CN1207058A - Heat ablative coating composition - Google Patents
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- CN1207058A CN1207058A CN 96199486 CN96199486A CN1207058A CN 1207058 A CN1207058 A CN 1207058A CN 96199486 CN96199486 CN 96199486 CN 96199486 A CN96199486 A CN 96199486A CN 1207058 A CN1207058 A CN 1207058A
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Abstract
A heat ablative coating composition is prepared by combining an epoxy silane resin, an epoxy resin, a silicone intermediate, a silicon-modified polyether, an aminosilane, at least one organometallic catalyst, at least one organic solvent, water, at least one filler, optional nonsilicon-containing amine catalyst, and optional pigments and thixotropic agents. The heat ablative coating composition is applied to a substrate to form a film having a build thickness in the range of from about 0.1 to 0.5 inches that is capable of curing at ambient outdoor temperature in about seven days, depending on ambient conditions. The heat ablative film so formed is designed to undergo a slow thermal decomposition when exposed to high temperature conditions without igniting or causing excessive smoke, and is designed to have good thermal conductivity to protect the underlying substrate from thermal decomposition. The heat ablative film has elastomeric properties of impact resistance and flexibility that serves to both protect an underlying structure from mechanical damage due to particle or other contact, and facilitate its use with flexible substrates.
Description
Field of the present invention
The present invention relates generally to heat ablative coating composition, more specifically relate to the coating composition that self-vulcanizing also can form Elastic Film.
Background of the present invention
Heat ablative coating is used for preventing that following base material is subjected to elevated temperature heat to expose the application of the influence that contacts with actual flame.This class coating forms the protection blocking layer suitably between thermal source and base material, reduce to minimum so that will be delivered to the heat energy of following substrate surface.If do not stop, then heat energy can cause base material to reduce physicals (as yield strength), causes base material to fight to cause the substrate surface oxidation, and this oxidation results causes base material to damage fully.Since following base material be generally with such as in the rocket body of installation rocket engine or the transmitting station of this rocket in the relevant important structure unit of living thermic devices, therefore any possible physicals reduction of this structure all is undesirable, has proved during use and can bring on a disaster.
Be used to prevent that the ordinary method that base material is exposed by elevated temperature heat or the flame contact influences from comprising use solid thermal brick, those as in space shuttle, using, these bricks impose on substrate surface with high-temperature adhesives.These bricks are only effective when time on the substrate surface below it remains adhered to, but known because the different power that act on the brick with high temperature heat source (being rocket engine tail gas) with the thermal expansivity of brick of base material cause brick to separate from substrate surface.In case remove brick, then Xia Mian base material is exposed under the deleterious high temperature heat source.In addition, use these bricks that the snappiness of any degree can not be provided, therefore be not suitable for flexible substrate (as in the umbilical cable that is connected between rocket and the transmitting station) use.
Be used to prevent that other method that base material is influenced by high temperature exposure or flame contact from comprising the use heat ablative coating composition.This conventional heat ablative coating composition provides heat to a certain degree to protect to following base material by in flame contact or be exposed to the component that pliotherm period chien shih coating ablates and form thus.Be applied to this heat ablative coating on the following base material and solidify to form the heat ablative film.
Yet; the heat ablative film that is formed by these conventional heat ablative coatings is based on epoxy and polyurethanes technology; this technology only provides about 200 to 250 limited thermotolerance, therefore can not satisfy the following rocket launching pad base material of protection and avoid about 5,000 temperature effect of at least 10 seconds.In addition, the heat ablative film that is formed by these conventional Resins, epoxy and polyurethane-based paints provides bad uviolresistance, weathering resistance and acid resistance, causes too early frosting, fades and tarnishes.The film of Resins, epoxy and polyurethane-base heat ablative coating composition formation simultaneously lacks snappiness, and when being exposed to hot conditions burning of following time and generating toxic smog.
Lost efficacy down in hot conditions (as rocket launching), peeled off or because of film contact propellant grain causes thin film corrosive, snappiness and shock resistance are the required performances of using in this uses of heat ablative coating from base material because of following base material bending for playing to eliminate or reduce film to greatest extent.Heat ablative film separation or corrosion are undesirable, because this is exposed under the elevated temperature heat following substrate surface, cause catching fire and the mechanical property reduction.
In addition, the heat ablative film that is formed by conventional heat ablative coating composition needs hot setting usually, promptly solidify being higher than under the environment external temperature, or even adopt a kind of curing or circulation that applied coating composition is exposed specific time under the temperature that raises gradually.Need hot setting and/or adopt this curing to make to use this heat ablative coating trouble and time-consuming.When applied base material is very big structure such as transmitting station or rocket, this situation is outstanding especially, because require curing to be undertaken, or undertaken by the thermal source order curing substrate coating fragment of using the part to apply by whole coatingsurface is exposed under the necessary solidification heat in very big baking oven etc.
Therefore, need preparation can prevent that following base material is subjected to the heat ablative coating composition of elevated temperature heat harmful effect.Need heat ablative coating composition can form rubber-like heat ablative film, so that snappiness and shock resistance to a certain degree to be provided.Need heat ablative coating composition to solidify at ambient temperature, and need not hot setting or complicated cure cycle.Also need heat ablative coating to form to have good uviolresistance, weathering resistance and acid resistance and when being exposed to the protective film that hot conditions following time do not burn or generate toxic smog.
The present invention's general introduction
Therefore, the invention provides a kind of heat ablative coating composition by epoxy silane resin, Resins, epoxy, polysiloxane intermediate, silicon-modified polyether, aminosilane, at least a organo-metallic catalyst, at least a organic solvent, water, at least a filler, non-essential not siliceous amine catalyst and non-essential pigment and thixotropic agent are mixed with.These compositions mix by two-pack, and pack and be stored in two containers, before use with its mixing.
With the coating of this heat ablative coating composition, form build about 0.1 to 0.5 inch and can under the environment external temperature in about 7 days (depending on envrionment conditions) solidified film.So the heat ablative film that forms can prevent that following substrate surface (as the rocket launching pad structure) is subjected to elevated temperature heat and/or the directly influence of fire exposure during preset time.So the heat ablative film that forms is designed to carry out thermolysis at a slow speed, and is missing of ignition or cause excessive smoke, and is designed to have good thermal conductivity to prevent following base material thermolysis.
This heat ablative film also shows elastic performance, and this performance provides the following base material physical damage of shock-resistance to prevent to cause because of particle or other contact (as the alumina particle by the rocket ejection).The elasticity of heat ablative film also provides snappiness, so that used heat ablative coating composition can be used for protecting flexible substrate, as the umbilical cable of moving between rocket and transmitting station.
These and other characteristics of the present invention, aspect and advantage are apparent by following description and appending claims.
Detailed description of the present invention
The present invention relates to heat ablative coating composition, said composition can be solidified the cured film that has the such elastic performance of heat ablative and snappiness and shock-resistance to provide at ambient temperature.According to the principle of the invention, by in the presence of the water of q.s, following component being mixed to be hydrolyzed and polycondensation, prepare heat ablative coating composition, described component is:
A. epoxy silane resin;
B. polysiloxane intermediate;
C. silicon-modified polyether;
D. aminosilane;
E. Resins, epoxy;
F. non-essential amine catalyst;
G. organo-metallic catalyst;
H. at least a organic solvent;
I. at least a filler; With
J. non-essential pigment and/or thixotropic agent etc. are mixed together these components and are hydrolyzed, and the crosslinked and interpenetrating(polymer)networks resin of the heat ablative film that forms elasticity, self-vulcanizing is produced in polycondensation, homopolymerization and heteropolymerization reaction.
For the epoxy silane resin, suitable epoxy silane resin comprises those epoxy silane resins with following general formula with one or more oxyethane rings:
R wherein
1Be selected from alkyl, wherein R with about 1 to 6 carbon atom
2Be preferably saturated hydrocarbyl, wherein each R with about 1 to 3 carbon atom
1Can be identical or different and wherein x be about 1 to 3.Need be with R
2Group is limited to about 3 carbon atoms to limit the space steric effect that these groups cause during hydrolysis and polycondensation, and this space steric effect can reduce the speed of these reactions, finally makes to realize that the solidified time is elongated.
Be to promote fast setting, preferred epoxy silane resin is R wherein
1Group is oxyalkyl and R
2Group is the epoxy silane resin of methyl.Particularly preferred epoxy silane resin is γ-glycidoxypropyltrimewasxysilane, and it is commercially available, for example presses ProductName OSI A-187 available from OSI Specialties, Terrytown, New York.
The epoxy silane resin is used to strengthen the snappiness that is coated with interlayer and base material sticking power and improvement solidified coating of coating.Preferred heat ablative coating composition is with about 0.5 to 5wt% epoxy silane resin formation.Be coated with interlayer and base material adhesion property with what the coating composition of the epoxy silane preparation that is lower than about 0.5wt% will have a reduction, and have the film integrity of reduction.Use more than the coating composition of the epoxy silane of about 5wt% preparation improper economically because the not obvious improvement coating adhesion of epoxy silane that increases or the snappiness of solidified coating.The particularly preferred heat ablative coating epoxy silane resins of about 1wt%.
For polysiloxane intermediate composition, suitable polysiloxane intermediate comprises those with following general formula:
Each R wherein
3Be selected from hydroxyl, and have alkyl, aryl and the alkoxyl group of about 1 to 6 carbon atom, wherein each R
3Can be identical or different, each R wherein
4Be selected from hydrogen, and have the alkyl and the aryl of about 1 to 6 carbon atom, wherein each R
4Can be identical or different, the n that wherein chooses should make the polysiloxane intermediate have about molecular-weight average of 500 to 3,500.Suitable is, for R
3And R
4The carbon-containing group that group is chosen has and is lower than about 6 carbon atoms, with restricted space steric effect during hydrolysis and polycondensation, and reduces set time thus.Use the polysiloxane intermediate so that coating composition has heat-resisting and resistivity against fire.
Preferred polysiloxane intermediate is R wherein
3Be methoxyl group (to promote fast setting) and R wherein by forming more volatile pure analogue
4Respectively the do for oneself polysiloxane intermediate of phenyl.Particularly preferred polysiloxane intermediate is phenylbenzene-methyl methoxy based polysiloxane, and this polysiloxane is commercially available, for example with ProductName DC-3074 available from Dow Corning Corp, Midland, Michigan; With with ProductName SY-231 available from Wacker, Adrain, Michigan.
Preferred heat ablative coating composition forms by the polysiloxane intermediate with about 0.5 to 5wt%.Can form the thermotolerance with reduction and the cured film of flame retardant resistance with the coating composition of the polysiloxane intermediate preparation that is lower than about 0.5wt%.Use more than the coating composition of the polysiloxane intermediate preparation of about 5wt% improper economically, because the thermotolerance or the flame retardant resistance of the not obvious improvement cured film of polysiloxane intermediate that increases, also can form the cured film of the thermal ablation speed of the snappiness of hardness with increase, reduction and reduction.The particularly preferred heat ablative coating polysiloxane intermediate preparation of about 2wt%.
For silicon-modified polyether, the suitable silicon modified polyether that is used to prepare heat ablative coating composition comprises those that following general formula is represented:
Each R wherein
5Can be selected from saturated hydrocarbyl, wherein each R with 1 to 6 carbon atom
5Can be identical or different, each R wherein
6Can be alkoxyl group, wherein each R with 1 to 3 carbon atom
6Can be identical or different, R wherein
7Can be selected from saturated or unsaturated alkyl, the n that wherein chooses with about 1 to 12 carbon atom
1Should make silicon-modified polyether have about molecular-weight average of 250 to 5,000.Need limit each R
5And R
6The carbonatoms of group to be reducing the space steric effect during hydrolysis and the polycondensation, and promotes fast setting thus.
Preferred silicon-modified polyether is R wherein
5Group respectively do for oneself methyl, R
6Group respectively do for oneself methoxyl group, R
7Group is propylidene and the n that chooses
1Silicon-modified polyether.Particularly preferred silicon-modified polyether be (for example) with the Silmod product line available from Kaneka, the silicon-modified polyether of Japan.
Silicon-modified polyether is used to prepare coating composition, because it makes cured film have the heat-resisting ablative and improved film integrity of snappiness, extensibility, wear resistance, increase.Preferred heat ablative coating composition forms with about silicon-modified polyether of 20 to 45wt%.The cured film that formation is had heat-resisting ablative, snappiness, elongation and heat-resisting and the fire performance of reduction with the coating composition of the silicon-modified polyether preparation that is lower than about 20wt%.Can form with the coating composition of the silicon-modified polyether preparation that is higher than about 45wt% have slow set time, the cured film of the heat-resisting and fire performance of bad film integrity, imperfect attachment and reduction.Particularly preferred heat ablative coating prepares with the silicon-modified polyether of about 35wt%.
For aminosilane, the suitable aminosilane that is used to prepare heat ablative coating composition comprises those aminosilanes with following general formula:
(NH
2)
N2-R
8-Si-(OR
9)
N3R wherein
8Be selected from the saturated or unsaturated alkyl that comprises 1 to 18 carbon atom, wherein R
9Be selected from alkyl, aryl and alkoxyl group, wherein n with 1 to 6 carbon atom
2Be 1 to 3, n wherein
3Be 1 to 3.Preferred aminosilane comprises wherein n
2Equal 2, R wherein
9Be methyl and n wherein
3Equal 3 those.Need be with R
8Be limited in be lower than about 18 carbon atoms with the viscosity limitation of aminosilane to acceptable level, and with R
9Be limited in and be lower than about 6 carbon atoms with restricted space steric effect, the promotion fast setting.
Particularly preferred aminosilane is that (for example) is with the N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan of ProductName A-1120 available from OSI Specialties.Other suitable aminosilane comprise (for example) with ProductName DC-Z6020 available from Dow Corning and with the A-1100 product line available from UnionCarbide, New York, those of New York.Aminosilane is for forming the Si-O-Si key as catalyzer and linking agent, also as the reactive component that forms the epoxy-amine key between polysiloxane intermediate and silane monomer.Therefore, the amount that is used to prepare the aminosilane of coating composition is stoichiometric aminosilane, by total epoxy equivalent (weight) (existing in epoxy silane and Resins, epoxy form) and total amine equivalent (existing with aminosilane and amine catalyst form).
Coating composition formation with substoichiometric aminosilane preparation has the set time of increase and the film of bad film integrity.Use more than the coating composition of stoichiometric aminosilane preparation and can produce film with limited working life.Particularly preferred heat ablative coating is with the aminosilane preparation of about 1wt%, based on the about 1wt% epoxy silane, 8wt% Resins, epoxy and the 1wt% amine catalyst that use.
For Resins, epoxy, the suitable epoxy that is used to form heat ablative coating composition is not siliceous Resins, epoxy, comprise those Resins, epoxy that contain at least two ethylene oxide groups, described Resins, epoxy can be aliphatic series or aromatics, and can comprise some monomers.Preferred Resins, epoxy is glycidyl (glycidal) type Resins, epoxy.Particularly preferred Resins, epoxy is modification Resorcinol type Resins, epoxy; Particularly, for example with ProductName Erisys RF-50 available from CVC SpecialtyChemicals, Cherry Hill, modification diglycidylether Bisphenol F-resorcinol formaldehyde of New Jersey.Resins, epoxy provides film integrity, film tear strength, reaches adhesion and cohesive performance.
Preferred heat ablative coating composition forms with about Resins, epoxy of 1 to 20wt%.The film that formation is had the set time of the film elongation of reduction, the snappiness that reduces and increase with the coating composition of the Resins, epoxy preparation that is lower than about 1wt%.Use more than the coating composition of the Resins, epoxy of about 20wt% preparation and can produce the snappiness with reduction and the heat-resisting ablative film of reduction.Particularly preferred heat ablative coating prepares with the Resins, epoxy of about 8wt%.
For amine catalyst, suitable amine catalyst comprises the tertiary amine with following general formula:
R wherein
10Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
11Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
12Be selected from alkyl, aryl, alkaryl, epoxy alkyl and hydroxyalkyl with 1 to 12 carbon atom.
Preferred amine catalyst comprises dimethyl methyl hydramine, dimethylethanolamine, dimethyl propanol amine, dimethyl butyrate hydramine, dimethyl-penten hydramine, dimethyl hexanol amine, methylethyl carbinolamine, methyl propyl carbinol amine, methylethyl thanomin, methylethyl Propanolamine, monoisopropanolamine, methyldiethanolamine, trolamine, diethanolamine, thanomin.Particularly preferred amine catalyst be (for example) with ProductName Ancamine K-54 available from Air Products, three-2-ethylhexanoate of Pennsylvania (tri-2-ethylhexoate).
The same with aminosilane, amine catalyst is for forming the Si-O-Si key as catalyzer and linking agent between polysiloxane intermediate and silane monomer, as the reactive component that forms the epoxy-amine key, but different with aminosilane, the homopolymerization of its catalysis epoxide group.Amine catalyst is inessential, and for realizing ambient temperature curing not necessarily.Yet amine catalyst can be used to quicken to solidify really.
Preferred heat ablative coating composition is used at the most, and the amine catalyst of about 5wt% forms.The coating composition that does not use amine catalyst to prepare can form the film of the set time with increase.Use more than the coating composition of the amine catalyst of about 5wt% preparation and can produce working life and reduce flexible film with reduction.Particularly preferred heat ablative coating prepares with the amine catalyst of about 1wt%.
For organo-metallic catalyst, preferred organo-metallic catalyst comprises the organo-tin compound with following general formula:
R wherein
13, R
14, R
15And R
16Be selected from alkyl, aryl and alkoxyl group separately with 1 to 12 carbon atom, and R wherein
13, R
14, R
15And R
16In any two also be selected from inorganic atoms, comprise halogen, sulphur or oxygen.
Organo-tin compound as catalyzer comprises tin tetramethide, tetrabutyl tin, tetra octyl tin, tributyltin chloride, the methacrylic acid tributyl tin, the dichloride dibutyl tin, dibutyltin oxide, butyl disulfide tin, dibutyltin diacetate, dibutyl tin laurate, dibutyltin maleate polymer, dilauryl mercaptan dibutyl tin, stannous octoate, two (iso-octyl thioglycolic acid) dibutyl tin, the tri-chlorination butyl tin, butyl stannonic acid, the dichloride dioctyl tin, di-n-octyltin oxide, two lauric acid dioctyl tins, the dioctyl tin maleate polymkeric substance, two (iso-octyl Thiovanic acid) dioctyl tin, the sulfuration dioctyl tin, 3-thiohydracrylic acid dibutyl tin.Other suitable organo-metallic catalyst comprises organic zinc compound.
Particularly preferred organo-metallic catalyst be (for example) with ProductName UA-220 available from Kaneka, the diacetyl acetone of Japan acid dibutyl tin.Preferred coating compositions prepares with the blend (comprising diacetyl acetone acid dibutyl tin and zinc octoate) of organotin and organic zinc compound.
Organo-metallic catalyst is used for promoting silane hydrolyzate and condensation in the presence of amine.Organo-tin compound is specially adapted to cause this hydrolysis and condensation reaction, and organic zinc compound is used to impel reaction to finish.Preferred heat ablative coating composition comprises 0.5 to 5wt% organo-metallic catalyst.The heat ablative film that formation is had the set time of increase with the coating composition of the organo-metallic catalyst preparation that is lower than about preferred amounts.The cured film of using the coating composition more than the preparation of the organo-metallic catalyst of aequum production to be had the heat-resisting and flame retardant resistance of reduction.
Particularly preferred heat ablative coating prepares with initiation hydrolysis and condensation with the blend of organo-tin compound and organic zinc compound, and impels reaction to finish.Particularly preferred catalyst blends comprises the organo-tin compound of about 0.3wt% and the organic zinc compound of about 0.1wt%.
For the water that is used to prepare heat ablative coating composition, need add the water of q.s (being stoichiometry) to promote epoxy silane and the hydrolysis of polysiloxane intermediate with the deionization form.In addition, after coating composition is applied on the required base material, need water in the atmosphere or moisture, form the heat ablative film to finish the curing of coating.Preferred heat ablative coating composition comprise 0.1 to 2wt% add entry (by composition total weight).To form with the coating composition of the water preparation that is lower than about 0.1wt% can not suitable solidified heat ablative film.Use coating composition can generate gel or hard solid more than the preparation of the water of about 2wt%.Particularly preferred heat ablative coating prepares with the water of about 0.5wt%.
For the solvent that is used to prepare heat ablative coating composition of the present invention, suitable solvent comprises conventional organic solvent, as alcohol, glycol acetic ester, ether, ester, aromatic hydrocarbon etc.Concrete solvent comprises (for example) MEK, MIBK, n-propyl ketone, methyl isoamyl ketone, Methyl amyl ketone, isobutyl acetate, butylacetate, 3-ethoxyl ethyl propionate, dimethylbenzene and high boiling aromatic hydrocarbon solvent, as glycidyl ether acetic ester, hexyl acetate, heptyl acetate etc.Solvent composition can be single solvent or can be the mixture of two or more solvents.Preferred coating compositions is to prepare with solvent mixture.Particularly preferred solvent mixture is what be mixed with by dimethylbenzene and glycidyl ether acetic ester.
Solvent composition is used to promote resin and filler blending and reduces viscosity to help the coating coating.Heat ablative coating composition comprises 5 to 20wt% solvent.The solvent that use is lower than preferred amounts can be produced can not well-mixed coating, causes forming the film with bad film integrity.Using solvent more than preferred amounts that formation is had film forming ability is lower than as the required coating composition of heat ablative film.Particularly preferred coating composition comprises the blend of about 12% solvent, and described blend is formed by the blend of dimethylbenzene, glycidyl ether acetic ester and methyl alcohol.
For filler, the suitable filler that is used to prepare heat ablative coating composition comprises SiO 2 powder, ceramic fiber, talcum (Magnesium Silicate q-agent), clay such as potter's clay (pure aluminium silicate), wollastonite (Calucium Silicate powder), lime carbonate, barite (barium sulfate, barium metaborate), aluminum trihydrate, graphite, zinc, aluminium, copper etc.Preferred filler comprises particle in small, broken bits, as barite (barium sulfate), clay, pottery, mica, micaceous iron oxide, aluminum slice, glass flake, stainless steel thin slice etc.
Filler is used to form the structural supports of film, to promote high film forming.The heat ablative film that is formed by coating composition of the present invention has about 0.1 to 0.5 inch build suitably.So the film of thickness is required because proved they for prevent following structure under the condition of being rapidly heated (as in transmitting station is used, in about 10 seconds in from environment mistress temperature rise to about 5,000 °F) damaged by heat and/or flame contact.
Preferred filler comprise when be exposed to high temperature or directly flame to contact following time be fire retardant and hinder those of smoke substance.Coating composition of the present invention can comprise the blend of single filler or different fillers, depends on the film performance that application-specific is required.For example, for as heat ablative transmitting station coating, prepare coating composition with the blend of clay, talcum and ceramic fiber filler.
Preferred heat ablative coating composition comprises 10 to 35wt% filler.For being used as heat ablative coating, the cured film that the coating composition for preparing with the filler that is lower than about 10wt% has formation build, flame retardant resistance and the anti-smokiness of reduction.Use the cured film that formation is had bad film integrity and bad coating performance more than the coating composition of the filler of about 35wt% preparation.Particularly preferred coating composition comprises the filler that the mixture by clay, talcum and ceramic fiber filler of about 25wt% forms.
Can also use pigment, as ferric oxide, aluminum oxide, titanium dioxide, chrome green etc.Should avoid plumbiferous pigment, because it can disturb curing.Also can use pigment dyestuff, as organic yellow, phthalocyanine (phthalo) is green and phthalocyanine blue make product painted.Zinc oxide also can be used for promoting the film sclerosis.
Coating composition can be used single pigment prepared, or prepares with the mixture of more than one pigment, depends on specific end use.Preferred heat ablative coating composition can comprise the pigment of about 15wt% at the most.Particularly preferred coating composition comprises the pigment of about 8wt%.
Coating composition prepared in accordance with the present invention also can comprise additive, as pigment wetting agent, tensio-active agent, defoamer, flow control agent, thixotropic agent and UV stablizer and softening agent.Coating composition also can comprise the additive of about wt% at the most.Preferred coating compositions can comprise the additive of about 2wt% at the most.Particularly preferred coating composition comprises about 0.5% additive.
Heat ablative coating composition of the present invention is pressed the bicomponent system preparation and is stored: epoxy silane resin, Resins, epoxy, polysiloxane intermediate, organo-metallic catalyst, water, a part of organic solvent, non-essential pigment, a part of filler and a part of additive are mixed forming first component in first container; Silicon-modified polyether, aminosilane, amine catalyst, residue filler, residue organic solvent and rest additive are mixed together second kind of component of formation in second container.Before the coating, the material in first and second containers merged and be mixed together the formation heat ablative coating composition.
Under the condition of not wishing to be subjected to the constraint of any particular theory or mechanism, it is believed that this heat ablative coating composition is by being prepared by the hydrolytie polycondensation of amine and catalytic polysiloxane of organo-metallic catalyst and silane in the presence of water.Meanwhile, homopolymerization and assorted the gathering because of having amine catalyst and aminosilane initial ring epoxy resins.These reactions of carrying out simultaneously produce crosslinked and interpenetrating(polymer)networks resin, form heat ablative film elastic, self-vulcanizing thus.
Coating composition of the present invention can be by conventional coating technique such as brushing, roller coat or spraying coating.Available one or more conventional organic solvents dilute coating to help spraying.The solvent that can be used for this purpose is with previously described to be used to prepare those of coating composition identical.If need, can use the solvent of 50wt% at the most, by the gross weight of solvent and coating composition.About 10 to 20wt% the organic solvent of preferred use is to meet government about discharging the regulation of volatile organic compounds amount.Particularly preferred Sprayable coating compositions forms by the organic solvent (based on the gross weight of solvent and coating composition) with about 12wt%.
A key feature according to the coating composition of principle of the invention preparation is to solidify at ambient temperature, forms the heat ablative film thus on various form substrate (being formed by concrete and metal etc. as those).In preferred embodiments, after various components mixing and being applied on the required base material, this applied coating composition was solidified in about 5 to 12 days, depend on such as factors such as ambient temperature conditions, relative humidity, uv light exposure, film thickness, wind conditions.In one embodiment, coating composition of the present invention after being applied on the metal base, can be in about 7 days under about 70 of envrionment temperature completely solidified.Coating composition of the present invention can be in about 50 to 120 coatings down of environment external temperature, so that its curing.
According to another key feature of the coating composition of principle of the invention preparation is that substrate surface below the heat ablative film produced can prevent in preset time is by elevated temperature heat and/or directly flame contact infringement.For example, in the time of on being applied to used rocket launching pad structure such as emission spacecraft, guided missile, this heat ablative film plays elevated temperature heat and the flame infringement that prevents that following metal and/or concrete structure from being produced by the rocket engine of spacecraft or guided missile.In this case, the heat ablative film in emission the time is exposed to short period of time at least 10 seconds from the environment external temperature under up to 5,000 being rapidly heated.
During so being exposed under the extreme temperature, the heat ablative film is designed to missing of ignition or do not cause under the excessive smog condition and carry out slow thermolysis, and has good thermal conductivity to prevent following base material thermolysis.Different with the GPF (General Protection False coating that is formed by non-silica-based Resins, epoxy and polyurethane composition, heat ablative coating of the present invention is not flammable, and does not produce toxic smog.In this example application, the base material temperature that this heat ablative film is designed to keep following is lower than about 150 °F.
Key feature again according to the coating composition of principle of the invention preparation is that gained heat ablative film is elastic, therefore shock resistance to a certain degree is provided and can be used for protecting flexible substrate.In an example application of coating transmitting station, the heat ablative film plays the influence that base material below the protection is not subjected to the known mechanical damage that is brought by the alumina particle of rocket ejection.The heat ablative film also is used to prevent flexible substrate, as being heated during launching in the umbilical cable of using between transmitting station and the spacecraft and the damaging influence of fire exposure.
A key feature again of heat ablative coating composition of the present invention is to compare with polyurethane coating with the non-silica-based Resins, epoxy of routine, and they provide fabulous uviolresistance, weathering resistance and acid resistance.
Prepare the heat ablative coating composition that on the transmitting station of spacecraft, rocket etc., uses according to following embodiment.
Embodiment
By will about 2g epoxy silane resin, 7.6g dimethylbenzene, 15g Resins, epoxy, 3.4g polysiloxane intermediate, 0.6g organo-tin compound and 0.3g organic zinc compound merge, and these compositions are mixed to evenly, first component of preparation heat ablative coating composition adds 12g clay filler, 0.8g methyl alcohol, 2.7g glycol ether acetate, 13.3g TiO 2 pigment, 2.3g black oxide pigment, 12g talc filler, 18g ceramic fiber filler, 0.9g deionized water, 8.4g dimethylbenzene and 0.3g thixotropic agent in this first component.Each composition of first component at room temperature is mixed together to evenly.
By will about 66g silicon-modified polyether, 0.6g thixotropic agent, 5g ceramic fiber filler, 16g clay filler merge, and these compositions is mixed together to evenly second component of preparation heat ablative coating composition.In the composition of this second component, add 7.6g dimethylbenzene, 2.4g aminosilane and 2.4g amine catalyst.The composition of second component at room temperature is mixed together to evenly.
Merge the composition that to merge by composition and at room temperature be mixed to evenly, the preparation heat ablative coating composition first and second components.Heat ablative coating composition according to the present embodiment preparation can be with 0.1 to 0.5 inch film thickness coating, under about 70 envrionment temperature in about 7 days completely solidified, and prevent that following base material is compromised during about 10 seconds under being exposed to up to about 5,000 °F.
Although described an embodiment of heat ablative coating composition of the present invention, carrying out multiple variation is conspicuous to those skilled in the art.Owing to can carry out multiple variation, should understand in the scope of following claims, the present invention also can be according to the embodied in other except that the ad hoc fashion of having described.
Claims (34)
1. the heat ablative coating composition of a self-vulcanizing, by following component is mixed with:
A kind of epoxy silane resin;
A kind of Resins, epoxy;
A kind of polysiloxane intermediate;
A kind of silicon-modified polyether;
A kind of aminosilane;
At least a organo-metallic catalyst;
At least a organic solvent;
Water; With at least a filler.
2. heat ablative coating composition as claimed in claim 1, wherein the epoxy silane resin has the following general formula that comprises one or more oxyethane rings:
R wherein
1Be selected from alkyl, wherein R with about 1 to 6 carbon atom
2Be selected from saturated hydrocarbyl with about 1 to 3 carbon atom and wherein x be about 1 to 3.
3. heat ablative coating composition as claimed in claim 1, wherein the polysiloxane intermediate has following general formula:
Each R wherein
3Be selected from hydroxyl, and have alkyl, aryl and the alkoxyl group of about 1 to 6 carbon atom, wherein each R
4Be selected from hydrogen, and have the alkyl and the aryl of about 1 to 6 carbon atom, the n that wherein chooses should make the polysiloxane intermediate have about molecular-weight average of 500 to 3,500.
4. heat ablative coating composition as claimed in claim 1, wherein silicon-modified polyether has following general formula:
Each R wherein
5Be selected from saturated hydrocarbyl, wherein each R with 1 to 6 carbon atom
6Be selected from alkoxyl group, wherein R with 1 to 3 carbon atom
7Be selected from saturated hydrocarbyl and unsaturated alkyl, the n that wherein chooses with about 1 to 12 carbon atom
1Should make silicon-modified polyether have about molecular-weight average of 250 to 5,000.
5. heat ablative coating composition as claimed in claim 1, wherein organo-metallic catalyst comprises the mixture of organotin and organic zinc.
6. heat ablative coating composition as claimed in claim 1 also comprises not siliceous amine catalyst.
7. heat ablative coating composition as claimed in claim 6, wherein amine catalyst is the tertiary amine with following general formula:
R wherein
10Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
11Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
12Be selected from alkyl, aryl, alkaryl, epoxy alkyl and hydroxyalkyl with 1 to 12 carbon atom.
8. heat ablative coating composition as claimed in claim 1, wherein filler comprises the mixture of clay, talcum and ceramic fiber filler.
9. heat ablative coating composition as claimed in claim 1 comprises 0.5 to 5wt% epoxy silane resin, 1 to 20wt% Resins, epoxy, 0.5 to 5wt% polysiloxane intermediate, 20 to 45wt% silicon-modified polyether, counts stoichiometric aminosilane, 0.5 to 5wt% organo-metallic catalyst, 5 to 20wt% organic solvent, 10 to 35wt% filler and 0.1 to 2wt% water by epoxy and amine equivalent.
10. the heat ablative coating composition of a self-vulcanizing, by following component is mixed with:
Contain one and a plurality of separately
A kind of epoxy resin ingredient of group and a kind of amine component;
A kind of not siliceous epoxy resin ingredient;
At least a recurring group that contains
Component;
A kind of not siliceous amine catalyst;
At least a organo-metallic catalyst;
A kind of have a recurring group
Contain silicon components, wherein R is selected from saturated and unsaturated alkyl;
At least a organic solvent;
Water; With
At least a filler.
11. the heat ablative coating composition of a self-vulcanizing, by following component is mixed with:
A kind of epoxy silane resin, it has following general formula:
R wherein
1Be selected from alkyl, wherein R with about 1 to 6 carbon atom
2Be selected from saturated hydrocarbyl with about 1 to 3 carbon atom and wherein x be about 1 to 3;
A kind of Resins, epoxy;
A kind of polysiloxane intermediate;
A kind of silicon-modified polyether has following general formula:
Each R wherein
5Be selected from saturated hydrocarbyl, wherein each R with 1 to 6 carbon atom
6Be selected from alkoxyl group, wherein R with 1 to 3 carbon atom
7Be selected from saturated hydrocarbyl and unsaturated alkyl, the n that wherein chooses with about 1 to 12 carbon atom
1Should make silicon-modified polyether have about molecular-weight average of 250 to 5,000;
A kind of aminosilane;
At least a organo-metallic catalyst;
A kind of not siliceous amine catalyst;
At least a organic solvent;
Water; With
At least a filler.
12. as the heat ablative coating composition of claim 11, wherein the polysiloxane intermediate has following general formula:
Each R wherein
3Be selected from hydroxyl, and have alkyl, aryl and the alkoxyl group of about 1 to 6 carbon atom, wherein each R
4Be selected from hydrogen, and have the alkyl and the aryl of about 1 to 6 carbon atom, the n that wherein chooses should make the polysiloxane intermediate have about molecular-weight average of 500 to 3,500.
13., comprise 20 to 45wt% polysiloxane-modified polyethers as the heat ablative coating composition of claim 11.
14., comprise 0.5 to 5wt% epoxy silane resin, 1 to 20wt% Resins, epoxy, 0.5 to 5wt% polysiloxane intermediate and 10 to 35wt% filler as the heat ablative coating composition of claim 12.
15. as the heat ablative coating composition of claim 11, include the organic metal catalyst mixture, this mixture contains organo-tin compound and organic zinc compound.
16., comprise 0.5 to 5wt% organo-metallic catalyst as the heat ablative coating composition of claim 15.
17. as the heat ablative coating composition of claim 12, wherein aminosilane has following general formula:
(NH
2)
N2-R
8-Si-(OR
9)
N3R wherein
8Be selected from the saturated or unsaturated alkyl that comprises 1 to 18 carbon atom, wherein R
9Be selected from alkyl, aryl and alkoxyl group, wherein n with 1 to 6 carbon atom
2Be 1 to 3, n wherein
3Be 1 to 3.
18., comprise stoichiometric aminosilane by total epoxy and amine equivalent as the heat ablative coating composition of claim 17.
19. as the heat ablative coating composition of claim 11, wherein amine catalyst has following general formula:
R wherein
10Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
11Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
12Be selected from alkyl, aryl, alkaryl, epoxy alkyl and hydroxyalkyl with 1 to 12 carbon atom.
20., comprise 0.2 to 5wt% amine catalyst as the heat ablative coating composition of claim 19.
21., comprise 0.5 to 5wt% epoxy silane resin, 1 to 20wt% Resins, epoxy, 0.5 to 5wt% polysiloxane intermediate, 20 to 45wt% silicon-modified polyether, count stoichiometric aminosilane, 0.2 to 5wt% amine catalyst, 0.5 to 5wt% organo-metallic catalyst, 5 to 20wt% organic solvent, 10 to 35wt% filler and 0.1 to 2wt% water by total epoxy and amine equivalent as the heat ablative coating composition of claim 11.
22. a method of protecting base material to avoid high temperature and fire exposure infringement is by being applied to the described heat ablative coating composition of claim 10 on the base material and solidifying the coating that is coated with at ambient temperature.
23. the heat ablative coating composition of a self-vulcanizing, by following component is mixed with:
A kind of epoxy silane resin;
A kind of not siliceous Resins, epoxy;
A kind of polysiloxane intermediate;
A kind of silicon-modified polyether with following general formula:
Each R wherein
5Be selected from saturated hydrocarbyl, wherein each R with 1 to 6 carbon atom
6Be selected from alkoxyl group, wherein R with 1 to 3 carbon atom
7The n that is selected from saturated hydrocarbyl with about 1 to 12 carbon atom and unsaturated alkyl and wherein chooses
1Should make silicon-modified polyether have about molecular weight of 250 to 5,000;
A kind of aminosilane with following general formula:
(NH
2)
N2-R
8-Si-(OR
9)
N3R wherein
8Be selected from the saturated or unsaturated alkyl that comprises 1 to 18 carbon atom, wherein R
9Be selected from alkyl, aryl and alkoxyl group, wherein n with 1 to 6 carbon atom
2Be 1 to 3, n wherein
3Be 1 to 3;
At least a organo-metallic catalyst;
A kind of not siliceous amine catalyst with following general formula:
R wherein
10Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
11Be selected from hydrogen, and have aryl, alkyl, alkaryl and the epoxy alkyl of 1 to 12 carbon atom, wherein R
12Be selected from alkyl, aryl, alkaryl, epoxy alkyl and hydroxyalkyl with 1 to 12 carbon atom;
At least a organic solvent;
Water; With
At least a filler.
24., comprise 20 to 45wt% silicon-modified polyether, count stoichiometric aminosilane, 0.2 to 5wt% amine catalyst and 10 to 35wt% filler by total epoxy and amine equivalent as the heat ablative coating composition of claim 23.
25. as the heat ablative coating composition of claim 23, wherein the epoxy silane resin has following general formula:
R wherein
1Be selected from alkyl, wherein R with about 1 to 6 carbon atom
2Be selected from saturated hydrocarbyl with about 1 to 3 carbon atom and wherein x be about 1 to 3.
26., comprise 1 to 20wt% Resins, epoxy as the heat ablative coating composition of claim 25.
27. as the heat ablative coating composition of claim 25, wherein the polysiloxane intermediate has following general formula:
Each R wherein
3Be selected from hydroxyl, and have alkyl, aryl and the alkoxyl group of about 1 to 6 carbon atom, wherein each R
4Be selected from hydrogen, and have the alkyl and the aryl of about 1 to 6 carbon atom, the n that wherein chooses should make the polysiloxane intermediate have about molecular-weight average of 500 to 3,500.
28., comprise 0.5 to 5wt% polysiloxane intermediate as the heat ablative coating composition of claim 27.
29. as the heat ablative coating composition of claim 23, wherein filler comprises the mixture of clay, talcum and ceramic fiber filler.
30. as the heat ablative coating composition of claim 23, wherein organic solvent comprises dimethylbenzene, glycol ether acetate and methanol mixture.
31., comprise 5 to 20wt% organic solvent as the heat ablative coating composition of claim 30.
32. as the heat ablative coating composition of claim 23, wherein organo-metallic catalyst includes the mixture of machine tin compound and organic zinc compound.
33., comprise 0.5 to 5wt% organo-metallic catalyst as the heat ablative coating composition of claim 23.
34. a method for preparing room temperature solidified heat ablative coating composition comprises the steps:
Following component is mixed first kind of mixture of formation:
A kind of epoxy silane resin;
A kind of Resins, epoxy;
At least a polysiloxane;
At least a organo-metallic catalyst;
Water;
At least a organic solvent; With
At least a filler;
Following component is mixed second kind of mixture of formation:
Silicon-modified polyether;
Aminosilane;
At least a filler; With
At least a organic solvent; With
First and second kinds of mixtures are mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96199486 CN1207058A (en) | 1995-11-30 | 1996-12-02 | Heat ablative coating composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/565,112 | 1995-11-30 | ||
| CN 96199486 CN1207058A (en) | 1995-11-30 | 1996-12-02 | Heat ablative coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1207058A true CN1207058A (en) | 1999-02-03 |
Family
ID=5129516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96199486 Pending CN1207058A (en) | 1995-11-30 | 1996-12-02 | Heat ablative coating composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1207058A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293242B (en) * | 2007-04-24 | 2010-09-01 | 中国石油天然气管道局 | Flame heating, solidifying technique of solvent-free epoxy paint |
| CN102566273A (en) * | 2010-11-18 | 2012-07-11 | 奇美实业股份有限公司 | Positive photosensitive resin composition and method for forming pattern |
| CN103850355A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Structure for thermal protective coating of rocket launching pad and application thereof |
| CN104924704A (en) * | 2014-03-20 | 2015-09-23 | 中国科学院大连化学物理研究所 | High-temperature-resistant coating structure for steel structure surface and applications thereof |
-
1996
- 1996-12-02 CN CN 96199486 patent/CN1207058A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293242B (en) * | 2007-04-24 | 2010-09-01 | 中国石油天然气管道局 | Flame heating, solidifying technique of solvent-free epoxy paint |
| CN102566273A (en) * | 2010-11-18 | 2012-07-11 | 奇美实业股份有限公司 | Positive photosensitive resin composition and method for forming pattern |
| CN103850355A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Structure for thermal protective coating of rocket launching pad and application thereof |
| CN103850355B (en) * | 2012-12-04 | 2016-08-03 | 中国科学院大连化学物理研究所 | The structure of a kind of rocket launching pad thermal protection coating and application thereof |
| CN104924704A (en) * | 2014-03-20 | 2015-09-23 | 中国科学院大连化学物理研究所 | High-temperature-resistant coating structure for steel structure surface and applications thereof |
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