Gelest and Andisil OH and MOH series from Speciality Silicones.
  • Carbinol-terminated such as DMS-C, DBE-C, DBP-C, CMS, MCR-C and MCS-C series from Gelest may also be suitable end-functional polysiloxanes.
  • catalysts may be added to accelerate curing rate of the composition.
  • Catalysts may be one or more organometallic derivatives of titanium, tin, bismuth, zinc, iron, lead, manganese, zirconium or cobalt. It is understood that the use of "catalyst” herein refers to a curing catalyst suitable for curing the composition, preferably in absence of added water. Preferably the catalyst is suitable to cure the composition within less than about 24 hours, preferably less than 12 hours or preferably less than 8 hours.
  • the catalyst that can be used include dimethoxy titanium bis(ethylacetoacetate), dimethoxy titanium bis(acetylacetonate), diethoxy titanium bis(ethylacetoacetate), diethoxy titanium bis(acetylacetonate), diisopropoxy titanium bis(ethylacetoacetate), diisopropoxy titanium bis(methylacetoacetate), diisopropoxy titanium bis(t-butylacetoacetate), diisopropoxy titanium bis(acetylacetonate), di(n-butoxy) titanium bis(ethylacetoacetate), di(n-butoxy) titanium bis(acetylacetonate), diisobutoxy titanium bis(ethylacetoacetate), diisobutoxy titanium bis(ethylacetoacetate), diisobutoxy titanium bis(acetylacetonate), di(t-butoxy) titanium bis(ethylacetoacetate), di(t-butoxy) titanium bis(ethylacetoacetate), di(t-butoxy
  • titanium catalyst it is preferred to use the following titanium catalyst, because they are commercially obtainable: diethoxy titanium bis(ethylacetoacetate), diethoxy titanium bis(acetylacetonate), diisopropoxy titanium bis(ethylacetoacetate), diisopropoxy titanium bis(acetylacetonate), dibutoxy titanium bis(ethylacetoacetate), and dibutoxy titanium bis(acetylacetonate).
  • Diisopropoxy titanium bis(acetylacetonate) is particularly preferred.
  • the catalysts are dibutyltin dilaureate commercially available as DABCO T-12 from Air Products together with diisopropoxy titanium bis(acetylacetonate) .
  • the coating composition may comprise additional agents such as solvents, adhesion promoters, stabilizing agents, reinforcers, fillers, corrosion inhibitors, pigments, plasticisers, suspending agents, thixotropic agents, diluents, reactive diluents, UV light stabilizers, HALS, surfactant, or mixture thereof.
  • additional agents such as solvents, adhesion promoters, stabilizing agents, reinforcers, fillers, corrosion inhibitors, pigments, plasticisers, suspending agents, thixotropic agents, diluents, reactive diluents, UV light stabilizers, HALS, surfactant, or mixture thereof.
  • additional agents such as solvents, adhesion promoters, stabilizing agents, reinforcers, fillers, corrosion inhibitors, pigments, plasticisers, suspending agents, thixotropic agents, diluents, reactive diluents, UV light stabilizers, HALS, surfactant, or mixture thereof.
  • the coating composition herein is free of added water. Stated differently, although water may be present in a trace amount in the reagents or may be in the present of atmospheric humidity, no additional water is added to the composition. The coating composition herein may therefore be qualified as substantially free of water.
  • the substrate is an epoxy or an unsaturated polyester type gelcoat, aluminum or steel.
  • the method for reducing ice-adhesion to a substrate as defined herein is for reducing ice-adhesion on vanes (or sails or blades) of windmills, above water line of ship vessels and oilrigs, bridges, power line structures, environmental control system (ECS) condensers and aircraft fuselages.
  • vanes or sails or blades
  • ECS environmental control system
  • said epoxy resin i) is non-aromatic epoxy resins comprising more than one epoxy group per molecule
  • said amino-functional silicone resin ii) is comprising the units: (R3SiOi 2 ) w (1); (R 2 Si0 2 / 2 ) x (2); (RSi0 3/2 ) y (3) and (Si0 4/2 ) z (4);
  • R is selected from the group consisting of an alkyl group having up to four carbon atoms, an aryl group, an aminofunctional hydrocarbon group having up to four carbon atoms or alkoxy groups having up to four carbon atoms, w has a value of less than 0.4, x has a value of greater than 0.15, y has a value greater than zero to 0.7, z has a value of less than 0.2, at least 10 mole percent of silicon atoms in unit (2) contain aminofunctional hydrocarbon groups, with an amine equivalent weight ranging from about 150 to about 350 g/NH
  • said methoxy-functional silicone resin iii) is comprising the units: (R' 3 SiOi/ 2 ) W ' (7');
  • R' is selected from the group consisting of an alkyl group having up to four carbon atoms, an aryl group or an alkoxy groups having up to four carbon atoms;
  • said end functional polydimethylsiloxane iv) is having the formula: wherein R 5 is an alkyl up to four carbon atoms, a hydroxyl group, a 3-aminopropyl, a 3- hydroxypropyl or a 3-(hydroxyethoxy)propyl; R6 is a hydroxyl group, a 3-aminopropyl, a 3- hydroxypropyl or a 3 -(hydroxy ethoxy)propyl and where n is selected so that the molecular weight for the polysiloxane is 400 to 110,000; and the viscosity of the end functional
  • polydimethylsiloxane is about 15 cPs to 50,000 cPs.
  • said catalyst is one or more organometallic derivatives of titanium, tin, bismuth, zinc, iron, lead, manganese, zirconium or cobalt.
  • said epoxy resin i) non-aromatic epoxide resin having two 1,2 epoxide groups per molecule
  • said amino-functional silicone resin ii) is comprising the units: (R 3 SiOi/ 2 )w (1); (R 2 Si0 2 / 2 ) x (2); (RSi0 3/2 ) y (3) and (Si0 4 / 2 ) z (4);
  • R groups are Methyl in (1), the R groups are Methyl and Phenyl, or Methyl and 3-Aminopropyl in (2), the R group is Phenyl or 3-Aminopropyl in (3);
  • at least 10 mole percent of silicon atoms in unit (2) contain aminofunctional hydrocarbon groups and said amino-functional silicone resin ii) having an amine content of about 250 g/NH and less than 2% of methoxy radicals;- said methoxy-functional silicone resin iii) is comprising the units: (R' 3 SiOi/ 2 ) w > CO; (R'2Si0 2/2 ) x > (2'); (R' Si0 3/2 ) y > ( ⁇ ?') and (Si0 4/2 ) z > ( ⁇ '
  • R' is selected from the group consisting of an alkyl group having up to four carbon atoms, an aryl group or an alkoxy groups having up to four carbon atoms and have a molecular weight in the range of from about 400 to about 10,000;
  • said end functional polydimethylsiloxane iv) is having the formula: wherein R 5 is an alkyl up to four carbon atoms, a hydroxyl group, a 3-aminopropyl, a 3- hydroxypropyl or a 3 -(hydroxy ethoxy)propyl and R 6 is a hydroxyl group, or alternatively both R 5 and R 6 are -OH and where n is selected so that the molecular weight for the polysiloxane is 400 to 110,000; and the viscosity of the end functional polydimethylsiloxane is about 15 cPs to 50,000 cPs;
  • said catalyst of a blend of i) and iv) is a titanium catalyst and said catalyst of a blend of ii) and iii) is organotin catalyst.
  • said epoxy resin i) non-aromatic epoxide resin having two 1,2 epoxide groups per molecule an epoxide equivalent weight of 100 to 5,000
  • said amino-functional silicone resin ii) is comprising the units: (R3SiOi 2 ) w (1); (R 2 Si0 2 / 2 ) x (2); (RSi0 3 2 ) y (3) and (Si0 4 2 ) z (4);
  • R groups are Methyl in (1), the R groups are Methyl and Phenyl, or Methyl and 3-Aminopropyl in (2), the R group is Phenyl or 3-Aminopropyl in (3);
  • at least 10 mole percent of silicon atoms in unit (2) contain aminofunctional hydrocarbon groups and said amino-functional silicone resin ii) having an amine content of about 250 g/NH and less than 2% of methoxy radicals;
  • said methoxy-functional silicone resin iii) is comprising the units: (R' 3 SiOi/ 2 ) W ' (7');
  • R' groups are Methoxy, Methyl and Phenyl, with a methoxy content of about 15% and a molecular weight in the range of from about 1200 to about 1900;
  • said end functional polydimethylsiloxane iv) is having the formula: wherein both R 5 and R 6 are -OH and where n is selected so that the molecular weight for the polysiloxane is about 26,000; and the viscosity of the end functional polydimethylsiloxane is about 1000 cPs; and
  • said catalyst is a tin or an organotin catalyst.
  • said epoxy resin i) non-aromatic epoxide resin having two 1,2 epoxide groups per molecule an epoxide equivalent weight of 100 to about 500
  • said amino-functional silicone resin ii) is comprising the units: (R3SiOi 2 ) w (1); (R 2 Si0 2 / 2 ) x (2); (RSi0 3/2 ) y (3) and (Si0 4/2 ) z (4);
  • R groups are Methyl in (1), the R groups are Methyl and Phenyl, or Methyl and 3-Aminopropyl in (2), the R group is Phenyl or 3-Aminopropyl in (3);
  • at least 10 mole percent of silicon atoms in unit (2) contain aminofunctional hydrocarbon groups and said amino-functional silicone resin ii) having an amine content of about 250 g/NH and less than 2% of methoxy radicals;
  • said methoxy-functional silicone resin iii) is comprising the units: (R' 3 SiOi/ 2 ) W ' (7');
  • R' groups are Methoxy, Methyl and Phenyl, with a methoxy content of about 15% and a molecular weight in the range of from about 1200 to about 1900
  • said end functional polydimethylsiloxane iv) is having the formula: wherein both R 5 and R 6 are -OH and where n is selected so that the molecular weight for the polysiloxane is about 26,000; and the viscosity of the end functional polydimethylsiloxane is about 1000 cPs; and
  • said catalyst said catalyst of a blend of i) and iv) is a titanium catalyst and said catalyst of a blend of ii) and iii) is organotin catalyst.
  • said epoxy resin i) hydrogenated bisphenol A-type epoxy resin having an epoxide equivalent weight is 100 to about 500;
  • said amino-functional silicone resin ii) is comprising the units: (R 3 SiOi/ 2 )w (1); (R 2 Si0 2 / 2 ) x (2); (RSi0 3/2 ) y (3) and (Si0 4 / 2 ) z (4);
  • R groups are Methyl in (1), the R groups are Methyl and Phenyl, or Methyl and 3-Aminopropyl in (2), the R group is Phenyl or 3-Aminopropyl in (3);
  • at least 10 mole percent of silicon atoms in unit (2) contain aminofunctional hydrocarbon groups and said amino-functional silicone resin ii) having an amine content of about 250 g/NH and less than 2% of methoxy radicals;
  • said methoxy-functional silicone resin iii) is comprising the units: (R' 3 SiOi/ 2 ) W ' (7');
  • R' groups are Methoxy, Methyl and Phenyl, with a methoxy content of about 15% and a molecular weight in the range of from about 1200 to about 1900
  • said end functional polydimethylsiloxane iv) is having the formula: wherein both R 5 and R 6 are -OH and where n is selected so that the molecular weight for the polysiloxane is about 26,000; and the viscosity of the end functional polydimethylsiloxane is about 1000 cPs; and
  • said catalyst of a blend of i) and iv) is a titanium catalyst and said catalyst of a blend of ii) and iii) is organotin catalyst.
  • said epoxy resin i) hydrogenated bisphenol A-type epoxy resin having an epoxide equivalent weight is 100 to about 500;
  • said amino-functional silicone resin ii) is comprising the units: (R 3 SiOi/ 2 )w (1); (R 2 Si0 2 / 2 ) x (2); (RSi0 3/2 ) y (3) and (Si0 4 / 2 )z (4);
  • R groups are Methyl in (1), the R groups are Methyl and Phenyl, or Methyl and 3-Aminopropyl in (2), the R group is Phenyl or 3-Aminopropyl in (3);
  • at least 10 mole percent of silicon atoms in unit (2) contain aminofunctional hydrocarbon groups and said amino-functional silicone resin ii) having an amine content of about 250 g/NH and less than 2% of methoxy radicals;
  • said methoxy-functional silicone resin iii) is comprising the units: (R' 3 SiOi/ 2 ) W ' (7');
  • R' groups are Methoxy, Methyl and Phenyl, with a methoxy content of about 15% and a molecular weight in the range of from about 1200 to about 1900
  • said end functional polydimethylsiloxane iv) is having the formula: wherein both R 5 and R 6 are -OH and where n is selected so that the molecular weight for the polysiloxane is about 26,000; and the viscosity of the end functional polydimethylsiloxane is about 1000 cPs; and
  • said catalyst of a blend of i) and iv) is diisopropoxy titanium bis(acetylacetonate) and said catalyst of a blend of ii) and iii) is dibutyltin dilaurate.
  • said composition is comprising: 15% to 50%) by weight of the epoxide resin, relative to the total weight of the solids of the composition of said epoxy resin i);
  • said composition is comprising: 20%o to 30%) by weight of the epoxide resin, relative to the total weight of the solids of the composition of said epoxy resin i);
  • composition comprising:
  • the % range amounts of i), ii) iii) and iv) one or more catalyst and any optional agent are understood to mean that the total % of all components can't be greater than 100%> when a combination of the upper ranges can theoretically lead to a value greater than 100%>. In other words, the total amount of all components combined together are selected to that it is no greater than 100% .
  • the curing process is accelerated by the addition of catalysts at the end of the formulation, i.e. when all other components are admixed.
  • the test sample aluminum beams for the test method were then dipped in the freshly prepared formulation, and allowed to drip and cure at room temperature for at least 5 days.
  • the coatings were dry to the touch within 8 hours, through cured after 24 hours and fully cured after 3-5 days. It is understood that kits of a least 2 parts could be prepared by combining/mixing chemically compatible components, such that the end-user can more easily prepare the pre-cured coating composition.
  • Eponex 1510 epoxy resin
  • DC 3055 amino-silicone resin
  • Eponex 1510 epoxy resin 3 24.6
  • Eponex 1510 epoxy resin 3 24.6
  • Example 13 Component wt (g) wt %
  • Eponex 1510 epoxy resin 3 24.6
  • Eponex 1510 epoxy resin 3 24.6
  • Eponex 1510 epoxy resin 3 24.6
  • Eponex 1510 epoxy resin 3 24.6
  • the tests were conducted on an impeller, a 6061 T6 aluminum flat bar, 32 mm wide, 0.6 mm thick, which is then cut into small beams 340 mm in length. Thereto, an impeller was coated with the test sample at one impeller tip over a surface of approximately 1500 mm .
  • the method is a two-step procedure performed in AMIL's low-speed, closed-loop Icing Wind Tunnel (IWT) using a standard conditions of:
  • an ice layer was built up by depositing a water fog on to the coated surface, resulting in an ice thickness of typically 8 mm over said surface of approximately 1152 mm 2 .
  • the impeller was balanced by a counter weight mounted on the other impeller tip.
  • the impeller was then mounted on a shaft in a centrifuge chamber.
  • accelerometers were mounted which could detect the impact of an object colliding to said centrifuge Wall.
  • the rotational speed of the impeller was gradually increased with about 270 rpm/sec up to the point that ice-like mass detached from the impeller tip.
  • the actual rpm value of the impeller was fixed. From 1) final fixed rpm value, 2) the radial distance between the mass centre point of ice and axis of rotation, 3) the ice mass and 4) the air shear force, the critical shear between ice and coating surface at which detachment occurs, was determined. The latter is referred to as ice adhesion strength (E).
  • the adhesion reduction factor (ARE) is defined as E alu/E coating, Wherein E alu corresponds to the force required to shear off the ice mass from the uncoated aluminum surface.
  • Example 12 0.092 6
  • Example 13 0.230 2
  • the coating composition which includes a hydroxyl-terminated-polydimethylsiloxane (Example 1) provided a surface with a greater ARF value as compared to non-functional polydimethylsiloxanes (Examples 2-4).
  • Tinuvin 123 an HALS light stabilizer from BASF
  • ARF value 30 (Example 9).
  • the choice of catalyst had a major influence on the coating's ice adhesion.
  • Ti( «-BuO) 4 commonly employed in the prior art, instead of Ti(0-z ' Pr) 2 acac 2 lead to a lower ARF value (Example 10) indicating a significant increase in ice adhesion.
  • Ti(0-/ ' Pr) 2 acac 2 was deemed a superior catalyst for preparing icephobic compositions of the present disclosure.
  • a comparative composition using a monomeric aminosilane provided a lower ARF value (Example 11).
  • epoxy-siloxane based on monomelic aminosilanes lead to a wrinkled surface, which increase surface roughness that, although not bound by any a particular theory, could explain the lower ARF value.
  • This surface wrinkling effect was not observed in the compositions of the present disclosure using polymeric amino-silicone resin.
  • epoxy-siloxane composions made from a "monomeric" aminoalkyl-trialkoxysilane require moisture from the air and the outer layer begins to solidify first to form a film on the surface, commonly referred to as a skin, while the subsurface mixture is initially in a liquid state.
  • a freshly prepared mixture according to example 7 was placed in a closed desiccated calcium chloride environment and through curing to a solid state occurred within 8 hours.
  • di-endfunctional PFPE perfluoropolyether
  • amine-terminated polydimethylsiloxane Example 14
  • carbinol-terminated and monosilanol-terminated polydimethylsiloxanes provided icephobic coatings (Examples 15 and 16).
  • ARF values obtained on commercially available icephobic coatings namely Enercode, Stay clean and NuSil. While the former exhibits icephobic properties, the silicone coating is fragile by vitue of its polyorganosiloxane nature.
  • coatings described herein will be also be useful for structures exposed to freezing elements, such as, but not limited to, navigation vessels, electric power infrastructures, ocean rigs, bridges and aircrafts.
  • compositions of the present disclosure can be prepared according to the procedures denoted in the examples or modifications thereof using readily available starting materials and conventional procedures or variations thereof well known to a practitioner of ordinary skill in the art.
  • the above examples are given for illustrative purposes only and are not intended to limit the invention in any way.

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Abstract

La présente invention concerne une composition de revêtement comprenant une résine époxyde ; une résine de silicone à fonctionnalité amino ; une résine de silicone à fonctionnalité méthoxy ; et un polydiméthylsiloxane à terminaison fonctionnelle ; un procédé de préparation de ladite composition par réticulation des trois résines en présence d'un polydiméthylsiloxane à extrémité fonctionnelle et un procédé d'utilisation associé.
PCT/CA2015/051260 2014-12-08 2015-12-02 Compositions de revêtement, procédé de préparation associé et utilisation associée Ceased WO2016090468A1 (fr)

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WO2018073460A1 (fr) * 2016-10-18 2018-04-26 Gamesa Innovation & Technology, S.L. Composition polymère à propriétés antigel et d'autonettoyage
WO2018195119A1 (fr) 2017-04-17 2018-10-25 Cornell University Revêtement oléophobe sans fluor, procédés de production de celui-ci et utilisations de celui-ci
US20200079897A1 (en) * 2018-09-11 2020-03-12 United States Of America As Represented By The Administrator Of Nasa Durable Contamination Resistant Coatings
WO2021193973A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Substance de revêtement et corps multicouche
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US11312869B2 (en) * 2019-07-18 2022-04-26 Integran Technologies Inc. Articles comprising durable water repellent, icephobic and/or biocidal coatings
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CN114921150A (zh) * 2022-04-25 2022-08-19 上海交通大学 降低结冰附着强度的生物基环氧防除冰涂层的制备方法
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WO2018001889A1 (fr) * 2016-06-28 2018-01-04 Evonik Degussa Gmbh Composition à base d'oxyde de polysiloxanes
WO2018073460A1 (fr) * 2016-10-18 2018-04-26 Gamesa Innovation & Technology, S.L. Composition polymère à propriétés antigel et d'autonettoyage
CN110114425A (zh) * 2016-10-18 2019-08-09 西门子歌美飒可再生能源创新与技术有限公司 具有防冰和自洁性质的聚合物组合物
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WO2018195119A1 (fr) 2017-04-17 2018-10-25 Cornell University Revêtement oléophobe sans fluor, procédés de production de celui-ci et utilisations de celui-ci
CN110799596A (zh) * 2017-04-17 2020-02-14 康奈尔大学 无氟防油涂层及其制作方法和用途
EP3612596A4 (fr) * 2017-04-17 2021-01-20 Cornell University Revêtement oléophobe sans fluor, procédés de production de celui-ci et utilisations de celui-ci
CN115717337A (zh) * 2017-04-17 2023-02-28 康奈尔大学 无氟防油涂层及其制作方法和用途
US20200079897A1 (en) * 2018-09-11 2020-03-12 United States Of America As Represented By The Administrator Of Nasa Durable Contamination Resistant Coatings
US11746183B2 (en) * 2018-09-11 2023-09-05 United States Of America As Represented By The Administrator Of Nasa Durable contamination resistant coatings
EP3924187A1 (fr) * 2019-02-11 2021-12-22 PPG Industries Ohio, Inc. Compositions élastomères et procédés d'utilisation
US11319450B2 (en) * 2019-07-18 2022-05-03 Integran Technologies Inc. Articles comprising durable icephobic coatings
US11312869B2 (en) * 2019-07-18 2022-04-26 Integran Technologies Inc. Articles comprising durable water repellent, icephobic and/or biocidal coatings
US11661518B2 (en) 2019-07-18 2023-05-30 Integran Technologies Inc. Anisotropic icephobic coating
US11667798B2 (en) 2019-07-18 2023-06-06 Integran Technologies Inc. Anisotropic icephobic and biocidal coatings
US12168736B2 (en) 2019-07-18 2024-12-17 Integran Technologies Inc. Anisotropic icephobic and biocidal coatings
US12503544B2 (en) 2020-02-10 2025-12-23 Ppg Industries Ohio, Inc. Elastomeric compositions and methods of use
WO2021193973A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Substance de revêtement et corps multicouche
US12474990B2 (en) 2020-05-28 2025-11-18 Siemens Industry Software Inc. Hardware-based sensor analysis
US11459482B2 (en) 2020-06-19 2022-10-04 Pall Corporation Icephobic coating and coated articles
CN114921150A (zh) * 2022-04-25 2022-08-19 上海交通大学 降低结冰附着强度的生物基环氧防除冰涂层的制备方法
CN114921150B (zh) * 2022-04-25 2022-12-02 上海交通大学 降低结冰附着强度的生物基环氧防除冰涂层的制备方法
WO2024059113A1 (fr) * 2022-09-14 2024-03-21 Phazebreak Coatings, Inc. Kit de revêtement à composants multiples et son procédé d'utilisation pour conférer des caractéristiques anti-givrage à des articles

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