KR20220024482A - Single-component polysiloxane anti-skid / anti-slip coating - Google Patents

Abstract

organosilane polymers, polyamide polymers; and an abrasive aggregate. The organosilane comprises: reacting an amine-functional alkoxysilane with one or more isocyanates to form one or more adducts having unreacted isocyanate groups; and reacting the adducts with one or more polyfunctional amino- and/or hydroxyl compounds such that the polymer does not contain unreacted isocyanate groups. The polyfunctional amino- and/or hydroxyl compound has an alicyclic group or an aromatic group. The composition can be used to make single-component polysiloxane anti-skid/anti-slip coatings subjected to rolling, spraying, or troweling and curing with atmospheric moisture.

Description

Single-component polysiloxane anti-skid / anti-slip coating

The present disclosure relates entirely to polysiloxane coatings.

A non-skid/non-slip coating is a viscous material that provides an aggressive surface that is rolled, sprayed, or brushed. . These materials are used on the inner and outer decks of aquatic vessels to provide traction for aircraft, crew and equipment during departure. Similar materials, albeit with less rough contours, are used to provide traction on the exterior of aerospace ground support equipment, on the floor of ground vehicles, and on the wings of helicopters.

Conventional anti-skid coatings for naval surface ships are viscous, two-component (2K) materials containing epoxy-functional and amine-functional molecules, pigments, solvents, fillers, thickeners and abrasive aggregates. . These ingredients are mixed together using mechanical equipment and then applied onto the ship deck via napless phenolic rollers or spray pumps. The Navy's anti-skid coating is MIL-PRF-24667 compliant and must be present on decks with flight operations. Unfortunately, epoxy-amine anti-skid coatings can recover from decking due to insufficient adhesion to the underlying primer, sun degradation resulting in color change and loss of abrasive profile before reaching the required service life. failure due to peak breakage producing foreign object debris (FOD). Sailors will often undercoat areas where the skid barrier has been delaminated in an effort to prevent corrosion and further delamination, but they do not have the ability to apply additional skid barrier material because they cannot mix these viscous materials by hand. couldn't As a result, sections of a ship's deck often remain free of abrasive surfaces at times of deployment, not to mention that the decks have an unsightly stained appearance when covered with skid arresters and peeled undercoating. none.

Disclosed herein are: organosilane polymers, polyamide polymers; and an abrasive aggregate. The organosilane polymer comprises: reacting an amine-functional alkoxysilane with one or more isocyanates to form one or more adducts having unreacted isocyanate groups; and reacting the adducts with one or more polyfunctional amino- and/or hydroxyl compounds to form the polymer. The polyfunctional amino- and/or hydroxyl compound has an alicyclic group or an aromatic group. The organosilane polymer does not contain unreacted isocyanate groups.

A more complete understanding will be readily obtained by reference to the following description of exemplary embodiments and the accompanying drawings.
1 shows an example of an organosilane polymer containing an alicyclic.
2 shows the organosilane polymer when crosslinked (cured).
3 shows a photograph of a single-component (1K) anti-skid/anti-slip coating after being applied with a fleece-resistant phenolic roller on a 6"x12"x¼" epoxy-primed panel.

In the following description, specific details are set forth for purposes of explanation and non-limiting purpose in order to provide a thorough understanding of the present disclosure.

However, it will be apparent to one skilled in the art that the subject matter may be practiced in other embodiments that depart from these details. In other examples, detailed descriptions of well-known methods and devices are omitted so as not to obscure the present disclosure with unnecessary detail.

Polysiloxane coatings containing silicon-oxygen bonds are gaining popularity in the global coating market due to their excellent external durability, chemical resistance, and increased thermal stability compared to coatings based on all-organic polymers. come. A single-component (1K) polysiloxane anti-skid/anti-slip coating is a material that can be rolled or sprayed without the need for metering and mixing of ingredients and that provides an abrasive surface with durability and color retention when exposed to sunlight. Overcoming the limitations of 2K epoxy-based coatings by providing

The single-component polysiloxane anti-skid/anti-slip coatings described in this disclosure are based on synthetic organosilane polymers containing cycloaliphatic and/or aromatic units in their backbone and terminated with alkoxysilane groups. These 1K anti-skid coatings also contain amide-containing polymers and abrasive aggregates in addition to fillers, pigments, solvents, additives and catalysts. The coating may be rolled, sprayed, brushed or plastered onto the surface. Once applied, the alkoxysilane groups in the polymer will hydrolyze with moisture to form silanols. These silanols will then condense to form a hard polysiloxane/sol-gel network to provide a durable anti-skid/anti-slip coating.

The organosilane polymer must include an alicyclic or aromatic unit in its main backbone, but may be synthesized using various molecules. These molecules are: 1) isocyanate-functional molecules such as aliphatic, cycloaliphatic, and aromatic difunctional or trifunctional isocyanates, 2) 3-aminopropyltrimethoxysilane, N- amine-functional alkoxysilane molecules such as butyl-3-aminopropyltrimethoxysilane, and (N-cyclohexylmethyl)methyldiethoxysilane, 3) isophorone diisocyanate, 1,6-hexamethylene diamine, difunctional and trifunctional primary and secondary amines, such as 4,4'-methylenebis(N-secbutylcyclohexanamine), meta -xylylene diamine, and propane-1,2,3-triamine, and/ or 4) hydroxyl-functional molecules such as 1,5-pentanediol, 4,4′-isopropylideenedicyclohexanol, 1,4-cyclohexanedimethanol, and dendritic polyester polyols include those

Several suitable organosilane polymers are disclosed in US Pat. No. 10,190,020. (All publications and patent documents mentioned throughout this application are incorporated herein by reference.) The organosilane polymer is formed by reacting an amine-functional alkoxysilane with an isocyanate to form an adduct. It has terminal alkoxysilane groups. There is an excess of isocyanic groups to amine groups such that the adduct has unreacted isocyanic groups. The adduct is then reacted with the difunctional amino- or hydroxyl compound to consume all unreacted isocyanine groups. A typical reaction scheme is shown below. Note that the use of a diol forms urethane groups in the polymer. Alternatively, the difunctional amino- or hydroxyl compound may be reacted first with the isocyanate and then with the amine-functional alkoxysilane to form the same compounds as claimed in this disclosure. The claimed compounds can be made by either method. Each of the reactants may include more than one such compound of general structure. Other reactants may or may not be present.

The value of a is 1, 2, or 3 in that there is at least one alkoxy group bonded to the silicon atom. The value of n is a positive integer in that the isocyanic salt has n+1 isocyanic groups. The organosilane polymer may be a mixture of the aforementioned compounds and other organosilane polymers. The mixture may contain a small amount of a polymer in which all isocyanic groups are reacted with the amine-functional alkoxysilanes as shown below.

The reaction may produce a mixture of compounds depending on the proportions of the reactants. For example, if more than 50 mol % of an amine-functional alkoxysilane is used, some of the isocyanates will fully react with the amine-functional alkoxysilane, as shown above. If more than 50 mol % of NH or OH from a difunctional amino- or hydroxyl compound is used, respectively, the reaction has a plurality of repeating units (m) of the difunctional amino- or hydroxyl compound as shown below It will produce some compounds.

The organosilane polymer has no unreacted isocyanate groups. As used herein, “having no unreacted isocyanate groups” means that sufficient isocyanate-reactive groups This means that it has been used to react with all isocyanine groups.

Each of the R ¹ groups of the amine-functional alkoxysilane can be an independently selected alkyl group such that all R ¹ groups can be of the same or more than one type. Each R ² group of the amine-functional alkoxysilane is independently selected hydrogen, aryl, alkyl, cycloalkyl, ester-containing aliphatic, ester-containing fluorinated aliphatic, amide-containing aliphatic, or It may be a polysiloxane. The amine-functional alkoxysilane is a compound different from the organosilane polymer itself, and may not have a urea group and a urethane group. Suitable amine-functional alkoxysilanes are N-butyl-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (N-cyclohexylmethyl)methyldiethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropylmethyldiethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, or N-[3-(trimethoxysilyl)propyl 1-β-alanine butyl ester. .

The R ³ group of the isocyanate may be aliphatic, cycloaliphatic, or aromatic. Aliphatic isocyanates can provide better flexibility and weatherability to the coating. Suitable isocyanates are hexamethylene diisocyanate, a homopolymer of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, a homopolymer of isophorone diisocyanate, or methylene diphenyl diisocyanate, and their mixtures of, but are not limited to. Commercially available polymeric isocyanates may include mixtures such as dimers and trimers of hexamethylene diisocyanate.

Each R ⁴ group of the difunctional amino compound is independently selected from hydrogen, aryl, alkyl, cycloalkyl, ester-containing aliphatic, ester-containing fluorinated aliphatic, amide-containing aliphatic, or polysiloxanyl can Each of the R ⁵ groups of the difunctional amino- or hydroxyl compound comprises a cycloaliphatic or aromatic group, or any combination thereof. Suitable difunctional amino- or hydroxyl compounds include isophorone diamine; 1,6-hexamethylene diamine; 1,3,3-trimethyl-N-(1-methylethyl)-5-[(1-methylethyl)amino]cyclohexanemethanamine; 4,4'-methylenebis(N-sec-butylcyclohexanamine); propane-1, 2, 3-triamine; 1,5-pentanediol; 4,4'-isopropylidenedicyclohexanol;1,4-cyclohexanedimethanol; or dendritic polyester polyols.

Alkoxysilane-terminated organosilane polymers may be certain polyureas disclosed in US Pat. Nos. 9,139,753 or 9,701,868, both of which are incorporated herein by reference, and their specific The objects are included below. The teachings of these applications are applicable to the presently disclosed polyelements.

The isocyanate may be aliphatic, cycloaliphatic or aromatic. Aliphatic isocyanates have greater weather resistance (ie, external durability) than aromatic isocyanates, thus providing greater color stability when utilized in external coatings. Aliphatic isocyanates can have varying numbers of reactive isocyanate (NCO) groups per molecule, depending on their structure. Typically, the number ranges from 2.5 to 5.5. For the present coating composition, the aliphatic isocyanate can have more than two NCO groups per molecule.

Suitable aliphatic isocyanates are isocyanurates (eg, HDI and IPDI trimers), biurets, uretdiones, allophanates, oxadiazinetriones , iminooxadiazinedione, and structures based on prepolymers containing urethanes. Mixtures of these isocyanates may also be used. There are many commercially available aromatic isocyanates, aliphatic isocyanates, and cycloaliphatic isocyanates.

The N-substituted amine functional alkoxysilane may be an N-substituted 3-aminopropyltrialkoxysilane, an N-substituted 3-aminopropylalkyldialkoxysilane or an N-substituted dialkylalkoxysilane, wherein the silicon The alkyl group attached to the atom may be methyl or ethyl, and the alkoxy group attached to the silicon atom may be methoxy, ethoxy, n -propoxy, or n -butoxy.

The N-substituted group of the N-substituted amine functional alkoxysilane may be C ₁ -C ₁₂ alkyl, cycloalkyl, or aryl. Examples are N-methyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltributoxysilane, N-ethyl-3-aminopropyltri Propoxysilane, N-iso-propyl-3-aminopropyltrimethoxysilane, N-tert-butyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N- butyl-3-aminopropylmethyldimethoxysilane, N-butyl-3-aminopropyldimethylmethoxysilane, N-butyl-3-aminopropyltriethoxysilane, N-butyl-3-aminopropyltripropoxysilane, N-Butyl-3-aminopropyltributoxysilane, N-iso-butyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-hexyl-3-aminopropyl trimethoxysilane, N-nonyl-3-aminopropytrimethoxysilane and N-dodecyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane doesn't happen Many of these are commercially available.

The N-substituted group of the N-substituted amine functional alkoxysilane may be an ester-containing aliphatic or an ester-containing fluorinated aliphatic group, which may be a reactive "ene" group such as an acrylate. ene” group) and a Michael addition (coupled addition) reaction between 3-aminopropyltrialkoxysilane, 3-aminopropylalkyldialkoxysilane, or 3-aminopropyldialkylalkoxysilane. The conditions for forming Michael addition adducts with amines are well known in the literature. Suitable acrylate salts are methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 4-tert-butylcyclohexyl acrylate, diethyl maleate, dimethyl maleate, maleic acid. dibutyl, acrylic acid ethylene glycol methyl ether, acrylic acid 1,1,1,3,3,3-hexafluoroisopropyl, acrylic acid 2,2,2-trifluoroethyl, and acrylic acid 3,3,4,4; 5,5,6,6,7,7,8,8,8-tridecafluorooctyl. Examples are 3-((3-(trimethoxysilyl)propyl)amino)methyl propanoate (text: methyl 3-((3-(trimethoxysilyl)propyl)amino)propanoate), 3-((3-(trimethyl Toxysilyl)propyl)amino)butyl propanoate, 3-((3-(trimethoxysilyl)propyl)amino)propanoate 2-ethylhexyl, 3-((3-(trimethoxysilyl)propyl)amino) octyl propanoate, 3-((3-(trimethoxysilyl)propyl)amino)propanoic acid 3,3,3-trifluoropropyl, (3-(trimethoxysilyl)propyl)dimethyl aspartate, and ( 3-(trimethoxysilyl)propyl)diethyl aspartate.

The N-substituted group of the N-substituted amine functional alkoxysilane may also be an amide-containing aliphatic group, which can be combined with a molecule having a reactive "ene" group such as acrylamide and 3-aminopropyltrialkoxysilane, 3- formed by Michael addition (coupled addition) reactions between aminopropylalkyldialkoxysilanes, or 3-aminopropyldialkylalkoxysilanes. Suitable acrylamides include N-ethylacrylamide, N-propylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide, N-ethyl maleimide, and N,N'-diethylmaleamide However, the present invention is not limited thereto. Examples are N-propyl-3-((3-(trimethoxysilyl)propyl)amino)propanamide, N-butyl-3-((3-(trimethoxysilyl)propyl)amino)propanamide, N- Cyclohexyl-3-((3-(trimethoxysilyl)propyl)amino)propanamide, and 1-ethyl-3-((3-(trimethoxysilyl)propyl)amino)pyrrolidine-2,5 - Including, but not limited to, dione.

One of ordinary skill in the art would appreciate that small amounts of isocyanide groups (eg, 1-5%) may remain unreacted in the polymer and thus be used to aid adhesion to the substrate; , or isocyanide-reactive materials not discussed herein. However, it should not be considered a separate polymer, as a small proportion of the isocyanine groups on the polymer are not expected to change the properties of the polymer by reacting with the non-disclosed material. For the purpose of making isocyanide-free coatings, it is recommended that all isocyanic groups react during the synthesis of the organosilane polymer.

Suitable solvents for the synthesis of the organosilane polymer are those that are not reactive with isocyanic groups. These solvents include xylenes, light aromatic naphtha, mineral spirits, butyl acetate, 1-methoxy-2-propyl acetate, tert-butyl acetate, butyl propionate, pentyl propionate, 3-ethoxypropionate ethyl , 4-chlorobenzotrifluoride, tetrahydrofuran, 1,4-dioxane, dimethylacetamide, and N-methyl pyrrolidone.

A catalyst may be used to speed up the hydrolysis of the alkoxysilane groups and promote crosslinking of the resulting silanol groups to form a cured coating. Suitable catalysts are organotin compounds such as dibutyl tin dilaurate, dibutyl tin diacetate and bis(2-ethylhexanoic acid) dibutyl tin, titanium tetraisopropoxylated, aluminum triethoxylated, tetrabutoxylated. zirconium, and metal alkoxides such as titanium chelates, including aminoalkoxysilanes, potassium hydroxide, organic acids, inorganic acids, tertiary amines, or mixtures thereof.

Suitable pigments are titanium dioxide, carbon black, red iron oxide, yellow iron oxide, copper phthalocyanine blue, sodium aluminum sulphosilicate, chromium oxide, cobalt chromite green spinel, chromium. chromium green-black hematite, nickel antimony titanium yellow rutile, and manganese-based pigments.

The polyamide polymer can be used to provide flexibility or thixotropic properties and can be any polymer containing an amide group comprising within its polymer backbone, which can be an aliphatic polyamide, cycloaliphatic polyamide or aromatic polyamide. can be Examples are fatty acid based polyamides, dimerized fatty acid based polyamides, para -phenylene terephthalamides, nylon, polyaspartates, and poly(hexamethylene adipamide) including, but not limited to.

The filler may be any material used to fill the volume of the composition, adjust the viscosity, or improve corrosion resistance. Examples are talc, ceramic microspheres, amorphous silica, hollow glass spheres, mica, aluminum flake, aluminum spheres, zinc particles, glass fragments, wollastonite. , and calcium carbonate.

Additives may be any material included in small amounts to tailor the viscosity, impact resistance, weather resistance, or other properties of the composition. These additives include pigment dispersing agents, rubber beads, polyethylene fibers, polypropylene fibers, hindered amine light stabilizers (HALS), ultraviolet absorbers (UVAs), conductive polyaniline, and graphene.

The abrasive aggregate may be any particle that is incorporated into the composition to increase the coefficient of friction of the surface of the composition when the composition solidifies. It can be round or angular particles consisting of a size of 0.10-2.5 mm and 3-9 Mohs hardness. Examples are brown aluminum oxide, white aluminum oxide, walnut shell, aluminum, crushed glass, glass beads, com cob, melamine, acrylic, and urea. (urea), but is not limited thereto.

When the composition is applied to a surface, it can cure to form a solid coating. The alkoxysilane groups of the organosilane polymer undergo hydrolysis and mutual condensation. Unlike two-component anti-skid coatings, single-component polysiloxane anti-skid coatings are an all-in-one-can system that does not require metering and mixing of components. Although its skid protection may be easy to agitate and apply, it provides an aggressive and hard profile when cured. The silicon-oxygen bonds in the coating are

1K skid protection provides greater resistance to degradation by sunlight than polymers based on all-organic bonds such as those used in epoxy-amine skid protection, thus providing 1K skid protection for a longer period of time in its color and contour. can keep 1K skid protection providing improved exterior durability can extend the service life of nonskids on ship decks and reduce maintenance costs.

The following examples are given to illustrate specific applications. These specific examples are not intended to limit the scope of the disclosure of this application.

Example 1

Synthesis of organosilane polymers - aliphatic isocyanate based on hexamethylene ureddione diisocyanate (Desmodur N-3400, Covestro) equipped with nitrogen inlet, mechanical stirrer, and thermometer 1 Dissolve in 4-chlorobenzotrifluoride (Sigma-Aldrich) (approximately 1.2/1 by weight isocyanate/solvent; ˜1.2/1 by weight isocyanate/solvent) in a liter (L) 4-necked round bottom flask. Then, vinyltrimethoxysilane (Gelest) (this water scavenger is added. Using an addition funnel, add N-butyl-3- to the solution while maintaining the temperature between 50 and 60 °C. Aminopropyltrimethoxy silane (Gelest) (3/5 ratio of equiv. NH to equiv. NCO) is added dropwise. When the addition is complete, again Aliphatic-cyclic diamine 1,3,3-trimethyl-1-aminomethyl-5-aminocyclohexane (Clearlink 1080, Dorf Ketal) while maintaining a temperature of 50 to 60 °C (2 NH equivalent to NCO equivalent ratio of /5) is added dropwise.After addition, the reaction is stirred for another 30 minutes to 1 hour until all isocyanine groups are consumed according to FTIR analysis. The structure of one made polymer is shown in FIG. 1 .

Example 2

Single-component anti-skid / anti-slip formulation - the organosilane polymer of Example 1 was mixed with titanium dioxide (R-960, Chemours), inorganic black pigment (Black 30C940, Shepard) A single-component anti-skid/anti-slip coating is prepared by mixing with Shepherd Pigments), inorganic blue pigment (Blue 30C527, Shepherd Pigments), and ceramic microspheres (W-610, 3M). . Then an amide-containing polymer (Crayvallac PA4BA20, Palmer Holland), fibrillated high-density polyethylene fibers (Mini Fibers, Inc.) )), 12-30 mesh glass beads (Blast-O-Lite), and dibutyl tin dilaurate (Sigma-Aldrich) followed. The ranges of percentages in the formulation are given in Table 1. Once mixed, the coating is applied over an epoxy-primed steel sheet using a 9-inch fleece resistant phenolic roller (Grainer), followed by 40-60 at 72°F for 14 days. % relative humidity. 2 shows the structure of the crosslinked (cured) organosilane polymer made by the above reaction. 3 shows an exemplary rolled anti-skid/anti-slip coating after overnight cure. The polysiloxane coating is hard-to-touch after a day.

The amount of organosilane polymer used depends on the application. For example, an anti-slip formulation for a stairway would use high proportions of polymer and low proportions of aggregates and fillers. High friction skid resistant surfaces for road use will use low proportions of polymers and high proportions of aggregates and fillers.

Obviously, many modifications and variations are possible in light of the above teachings. Accordingly, it should be understood that the claimed subject matter may be practiced otherwise than as specifically described. For example, any reference to claim elements in the singular using the articles "a", "an", "the", or "said" is intended to limit the element to the singular. not to be construed as

Claims (11)

As a composition:
An organosilane polymer, the freesilane polymer comprising:
reacting an amine-functional alkoxysilane with one or more isocyanates to form one or more adducts having unreacted isocyanate groups; and
made by a method comprising reacting the adducts with one or more polyfunctional amino- and/or hydroxyl compounds such that the polymer does not contain unreacted isocyanine groups; wherein the polyfunctional amino- and/or hydroxyl compound comprises an alicyclic group or an aromatic group;
polyamide polymers; and
abrasive aggregate
A composition comprising The method of claim 1,
wherein the amine functional alkoxysilane is N-butyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, or (N-cyclohexylmethyl)methyldiethoxysilane. According to claim 1,
The isocyanate is hexamethylene diisocyanate, a homopolymer of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, a homopolymer of isophorone diisocyanate, or methylene diphenyl diisocyanate. . The method of claim 1,
The polyfunctional amino- and/or hydroxyl compound may be selected from isophorone diamine; m-xylylene diamine; 1,6-hexamethylene diamine; 1,3,3-trimethyl-N-(1-methylethyl)-5-[(1-methylethyl)amino]cyclohexanemethanamine; 4,4'-methylenebis(N-sec-butylcyclohexanamine);propane-1,2,3-triamine;1,5-pentanediol;4,4'-isopropylidenedicyclohexanol;1,4-cyclohexanedimethanol; or a dendritic polyester polyol. The method of claim 1,
wherein the polyamide polymer contains aliphatic groups, aromatic groups, or both. According to claim 1,
wherein the abrasive aggregate is round or angled particles. According to claim 1,
the abrasive aggregate is particles having an average diameter of 0.10 to 2.5 mm;
wherein the abrasive aggregate has an average hardness of 3 to 9 Mohs. According to claim 1,
The composition comprises:
Solvents, Colors, Fillers, Additives, or Catalysts
Further comprising a composition. As a method:
applying the composition of claim 1 onto a surface; and
allowing the composition to cure by reaction of the alkoxysilane groups with atmospheric moisture and subsequent condensation of the silanol groups
A method comprising A single-component polysiloxane anti-skid / anti-slip coating made by the method of claim 9 . 10. The method of claim 9,
wherein the composition is applied by rolling, spraying, or troweling.

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