CA3123892A1 - Polyurethane with high heat tolerance and other desirable properties including transparency, surface smoothness, desirable adhesiveness, resistance to impact damage, scratches and moisture, and method and use thereof - Google Patents

Abstract

A polyurethane composition including: a) at least one polyfunctional isocyanate with three or more backbone carbons; b) at least one polyol with at least two hydroxyl groups; and optionally at least one of a) at least one additive; b) at least one catalyst;
c) at least one surface modification agent; and combinations thereof.

Description

TITLE OF THE INVENTION
POLYURETHANE WITH HIGH HEAT TOLERANCE AND OTHER
DESIRABLE PROPERTIES INCLUDING TRANSPARENCY, SURFACE SMOOTHNESS, DESIRABLE ADHESIVENESS, RESISTANCE TO
IMPACT DAMAGE, SCRATCHES AND MOISTURE, AND
METHOD AND USE THEREOF
FIELD OF THE DISCLOSURE
[0001]
A polyurethane material (also described herein as a polyurethane composition) that is high in heat tolerance, impact and scratch resistance, and moisture resistance. Along with having properties such as transparency, surface smoothness, and adequate adhesion to glass or ceramic surfaces, the polyurethane material disclosed may be useful for coating glass or ceramic substrates especially in the field of pharmaceutical packaging, such as coating primary packaging containers for pharmaceutical products. Also provided are methods of manufacture and application.
BACKGROUND OF THE DISCLOSURE

[0002]
Polyurethane is a family of polymers commonly used in many aspects of the modern industry. It is generally obtained from the polymerization reaction between poly-alcohol and isocyanate, where it can contain other functional groups such as esters, ethers, urea, and aromatic groups in addition to the main urethane groups. Based on the polyols and the multi-functional isocyanates used to make up the polyurethane, a wide range of physical and chemical properties can be imparted onto the material [Akindoyo JØ, et al.
Polyurethane types, synthesis and applications ¨ a review. RSC Adv., 2016, 6, 114453; M.
Soto, R. M. Sebastian and J. Marquet, Photochemical Activation of Extremely Weak Nucleophiles: Highly Fluorinated Urethanes and Polyurethanes from Polyuoro Alcohols, J. Org. Chem., 2014, 79, 5019-5027]. Some physical characteristics which can be imparted by adjusting the makeup of the polyurethane include flexibility, elasticity, strength, water susceptibility, thermal sensitivity, and sensitivity to other chemicals.

[0003] The available selection of raw material components used in making polyurethane, such as di- or tri-isocyanates, polyols, and other chain extenders have made it possible to Date Recue/Date Received 2021-07-06 greatly customize the properties of polyurethane. The most commonly used polyols include polyethers, polyester polyols or acrylic polyols, and the widely used diisocyanates include methylene diphenyl diisocyanate, hydrogenated methylene diphenyl diisocyanate, toluene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Furthermore, polyurethanes are available as both thermoplastics and thermosets. Thermoplastic polyurethanes are linear, segmented copolymers consisting of alternating hard and soft segments. Hard segments are rigid and highly polar, composed of diisocyanate and short chain extender molecules such as diols or diamines, and have high inter-chain interaction due to hydrogen bonding between the urethane and urea groups. On the other hand, soft segments are formed from linear long-chain diols or polyols, flexible, and weakly polar. Softer polyurethanes can be made using longer polyols with lower degree of crosslinking, while harder polyurethanes are made using shorter polyol segments with higher degree of crosslinking [Bayer 0. The diisocyanate polyaddition process (polyur- ethanes). Description of a new principle for building up high-molecular compounds. Angew Chem 1947;A59:257; Janischewski K, Reichel D. Aqueous two component polyurethane coatings, preparation thereof and use thereof. US
patent 6048926, 2000; Blencowe A, Clarke A, Drew MGB, Hayes W, Slark A, Woodward P.
Alternative syntheses of linear polyurethanes using masked isocyanate monomers. React Funct Polym 2006;66:1284-95; Yoo S, Lee HS, Seo SW. Orientation and phase separated structure of polyurethanes having various chemical struc- tures. Pollimo 1997;21:459-67;
Halimann B, Duffy JV, Lee GF, Balizer E. Thermal and dynamic mechanical properties of polyurethaneureas. J Appl Polym Sci 1988;35:1829-52; Camargo RE, Macosko CW, Tirre UM, Wellinghoff ST. Phase separation studies in rim polyurethanes catalyst and hard segment crystallinity effects. Polymer 1985;26: 1145-54; Petrovic ZS, Javni I.
The effect of soft-segment length and concentration on phase separation in segmented polyur-ethanes. J Polym Sci: Part B: Polym Phys 1989;27:545-60; Markovs RA. Effect of polyol structure in diamine extended rim systems. J Cell Plast 1985;21:326-31].
Depending on its wide variety of properties, polyurethane has been used in coatings for digital chips and displays, cushion materials, binders and sealants, thermal and sound insulators, and protective panels [Chattopadhyay, D.K. and Webster, D.C., 2009. Thermal stability and flame retardancy of polyurethanes. Progress in Polymer Science, 34(10), pp.1068-1133].

Date Recue/Date Received 2021-07-06

[0004]
Despite the use of polyurethane across many different modern industries, there has been a lack in the types of polyurethane suitable for use in pharmaceutical primary packaging. The reason for this is the level of transparency and integrity a polyurethane material has to keep throughout the sterilization and downstream fill-and-finish processing steps often needed to package a pharmaceutical product in a glass or ceramic container.
Tolerance to high heat, moisture, and tendency to scratch, in addition to the requirement to keep transparent, during pharmaceutical processing has prohibited the use of a polyurethane based coating on the glass and ceramic containers.

[0005]
There is a need for a polyurethane composition that may be used as an external coating on primary pharmaceutical packaging articles, with qualities such as improvement of surface smoothness, lower coefficient of friction, and higher impact resistance of the glass articles during the fill-and-finishing steps. Therefore, this disclosure aims to provide a high performance polyurethane composition, methods of manufacture and application of the high performance polyurethane composition exhibiting high heat tolerance, resistance to moisture, scratch resistance, including high scratch resistance, surface transparency and smoothness, and chemical resistance, including high chemical resistance.

[0006]
Other industries that may benefit from the external polyurethane coating described here include food and beverage containers, automobile windows and finishes, building structure windows, and textiles.
BRIEF SUMMARY OF THE DISCLOSURE

[0007]
According to one aspect, there is provided a polyurethane composition with at least one characteristic selected from tolerance to high heat or elevated temperatures, and other characteristics including (scratch resistance, impact resistance, moisture resistance, transparency, antimicrobial, antiviral, adhesion to glass and ceramic surfaces), said polyurethane composition comprising: i) at least one isocyanate; ii) at least one polyol and optionally at least one of: iii) at least one additive; iv) at least one catalyst, and v) at least one surface modification agent, and combinations thereof.

[0008] In one alternative, the at least one isocyanate is a polyfunctional isocyanate, having three or more backbone carbons in its structure, aromatic, aliphatic, cycloaliphatic or Date Recue/Date Received 2021-07-06 polycyclic. In one alternative, said at least one isocyanate is selected from the group consisting of i sophorone dii socyanate, hexamethylene dii socyanate, 4,4 '-methylenebi s(cyclohexyl isocyanate), or 3-(triethoxysilyl)propyl isocyanate, any of their derivatives, and combinations thereof.

[0009] In another alternative, the at least one polyol has at least two functional groups, in one alternative, two hydroxyl groups, to increase degree of crosslinking with the at least one isocyanate and the optionally at least one additive, and optionally at least one other functional group. In one alternative, said at least one other functional group has a Nitrogen (N), Sulphur (S) or Phosphorus (P) group on the polyol. In one alternative, six hydroxyl groups is the maximum number in alcohols that are known to be safe for transport and reaction. In one alternative, said at least one polyol is selected from the group consisting of 1,4-butanediol, 1,6 hexanediol, triethylene glycol, glycerol, polyethylene terephthalate, polyethylene succinate, tris(hydroxymethyl)propane, 1,1,1-tris(hydroxymethyl)propane, ethylene glycol, propylene glycol, xylitol, mannitol, 2,3-butanediol, 4,4'-isopropylidenedicyclohexanol, any of their derivatives, and combinations thereof. In one alternative, a molar ratio of the polyfunctional isocyanate used in the composition, to that of the polyol, is calculated based on the number of functional groups present in the specific isocyanate or alcohol used. In one alternative, the molar ratio of the number of isocyanate functional groups on the polyfunctional isocyanate to the number of hydroxyl groups on the polyol is about 1:1. In another alternative, the molar ratio is selected from the group consisting of about 1:1.1, 1:1.05, 1:1.01, 1:1, 1.01:1, 1.05:1, and 1.1:1. We have found when the ratio of isocyanate to hydroxyl groups strays from this range, reaction dynamics change and reaction completion may be compromised. Furthermore, having too much unreacted reagents (either isocyanate or alcohol) may lead to unnecessary waste generation and possible harm to the environment during scale up of the process.

[0010]
In another alternative, said at least one additive may be optionally added to the polyurethane composition. In one alternative, the concentration of said at least one additive that is added to the composition is between about 0 to 10 % by molar weight of total reagents (not including solvent). In one alternative, each said at least one additive added to the polyurethane composition is between 0.1-2 % by molar weight.

Date Recue/Date Received 2021-07-06

[0011]
In another alternative, there are two types of additives that may be added to the polyurethane composition.

[0012]
In one alternative, the first type of additive are additives with one or two terminal reactive groups in their chemical structure, which may react with either or both, of the hydroxyl group(s) on the polyol, and/or the isocyanate group on the multifunctional isocyanate, therefore being crosslinked within the polyurethane network. In one alternative, the first type of additive is selected from the group consisting of a water molecule, 2,6-di-tert-butyl-4-methylphenol, monohydroxy-terminated poly(dimethylsiloxane), bishydroxy-terminated poly(dimethylsiloxane), poly(ethylene glycol) diglycidyl ether, octafluoro-pentanol, polyethylene terephthalate, polyethylene succinate, bis-(2-hydroxy-ethyl)-methyl-tetradecyl-ammonium chloride, any of their derivatives and combinations thereof.

[0013]
In one alternative, the second type of additives are additives that are not reactive with the polyurethane polymer (or composition), but are embedded within the polymeric matrix. The second type of additive are additives able to migrate within the polyurethane slowly over time, which may be random but is often driven by charge or other factors at the surfaces of the polyurethane polymer block or coating. This migration may take place over days or years depending on crosslinking density of the polyurethane, or the size of the embedded additive. These second type additives include metal oxide nanoparticles such as titanium oxide and silicon oxide, cationic metal nanoparticles such as silver and copper particles, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, calcium compounds such as calcium carbonate and calcium hydroxide, and 2-(4,6-Dipheny1-1,3,5-triazin-2-y1)-5-[(hexyl)oxy]-phenol, and any of their derivatives, and combinations thereof.

[0014]
In another alternative, said at least one additive may have an antioxidative property, which may assist in the thermal stability in the polyurethane, as well as other characteristics of the polyurethane (for example but not limited to, shelf life and/or durability), be a transparent or colored dye, an antimicrobial compound or peptide, a colored compound or peptide, an ultra-violet (uv)-resistant compound, an uv-sensitive compound, an infrared-sensitive compound, or increase the surface smoothness, increase the surface hardness and scratch resistance, or increase water repellency and solvent resistance.

Date Recue/Date Received 2021-07-06

[0015]
In the case that the additive is a transparent or colored dye, it may further be thermochromic. The color change may be either dynamically or permanently triggered by changes in temperature. The dye may be uniformly distributed within the composition prior to coating a substrate or material, or be restricted to only one small location on the surface of the coated substrate or material. The latter case may be useful in the application case where the dyed area of the coating is to be used as a static or dynamic temperature marker, or a thermal change indicator. Examples of thermochromic dyes that may be used with the disclosed polyurethane composition include titanium dioxide, zinc oxide, silver mercury iodide, cuprous mercuric iodide, bis(diethylammonium) tetrachlorocuprate, cobalt(II) chloride, any of their derivatives, and combinations thereof.

[0016]
In the case that the additive is an antimicrobial (herein including anti-bacterial and anti-viral functionalities) component, said antimicrobial component is chosen from tertiary ammonium compounds, tertiary phosphonium compounds, quaternary ammonium compounds, alkyl halides, benzotriazole-containing compounds, metal oxides, metal nanoparticles, antibiotics, amino acids, any of their derivatives, and combinations thereof.

[0017]
In one alternative, the antimicrobial component includes compounds with amino and etherified hydroxy groups bound to the same carbon skeleton, having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton, the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted. The oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom.

[0018] In yet another alternative, the antimicrobial compounds comprise:
= N,N-Bis(2-hydroxyethyl)-N-methyldodecan- 1 -aminium salts including but not limited to N,N-Bis(2-hydroxyethyl)-N-methyldodecan-l-aminium chloride and N,N-Bis(2-hydroxyethyl)-N-methyldodecan-1-aminium bromide.
= Bis-(2-Hydroxyethyl)methyl-tetradecylammonium salts, including but not limited to Bis-(2-Hydroxyethyl)methyl-tetradecylammonium chloride = N,N-bis(2-hydroxyethyl)-N-methyl-hexadecan- 1 -ammonium salts, including but not limited to N,N-bis(2-hydroxyethyl)-N-methyl-hexadecan-1-ammonium chloride Date Recue/Date Received 2021-07-06 In one alternative, the antimicrobial compounds have a concentration in the polyurethane coating composition comprising:
= N,N-Bis(2-hydroxyethyl)-N-methyldodecan-l-aminium chloride o 2.5-6% w/w of the dry components in the polyurethane formulation, in one alternative, we found optimal bacteria elimination on a coated surface when used at 5% w/w = N,N-Bis(2-hydroxyethyl)-N-methyldodecan-l-aminium bromide o 1.5-8% w/w of the dry components in the polyurethane formulation, in one alternative, we found optimal bacteria elimination on a coated surface when used at 2.8% w/w = Bis-(2-Hydroxyethyl)methyl-tetradecylammonium chloride o 2.5-6% w/w of the dry components in the polyurethane formulation, in one alternative, we found optimal bacteria elimination on a coated surface when used at 5% w/w.
At the optimal concentration, the antimicrobial components embedded within the polyurethane coating can eliminate between 99.99 - 99.9999% bacteria (various strains) that come into contact with the coated surface, and between 97-99.42% corona-virus surrogate (hCoV-229E) that come into contact with the coated surface.

[0019] In one alternative, said at least optional one catalyst is selected from the group consisting of triethyl amine, dibutyltin dilaurate,1,4-diazabicyclo [2.2.2]
octane, tin(II) 2-ethylhexanoate,(neodecanoate-0)phenylmercury and combinations thereof. In one alternative, said at least one optional catalyst may be added in solid powder or liquid solution form. In one alternative, when said at least one optional catalyst is added as a liquid solution, the solvents used to dissolve it are selected from the group consisting of water, dimethylformamide, acetone, acetonitrile, ethanol, dimethyl sulfoxide, Cyrene(R), chloroform, diethyl carbonate, dimethyl carbonate, tetrahydrofuran, and combinations thereof.

[0020] The polymerization process for the manufacture of the polyurethane composition involves at least one polymerization solvent, which may be selected from the group Date Recue/Date Received 2021-07-06 consisting of water, dimethylformamide, acetone, ethanol, dimethyl sulfoxide, dihydrolevoglucosenone, chloroform, diethyl carbonate, dimethyl carbonate, tetrahydrofuran, and any combinations thereof. The solvent(s) used for the polymerization process may be the same or different from the solvent used to dissolve the said at least one optional catalyst.

[0021] In another alternative, to make the polyurethane formulation curable by ultra-violet (UV) irradiation, a crosslinkable monomer with a free radical, a UV-crosslinker with a free radical, and a photoinitiator may be added. A large range of combinations may be used by people skilled in the art. In one alternative, some examples include, but are not limited to:
= 2-hyroxyethyl acrylate as the crosslinkable monomer with a free radical which may be activated by the presence of a photoinitiator and UV-irradiation = Ethylene Glycol Dimethacrylate as the UV-crosslinker with a free radical which may be activated by the presence of a photoinitiator and UV-irradiation; and = 2,2-Dimethoxy-2-phenylacetophenone as the photoinitiator.

[0022] In another alternative, the combination of monomer + uv-crosslinker +
photoinitiator may be used for a polyurethane coating with or without an antimicrobial component therein

[0023] In one alternative, when the polyurethane composition is used as a coating on a substrate surface, the polyurethane composition may be applied by deposition methods.
Deposition methods primarily include dip, brush, or spray depositions, as understood by persons of ordinary skill in the art, either depositing the polyurethane composition on a substrate surface in its entirety at once, or depositing the polyurethane composition in parts over time to allow a reaction to occur during or between the partial deposits on the substrate surface resulting in the formation of the polyurethane composition. Other methods of deposition may be adapted by persons of ordinary skill in the art, slight modifications may be made to the ratio of dry components to solvents when the composition is adapted for other deposition methods.

[0024] In one alternative, heat curing of the deposited coating is performed to enhance the physical robustness and coefficient of friction of the final formed polyurethane composition. Curing may be performed using a conventional muffle furnace or vacuum Date Recue/Date Received 2021-07-06 oven by heating using either a stepwise approach or at a fixed temperature.
When using fixed temperature, curing may be performed between about 140 C to 200 C for about 40-180 min, more specifically at 140 C for 90 min, 160 C for 60 min, 170 C for 40 min, 180 C for 15 min, 180 C for 30 min, 180 C for 90 min, 200 C for 15 min, or 200 C for 60 min. When using a stepwise approach, heat is ramped up from about 70 C to 170 C at an interval of about 15 C /min, with extended holding times at every 15 to 30 degrees. For example, a stepwise curing program can start at 85 C for 20 min, then with the heat increased to 100 C at about 15 C /min, then hold at 100 C for 20 min, heat increased to 125 C and hold for 60 min, then finally with heat increased to 170 C and heat for 30 min before cooling back down to ambient temperature. Another example program could start at 80 C for 20 min, increase temperature at about 20 C /min, hold at 125 C for 60 min, increase temperature again at about 20 C /min, then finally hold at 170 C for 100 min.

[0025] In one alternative, when used with ammonium salts to be an antimicrobial polyurethane coating, heat curing at about 70-90 C by ramping up heating from room temperature at an interval of about 15-30 C /min for about 2-24 hours is adequate. In yet another alternative, optimal conditions are: ramping up heating from room temperature at 15 C /min, to 80 C, and maintaining the temperature for 4 hours.

[0026] In another alternative, when said polyurethane composition is made into a version that is compatible with UV-curing, by adding the set of monomer + uv-crosslinker +
photoinitiator, curing may be carried out at an intensity of 0.57W/m2, a wavelength of 300-400 nm, for 20 seconds to 2h, at 26-28 C. In yet another alternative, optimal conditions for a UV-curing compatible polyurethane composition are: an intensity of 0.57W/m2, a wavelength of 340 nm, for 5 minutes, at 28 C.

[0027] In one alternative, the final formed polyurethane composition has a density of about 1.17 to 1.27 g/cm2. In one alternative where the composition is coated onto a substrate using dip coating, the final formed polyurethane coating has a thickness of about 10 to 200 m. In another alternative, the final formed polyurethane coating has a thickness of about 10 [tm to 30 [tm. In another alternative, the final formed polyurethane coating has a thickness of about 30 [tm to 80 [tm. In one alternative, on the Vicker's hardness scale, the final formed polyurethane composition has a hardness of between 30-55Hv. In one alternative where the composition is coated onto a substrate using dip Date Recue/Date Received 2021-07-06 coating, the final formed polyurethane composition coating has a hardness of about 45Hv. In one alternative, the polyurethane composition has an adhesion value of about 4-according to the scale established by ATSM D3359-17 Adhesion by Tape test.

[0028]
To reach a desired thickness, the consistency, concentration, and other aspects of the polyurethane composition may be modified as understood by those skilled in the art, when said polyurethane composition is in the liquid form. Multiple layers of the composition may also be applied onto the same substrate over time (optimal optical properties are achieved when the previous layer is fully dried but not cured before applying the next layer). The polyurethane composition presented is optimized for a ceramic or glass substrate, but other suitable substrates include but are not limited to plastic, metal, wood, rubber, and cement. To prepare the substrate surface before the deposition of the polyurethane composition, surface modification agents may be added to the substrate surface.

[0029]
In one alternative, the plastic substrates include, but are not limited to acrylonitrile butadiene styrene (ABS), polyvinyl Chloride (PVC), and acrylics. In another alternative, the metal substrates include, but are not limited to, stainless steel, such as stainless steel type 304.

[0030]
In one alternative, the optional surface modification agent may comprise at least one inorganic oxide or mineral that may be covalently bound to any free hydroxyl group or groups on the surface of the substrate. In one alternative, said at least one inorganic and/or organic oxide suitable for substrate surface modification comprises, but is not limited to, TiO2, TiC14, SiO2, InSn02, CaCO3, ZnO, BaO, ZrO2 siloxane, aluminum silicate, silica, alkoxysilanes, tri-alkoxysilane (such as beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane), tri-alkoxysilane amine, and combinations thereof. The optional surface modification agent(s) are typically applied in liquid form onto the substrate. Therefore, the solvents used to dissolve or suspend the optional surface modification agent(s) include toluene, xylene, butyl acetate, acetone, methylisobutyl ketone, amyl alcohol, propanol, diacetone alcohol, mineral spirits, petroleum naphtha, turpentine, dipentene, pine oil, mineral oil, cyclohexanol, petroleum hydrocarbons, and any Date Recue/Date Received 2021-07-06 combinations thereof. In one alternative, the percentage weight of this surface modification agent in the final formed coating should be between 0-5%.

[0031] In one alternative, alkoxysilanes may include (3-Aminopropyl)triethoxysilane, gamma-glycidoxypropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, vinyltrimethoxysilane, Gamma-methacryloxypropyltrimethoxysilane, 5-hexenyltrimethoxysilane, n-(2-aminoethyl)-3-aminopropylsilanetriol, n-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)amine, dimethyloctadecy13-(trimethoxysilyl)propylammonium chloride, n,n'-bis(3-trimethoxysilylpropyl)urea, [3-(1-piperazinyl)propyl]methyldimethoxysilane, and tris(3-trimethoxysilylpropyl)isocyanurate.

[0032] In yet another alternative, when used with a polyurethane coating with antimicrobial components, we found the surface modification agent bis(3-trimethoxysilylpropyl)amine worked the best for both adhesion as well as solvent resistance. When used on substrate surfaces such as stainless steel, mixing bis(3-trimethoxysilylpropyl)amine with dimethyloctadecy13-(trimethoxysilyl)propylammonium chloride resulted in a superior adhesion score. Without this mixture of surface modification agents, the adhesion score of the antimicrobial polyurethane coating to a stainless steel surface is 2 under the ATSM D3359-17 Adhesion by Tape test. With the mixture of surface modification agents bis(3-trimethoxysilylpropyl)amine with dimethyloctadecy13-(trimethoxysilyl)propylammonium chloride on the stainless steel, the adhesion score of the polyurethane coating improved to 3-5. In addition to improving adhesion score of the polyurethane coating to the substrate surface, surface modification agents may also reduce curing time, balance the pH of the formulation to increase storage stability, reduce static charges on the final coating surface, reduce fouling, reduce corrosion, increase resistance to temperature changes in the surrounding, and increase water resistance.

[0033] In one alternative, the final formed polyurethane composition has a thermal conductance of about 0.025W/mK, coefficient of friction of about 0.63 , and is able to tolerate dry heat of up to 260 C for 60 min without visible change in thickness or color. It is insoluble in water, ethanol, acetone, dimethylformamide, and other commonly used Date Recue/Date Received 2021-07-06 solvents, in addition to being chemically resistant to each of the solvents.
In addition, it tolerates water vapor at 121 C at 15-18psi for at least 30 min.

[0034]
According to one aspect, there is provided a polyurethane composition comprising:
a.
At least one polyfunctional isocyanate with three or more backbone carbons;
b. At least one polyol with at least two hydroxyl groups; and Optionally at least one of c. At least one additive;
d. At least one catalyst;
e. At least one surface modification agent; and combinations thereof.

[0035]
According to one alternative, the polyurethane composition said at least one polyfunctional isocyanate is selected from the group consisting of aromatic, aliphatic, cycloaliphatic, polycyclic, and combinations thereof.

[0036]
According to another alternative, said at least one polyol is selected from the group consisting of 1,4-butanediol, 1, 6 hexanediol, triethylene glycol, glycerol, polyethylene terephthalate, polyethylene succinate, tris(hydroxymethyl)propane, 1,1,1-tri(hydroxymethyl)propane, ethylene glycol, propylene glycol, xylitol, mannitol, 2,3-butanedil, 4,4'-isopropylidenedicyclohexanol, a derivative of the above and combinations thereof.

[0037]
According to another alternative, the polyfunctional isocyanate is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 3-triehtoxysilyl)propyl isocyanate, a derivative of the above and combinations thereof.

[0038]
According to another alternative, the polyurethane composition has a molar ratio of isocyanate functional groups of the polyfunctional isocyanate to hydroxyl groups of the polyol is selected from 1:1, 1:1.1, 1:1.05, 1:1.01, 1.01:1, 1.05:1 and 1.1:1.

[0039]
According to one alternative, said at least one additive being from 0 to about 10%
by molar weight of total reagents excluding solvents.

[0040] According to one alternative, the molar weight is between about 0.1 to about 2%.

[0041]
According to one alternative, the at least one additive is selected from the group consisting of a reactive additive, non-reactive additive and combinations thereof. In one alternative, the reactive additive contains at least one terminal reactive group, wherein said Date Recue/Date Received 2021-07-06 reactive group reacts with i) at least one hydroxyl group of said polyol; ii) an isocyanate group of said multifunctional isocyanate; and combinations thereof. In another alternative, said reactive additive is selected from the group consisting of water, 2,6-di-tert-buty1-4-methylphenol, monohydroxy-terminated poly(dimethyl siloxane), bishydroxy-terminated poly(dimethylsiloxane), poly(ethylene glycol) diglycidyl ether, octafluoro-pentanol, polyethylene terephthalate, polyetheylene succinate, bis-(2-hydroxy-ethyl)-methyl-tetradecyl-ammonium chloride and derivatives thereof.

[0042]
According to one alternative, the non-reactive additive is selected from the group consisting of a metal oxide, a cationic metal, a phosphite compound, a calcium compound, 2-(4,6-dipheny1-1,3,5-triazin-2-y1)-5-[(hexyl)oxy]-phenol, and a derivative of any of the above.

[0043]
According to one alternative, the metal oxide is selected from titanium oxide and silicon oxide; the cationic metal is selected from silver and copper; the phosphite compound is tris(2,4-di-tert-butylphenyl)phosphite; and the calcium compound is selected from calcium carbonate and calcium hydroxide.

[0044]
According to one alternative, the at least one additive further comprises at least one of an antioxidant, a dye, an antimicrobial, a coloured compound, an ultra-violet resistant compound, an ultra-violet sensitive compound, an infrared sensitive compound, a surface smoothness increasing compound, a surface hardness increasing compound, a surface scratch resistance increasing compound, a ware repellent increasing compound, a solvent resistance increasing compound and combinations thereof.

[0045]
In one alternative, the at least one catalyst is selected from the group consisting of triethyl amine, dibutyltin dilaurate, 1,4-diazabicyclo [2.2.2] octane, tin (II) 2-ethylhexanoate, (neodecanoate-0)phenyl mercury, and combinations thereof.

[0046] In one alternative, said at least one catalyst is in solid powder or liquid solution.

[0047]
In one alternative, said catalyst is in liquid solution, said catalyst is dissolved in a solvent selected from the group consisting of water, dimethylformamide, acetone, acetonitrile, ethanol, dimethyl sulfoxide, Cyrene0, chloroform, diethyl carbonate, dimethyl carbonate, tetrahydrofuran, and combinations thereof.

[0048] In one alternative, the polyurethane composition is selected from the group consisting of: [hexane-1,6-diol-alt-l-isocyanato-4-[(4-Date Recue/Date Received 2021-07-06 isocyanatocyclohexyl)methyl]cyclohexane], [1,2,3-propaetriol-alt-1-isocyanato-4[(4-isocyanatocyclohexyl)methyl]cyclohexane] [2-(hydroxymthyl)-2-ethylpropane-1,3-diol-alt-l-i socy anato-4- [(4-i socy anatocyclohexyl)m ethyl]cyclohexane] -ran-[polydimethylsiloxane-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane], [1,2,3 -propaetriol-alt-l-isocyanato-isocyanatocyclohexyl)methyl]cyclohexane]-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate], [(2R,3R,4S)-P entane-1,2,3,4,5-p entol-alt-l-i s ocy anato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Ethane-1,2-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane], and [(2R,3R,4R,5R)-1,2,3,4,5,6-Hexanehexol-alt-l-isocyanato-4-[(44 socyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

[0049] In one alternative, the polyurethane composition has a density of about 1.17 to about 1.27 g/cm2.

[0050] According to another aspect, there is provided the use of a polyurethane composition as a heat resistant coating on a substrate.

[0051] According to one alternative, said substrate is selected from the group consisting of ceramic, glass, plastic, metal, wood, rubber and cement.

[0052] According to another aspect, there is provided coating for a substrate comprising a polyurethane composition as described herein.

[0053] According to one alternative, said substrate is selected from the group consisting of ceramic, glass, plastic, metal, wood, rubber and cement.

[0054] According to one alternative, the coating has a density of about 1.17 to about 1.27 g/cm2.

[0055] According to another alternative, said coating has a thickness of about 10 to 200 gm, and preferably of about 50 to 100 gm.

[0056] According to another alternative, said coating has a hardness of from 30-55 Hv.

[0057] According to another alternative, said coating has an adhesion value of about 4-5 according to ATSM D33359-17.

Date Recue/Date Received 2021-07-06

[0058] According to another alternative, said coating has a thermal conductance of about 0.017 to 0.038 and preferably 0.025 W/mK.

[0059] According to another alternative, said coating has a static coefficient of friction of about 0.6 to 0.8 and preferably 0.631.1.

[0060] According to another alternative, said coating maintains i) structural integrity including visual appearance and transparency; ii) chemical stability (no chemical degradation) and iii) hardness value, adhesion value, thermal conductance and coefficient of friction; at dry heat up to 260C for about 60 minutes.

[0061] According to another alternative, said coating tolerates water vapour at 121 C at 15-18 psi for at least 30 minutes.

[0062] According to another alternative, % light transmittance through said coating after heating at 250 C for at least 30 minutes is at least 95% at a wavelength of from 370 nm to 800 nm.

[0063] According to another aspect, there is provided a process to manufacture a polyurethane composition [hexane-1,6-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. mix 4,4'-methylenebis(cyclohexyl isocyanate), glycerol, and 1,6-hexanediol into N,N-dimethylformamide and allow to stir; in one alternative stifling at 400 rotations per minute (rpm) at 15 - 60 C for 2-20 minutes;
b. add dibutyltin dilaurate.

[0064] According to another aspect, there is provided a process to manufacture a polyurethane composition11,2,3-Propanetriol-alt-l-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. mix 4,4'-methylenebis(cyclohexyl isocyanate), glycerol and butylated hydroxytoluene into N,N-dimethylformamide and allow to stir; in one alternative stifling at 100-400 rpm at 15 - 60 C for 2-20 minutes;
b. add dibutyltin dilaurate in acetone.

[0065] According to another aspect, there is provided a process to manufacture a polyurethane composition [2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
Date Recue/Date Received 2021-07-06 a. mix 4,4'-methylenebis(cyclohexyl isocyanate), tris(hydroxymethyl)propane, and poly(dimethylsiloxane) into N,N-dimethylformamide and allow to stir to make a polyurethane reaction solution; in one alternative stirring at 100-400 rpm at 15 - 60 C for 2-4 hours;
b. dissolve dibutyltin dilaurate in acetone and add into the polyurethane reaction solution.

[0066] According to another aspect, there is provided a process to manufacture a polyurethane composition [1,2,3-Propanetriol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate]: said process comprising:
a. dissolve polymethyl methacrylate-co-ethyl acrylate, tris(hydroxymethyl)propane, glycerol, 1,4-butanediol, and 4,4'-Methylenebis(cyclohexyl isocyanate) in tetrahydrofuran and allowed to stir to make a polyurethane reaction solution; in one alternative stirring at 100-400 rpm at 15 - 60 C for 30-60 minutes;
b. add a dibutyltin dilaurate solution into the polyuerethane reaction solution.

[0067] According to another aspect, there is provided a process to manufacture a polyurethane composition [(2R,3R,4S)-Pentane-1,2,3,4,5-pentol-alt-1-isocyanato-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Ethane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. dissolve xylitol in N,N-dimethylformamide to form a solution;
b. mix the solution with 4,4'-methylenebis(cyclohexyl isocyanate), ethylene glycol, 2-(4,6-dipheny1-1,3,5-triazin-2-y1)-5-[(hexyl)oxy]-phenol, butylated hydroxytoluene, and Tris(2,4-di-tert-butylphenyl) phosphite and allow to stir to make a homogeneous polyurethane reaction solution; in one alternative stifling at 100-400 rpm at 140 -190 C for 10-20 minutes;
c. cool to ambient temperature and add dibutyltin dilaurate catalyst solution.

[0068] According to another aspect, there is provided a process to manufacture a polyurethane composition [(2R,3R,4R,5R)-1,2,3,4,5,6-Hexanehexol-alt-1-isocyanato-4-Date Recue/Date Received 2021-07-06 [(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocy clohexyl)methyl]cyclohexanet said process comprising:
a. mix mannitol, propylene glycol, butylated hydroxytoluene, 4,4'-methylenebis(cyclohexyl isocyanate) and tris(2,4-di-tert-butylphenyl) phosphite in N,N-dimethylformamide and allow to stir to make a homogeneous polyurethane reaction solution; in one alternative stifling at 100-400 rpm at 140-190 C for 10-20 minutes;
b. cool the solution to ambient temperature and add dibutyltin dilaurate solution.

[0069]
According to another aspect, there is provided a process to manufacture a polyurethane composition with quaternary ammonium compounds as antimicrobial additives, said process comprising:
a. add an polyfunctional isocyanate with at least one functional group, a quaternary ammonium compound with at least one optional terminal hydroxyl group, and a polyol with at least two terminal hydroxyl groups selected for polyurethane formation into N,N-dimethylformamide wherein the isocyanate functional groups of the polyfunctional isocyanate to the sum of i) the terminal hydroxyl groups on the polyol and ii) the optional terminal hydroxyl groups of the quaternary ammonium compound and iii) the amino groups of the quaternary ammonium compound has a molar ratio of from 1:1 to 1.1:1, and mix until solution becomes homogenous;
b. add dibutyltin dilaurate;
c. wherein said quaternary ammonium compound is present in the polyurethane composition at a final concentration of between 1.5-8% w/w.

[0070]
According to another alternative, said glass substrate includes primary pharmaceutical packaging, digital display, architectural window glass; said plastic substrate includes vehicle interior; and said metal substrate include metal containers.

[0071]
According to another alternative, said polyurethane composition is heat tolerable, maintains hardness, adhesion and coefficient of friction within the temperature under the dotted curve of the following graph:

Date Recue/Date Received 2021-07-06 Time-temperature combinations of polyurethane compositions 300 r 250 ¨
_ a 200 100 _______________ 50 ______________________________________________________________________ Time (min)

[0072]
Several advantages of the disclosed polyurethane composition include tolerance to high heat, surface smoothness, low surface friction, resistance to scratching, anti-oxidation, transparency, and biocompatibility. In addition, it keeps the advantages of conventional polyurethane such as corrosion resistance, durability, processability, and ease of application onto the substrate surface.

[0073]
Additionally, depending on the specific method of application or intended use case, the polyurethane composition may be used along with other components including: i) fillers selected from, but not limited to a siliceous filler, ii) extenders, iii) flow additives, iv) hardeners, v) pigments selected from, but not limited to, barium sulfate, calcium sulfate, or magnesium silicate, or vi) other additives to modify the texture of the polyurethane composition.

[0074]
In one alternative, applications of the polyurethane composition include, but are not limited to, external coating of a primary packaging vial made of glass, ceramic and combinations thereof, for pharmaceutical and therapeutic packaging; external coating of a food-grade glass or ceramic bottle; external coating of a medical-grade glass or ceramic substrate surface; and the external coating of a glass or ceramic pane on vehicles or building structures; surface of furniture in food preparation areas; wall and equipment surface in Date Recue/Date Received 2021-07-06 hospitals; surface of medical and electrical devices; and surfaces of public transportation fixtures.

[0075] The specifications described herein are one alternative general guidelines for producing the polyurethane composition described herein, while minor variations in the specific chemical composition used may be made by persons skilled in the art for situations of unique application.
BRIEF DESCRIPTION OF THE DRAWINGS

[0076] The disclosure, together with additional objects, features, advantages and aspects thereof, will be best understood from the following description, the appended claims and the accompanying drawings, in which:

[0077] Figure 1 depicts the structure of the polyurethane [hexane-1,6-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane] of the heat tolerant polyurethane composition formed by following Example 1.

[0078] Figure 2 depicts the structure of the polyurethane [(2R,3R,45)-Pentane-1,2,3,4,5-pentol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Ethane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane] of the polyurethane composition formed by following Example 5.

[0079] Figures 3A and 3B provide the visual appearance of glass bottles uncoated as well as coated and cured with the polyurethane composition following Example 5.

[0080] Figure 4A provides percent light transmittance of the polyurethane composition as per Example 5, according to one alternative, after being coated onto a glass slide, the same polyurethane composition after being coated onto a glass slide and subjected to dry heat at 250 C for more than 30 minutes, and an uncoated glass slide for reference.

[0081] Figure 4B provides the light absorbance across the visible light and ultra-violet regions (190-1000nm), of a heat-tolerable polyurethane film made by using the polyurethane composition according to Example 6, prior to any heat or depyrogenation challenges.

[0082] Figures 5A, 5B and 5C provide Fourier-transform infrared spectroscopy of the extractant from the polyurethane composition, according to Example 5, through a glass Date Recue/Date Received 2021-07-06 surface in water (FIG. 5A), dimethylformamide (FIG. 5B), and acetone (FIG 5C) after 5 hours, 1 month, and 4 months respectively.

[0083] Figure 6 provides the thermal gravimetric analysis of one alternative of the polyurethane composition.

[0084] Figure 7 depicts the structure of the polyurethane [(2R,3R,4R,5R)-1,2,3,4,5,6-Hexanehexol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-di ol-alt-l-i s ocy anato-4- [(4-i s ocy anatocycl ohexyl)m ethyl] cyclohexane] of the polyurethane composition formed by following Example 6.

[0085] Figure 8 is a table providing the characteristics of hardness, adhesion and static coefficient of friction of the polyurethane composition formed following Example 6, after the polyurethane composition is subjected to various time-temperature conditions.

[0086] Figure 9 is a graph of the time-temperature conditions of Figure 8.

[0087] Figure 10 depicts the structure of the polyurethane [1,2,3-Propanetriol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane] formed by following Example 2.

[0088] Figure 11 depicts the structure of the polyurethane [2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane] formed by following Example 3.

[0089] Figures 12A and 12 B depict a blend including a polyurethane and a polymethylmethacrylate-co-polyethylacrylate formed by following the procedure in Example 4, as per the disclosure, [1,2,3-Propanetriol-alt-l-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexanej-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-di ol-alt-l-is ocy anato-4- [(4-i socy anatocy cl ohexyl)m ethyl]cycl ohexanej-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate]formed by following Example 4.

[0090] Figure 13 provides a table of bacteria elimination efficacy results of one alternative of the polyurethane composition on stainless steel where antimicrobial components are added to the polyurethane composition, formed by following Example 8.
The bacteria elimination testing used ISO 22196:2011 protocol. The various bacteria Date Recue/Date Received 2021-07-06 families tested included Staphylococcus Aureus, Pseudomonas Aeruginosa, and Salmonella Enterica.

[0091] Figure 14 provides the corona-virus surrogate (hCoV-229E) elimination efficacy results on stainless steel of one alternative of the polyurethane composition where antimicrobial components are added, formed following Example 8. The viral surrogate elimination testing used ISO 21702:2011 protocol.

[0092] Figure 15A provides the weathering resistance results as tested using ASTM
D5894-16 using the polyurethane composition formed by following Example 5 coated on stainless steel panels.

[0093] Figures 15B and 15C provide the visual appearance of polyurethane composition prepared following Example 5 coated on stainless steel panels, before (Fig.
15B) and after (FIG. 15C) challenged with salt fog/ UV exposure weathering cycles under ASTM
D5894-16.
DETAILED DESCRIPTION OF THE DISCLOSURE

[0094] The present disclosure will now be described more fully, with reference to the accompanying drawings, in which several alternatives are shown. This disclosure may be embodied in many different forms and should not be construed as limited to the alternatives set forth here.

[0095] Within the context of this application, the term "derivative" when used with respect to a monomer, oligomer, or polymer of a hydrocarbon, anhydride, acrylic or urethane means that the monomer, oligomer, or polymer of the hydrocarbon, anhydride, acrylic or urethane has at least one modification to the side chain groups and/or functional units. The at least one modification to the side chain group and/or functional units may be the alteration, addition, or reduction of single atoms, halogens, straight-chain or branched alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, aromatic, hydroxy, carboxy, nitro, cyano, isocyano, thiocyano, isothiocyano, or azide groups to one or more repeating units of the monomer, oligomer or polymer.

[0096] As used herein, the term "pharmaceutical agent" means any active pharmaceutical ingredient known the art in view of the present disclosure. Preferably, a pharmaceutical agent is a biopharmaceutical agent. Biopharmaceutical agents are typically sensitive to Date Recue/Date Received 2021-07-06 heat and temperature fluctuations, e.g., temperature increases.
Examples of biopharmaceutical agent include, but are not limited to, vaccines, monoclonal and recombinant-antibody drugs, genetic and cellular therapies, and other biologic drugs.

[0097]
As used herein, the term "biocompatible" refers to a substance or material that is not harmful or toxic to living humans and animals when ingested, contact exposed, or implanted.

[0098]
Referring now to FIG. 1, there is shown the chemical structure of a polyurethane formed by following the procedure in Example 1, as per the disclosure, [hexane-1,6-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

[0099]
Referring now to FIG. 2, there is shown the chemical structure of another polyurethane formed by following the procedure in Example 5, as per the disclosure, [(2R,3R,4S)-Pentane-1,2,3,4,5-pentol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexanej-ran-[Ethane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

[00100] Referring now to FIGS. 3A and 3B, there is shown glass bottles (as an example of a substrate), wherein one glass bottle was coated with one alternative of the polyurethane composition prepared by following the procedure in Example 5, via dipping and heat curing, as per the disclosure. In FIG. 3A the bottom bottle is coated and the top bottle is uncoated. In FIG. 3B, the right bottle is coated and the left bottle is uncoated. As may be seen the visual appearance and thus the transparency is essentially the same for both the coated and uncoated bottles.

[00101] Referring now to FIG. 4A, there is shown percent light transmittance data of an uncoated flat glass slide ("reference"), the same type of slide dip coated on a single side with one alternative of the polyurethane formulation prepared by following the procedure in Example 5 ("coated"), and the same type of slide dip coated on a single side after being subjected to dry heat treatment at 250 C for at least 30 minutes excluding oven ramp up and cool down time ("coated, heated"). As may be seen by the data, the coated sample has percent light transmittance that closely conforms to that of the reference, demonstrating that the coating exhibits high transparency within the visual spectrum (between 370 to 800nm). Further, the coated, heated sample has a percent light transmittance that generally conforms to that of the reference, only decreasing to 95% near the infrared end of the Date Recue/Date Received 2021-07-06 spectrum (370nm), demonstrating that the polyurethane maintains high transparency after being subjected to high heat.

[00102] Referring now to FIG. 4B, there is shown the light absorbance across the visible light and ultra-violet regions (190-1000nm) of a film made by using one alternative of the polyurethane formulation prepared by following the procedure in Example 6 prior to any heat or depyrogenation challenges. As may be seen by the data, the film demonstrated light absorbance above 1.5 in the ultraviolet region between 190-226nm, corresponding to less than 4% of transmittance in that region. Further, the film demonstrated light absorbance above 1.0 in the ultraviolet region between 227-384nm, corresponding to less than 10% of transmittance in that region. The absorbance maintains below 0.5 in the visible light and infrared regions between 399-1000nm, corresponding to visible transparency to the eye.
The results confirm the film is able to block both UV-A and UV-B light transmission.

[00103] Referring now to FIGS. 5A, 5B and 5C, there is shown Fourier-transform infrared spectroscopy confirming no detectable extractants from the composition coated on a glass surface, in water (FIG. 5A), in dimethylformamide (FIG 5B), and in acetone (FIG 5C) after 5 hours, 1 month, and 4 months at ambient temperature storage respectively.
Extractants through an uncoated glass surface is provided for reference. In all of FIGS.
5A, 5B AND
5C, the spectroscopy data does not show contamination (i.e. extractants) from the coating (i.e. peaks exemplified by isocyanate or additive groups under all conditions), demonstrating the polyurethane composition coating's stability on glass surface during ambient storage, and that it does not corrode or leach through glass.

[00104] Referring now to FIG. 6, there is shown thermal gravimetric analysis of one alternative of the polyurethane composition. The percent weight is shown as a dashed line, while derivative of percentage weight is shown in solid line. As may be seen by the data, the polyurethane composition begins to experience weight loss when temperature exceeds 250 C, with the most significant weight loss occurring at 295-300 C. This further demonstrates the ability of the polyurethane composition disclosed to tolerate heat past 250 C without significant changes in weight or mass.

[00105] Referring now to FIG. 7, there is shown the chemical structure of a polyurethane formed by following the procedure in Example 6, as per the disclosure, [(2R,3R,4R,5R)-1,2,3,4,5,6-}lexanehexol-alt-1-isocyanato-4-[(4-Date Recue/Date Received 2021-07-06 isocyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

[00106] Referring now to FIG. 8, there is provided a table of time temperature combination conditions of a polyurethane composition of Example 6, and the associated hardness, adhesion and coefficient of friction measurements of said polyurethane composition, it may be seen that the polyurethane composition maintains hardness, adhesion and coefficient of friction after being subjected to various time/temperature conditions.

[00107] Referring now to FIG. 9, the graph provides a dotted line such that the polyurethane compositions of as per Examples 5 and 6 exhibit the desired property of high heat tolerance described herein at all conditions under the dotted line.

[00108] Referring now to FIG. 10, there is shown the chemical structure of a polyurethane formed by following the procedure in Example 2, as per the disclosure, [1,2,3-Propanetriol-alt-l-i socy anato-4- [(4-i socy anatocyclohexyl)m ethyl] cyclohexane] .

[00109] Referring now to FIG. 11 there is shown the chemical structure of a polyurethane formed by following the procedure in Example 3, as per the disclosure, [2-(hydroxym ethyl)-2-ethylpropane-1,3 -di ol-alt-l-i s ocy anato-444-i socyanatocyclohexyl)methyl] cyclohexane]-ran- [polydimethylsiloxane-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

[00110] Referring now to FIGS. 12A and 12 B, there is shown the chemical structures of each compound forming a blended compositions including a polyurethane (FIG.
12A) and a polymethylmethacrylate-co-polyethylacrylate (FIG. 12B) formed by following the procedure in Example 4, as per the disclosure, [1,2,3-Propanetriol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-di ol-alt-l-is ocy anato-4- [(4-i socy anatocy clohexyl)m ethyl]cyclohexan e]-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate].

[00111] Referring now to FIG. 13, there is shown the bacteria elimination efficacy of a film on stainless steel, made by using one alternative of the polyurethane formulation by following the procedure in Example 8. The bacteria elimination testing used ISO
22196:2011 protocol. The various bacteria families tested included Staphylococcus Aureus, Pseudomonas Aeruginosa, and Salmonella Enterica. It can be seen that a log Date Recue/Date Received 2021-07-06 reduction of at least 5 is consistently achieved by the polyurethane formulation with N,N-bis(2-hydroxyethyl)-N-methyldodecan-1-aminium bromide as the antimicrobial component across all three bacteria families. In the S. Aureus study, the polyurethane coating was able to eliminate 99.9999% of the colony-forming units (CFU) after being in contact with the bacteria culture for 30 minutes. In the P. Aeruginosa study, the polyurethane coating was able to eliminate 99.99% of the colony-forming units (CFU) after being in contact with the bacteria culture for 24 hours. In the S.
Enterica study, the polyurethane coating was able to eliminate 99.995% of the colony-forming units (CFU) after being in contact with the bacteria culture for 24 hours, and was able to eliminate 99.9921% of it within the first 10 minutes of contact.

[00112] Referring now to FIG. 14, there is shown the corona-virus surrogate (hCoV-229E) elimination efficacy of a film on stainless steel made by using one alternative of the polyurethane formulation by following the procedure in Example 8. The viral surrogate elimination testing used ISO 21702:2011 protocol. It can be seen that, the polyurethane coating with N,N-bis(2-hydroxyethyl)-N-methyldodecan-1-aminium bromide as the antimicrobial component was able to eliminate up to 99% of the colony-forming units (CFU) after being in contact with the viral culture for 10 minutes, and generally above 97% within 30 minutes, and up to 99.4% when it is in contact with the viral culture for 24 hours.

[00113] Referring now to FIG. 15A, there is shown the weathering resistance results of a coating on a stainless steel panel, made by using one alternative of the polyurethane formulation by following the procedure in Example 5. Weatherability test ASTM

16 was used to challenge the coating with cyclic salt/fog followed by UV
exposure for 1000 hours, which is used to simulate more than 1 year of severe outdoor weather in the northern hemisphere. As may be seen, the results demonstrate the coated stainless steel panel resists degradation such that low rust formation and a low to medium degree of blister formation occurs on the coated stainless steel panel only after 1000 hours of weatherability challenge. The polyurethane coating may be suitable for outdoor use and survive natural weather conditions in the Northern hemisphere as well as provide anti-rust and anti-weathering protection to the stainless steel panel.
Date Recue/Date Received 2021-07-06

[00114] Referring now to FIGS. 15B and 15C, there is shown the coated stainless steel panels before (FIG. 15B) and after (FIG. 15C) the challenge of the coated stainless steel panels of FIG. 15A. It can be seen that the bulk body of the coating is unchanged, with some accumulations of salt spots on it (SEE FIG. 15C). As demonstrated by Figure 15A, some blistering was present but the coating proved to be robust for outdoor uses.
EXAMPLES

[00115]
With the sole intention of illustrating certain principles and practices of the disclosure, and by no way limiting the scope of the disclosure, we provide here example compositions that may be used to externally coat a glass substrate.
Example 1: Polyurethane: [hexane-1,6-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]

[00116]
1.4705g 4,4'-methylenebis(cyclohexyl isocyanate), 0.2095g glycerol, and 0.1080g 1,6-hexanediol were mixed into 1.50m1N,N-dimethylformamide and allowed to stir at 200 rpm and 25 C for 5 minutes. 0.0033g dibutyltin dilaurate was added as the catalyst and the solution was further mixed for 2 minutes. 0.20mL of the polyurethane was cast onto a flat glass slide. The sample was then allowed to air dry for 8 hours at room temperature before heat curing at 160 C in a ventilated oven for 60min. Once cured, the thickness of the polyurethane film was 80 gm, and had a hardness of 25 on the Vicker's Hardness scale, a peel score of 4.5 under the ASTM D3359-17, and full transparency. The coating was stable after being dry heat challenged at 225 C for at least 60min.
Example 2: Polyurethane: [1,2,3-Propanetriol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]

[00117]
1.3672g 4,4'-methylenebis(cyclohexyl isocyanate), 0.3047g glycerol, and 0.0188g butylated hydroxytoluene were mixed into 1.50m1 N,N-dimethylformamide and allowed to stir at 350 rpm for 10 minutes to make a polyurethane reaction solution. A
separate catalyst solution was made by dissolving lg dibutyltin dilaurate in 10m1 acetone. 50 1 catalyst solution was added into the polyurethane reaction solution and further mixed for 2 minutes. The solution temperature was closely monitored using a digital thermometer.

Date Recue/Date Received 2021-07-06 When the solution temperature increased to 38 C, 0.20m1 of the polyurethane was cast onto a flat glass slide by spraying. The sample was then allowed to air dry for 6 hours at room temperature before heat curing at 160 C in a vacuum oven for 60min. Once cured, the polyurethane had a hardness of 32 on the Vicker's Hardness scale, a peel score of 4 under the ASTM D3359-17, and full transparency. The coating was stable after being dry heat challenged at 225 C for at least 60min.
Example 3: Polyurethane: [2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexanej-ran-[polydimethylsiloxane-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]

[00118] 1.4429g 4,4'-methylenebis(cyclohexyl isocyanate), 0.4468g tris(hydroxymethyl)propane, and 0.0280g poly(dimethylsiloxane) were mixed into 1.50m1 N,N-dimethylformamide and allowed to stir at 100 rpm for 3.5h to make a polyurethane reaction solution. A separate catalyst solution was made by dissolving 0.01g dibutyltin dilaurate in 0.100m1 acetone, and added into the polyurethane reaction solution and further mixed for 4 minutes. The solution temperature was closely monitored using a digital thermometer. When the solution temperature increased to 41 C, 0.10m1 of the polyurethane composition was cast onto a flat glass slide that was previously primed using an alkyl silane solution for better adhesion. The sample was then allowed to air dry for 6 hours at room temperature before heat curing at 180 C in a ventilated oven for 15 mins. Once cured, the thickness of the polyurethane film was 50 gm, and had a hardness of 40 on the Vicker's Hardness scale, a peel score of 5 under the ASTM D3359-17, and full transparency. The coating was stable after being subject to dry heat challenged at 250 C for at least 30min.
Example 4: polyurethane with acrylate additives for water resistance: [1,2,3-Propanetriol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexanej-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate]

[00119] 0.0543g polymethyl methacrylate-co-ethyl acrylate, 1.4429g 1,1,1-tris(hydroxymethyl)propane, 0.1763g glycerol, 0.0451g 1,4-butanediol, and 1.386g 4,4'-Methylenebis(cyclohexyl isocyanate) were dissolved in 2m1tetrahydrofuran. The reagents Date Recue/Date Received 2021-07-06 were allowed to stir at 100 rpm and for 60min to make a polyurethane reaction solution.
0.5m1 of a 10% w/v dibutyltin dilaurate catalyst solution was added into the reaction solution and further mixed for 5min. The solution temperature was closely monitored using a digital thermometer. When the solution temperature increased to 38 C, 0.10m1 of the polyurethane composition was cast onto a flat glass slide by spreading. The sample was then allowed to air dry for 6 hours at room temperature before heat curing at 140 C in a ventilated oven for 60 min. Once cured, the polyurethane had a hardness of 45 on the Vicker's Hardness scale, a peel score of 5 under the ASTM D3359-17, and full transparency. The coating was stable after being dry heat challenged at 250 C
for at least 30min.
Example 5: polyurethane with antioxidative additives: [(2R,3R,4S)-Pentane-1,2,3,4,5-pentol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Ethane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

[00120] 7.6g xylitol was first dissolved in 100 ml N,N-dimethylformamide at 100 C for 10min. The solution was then mixed with 72.2g 4,4'-methylenebis(cyclohexyl isocyanate), 0.25g ethylene glycol, 0.007g 2-(4,6-dipheny1-1,3,5-triazin-2-y1)-5-[(hexyl)oxy]-phenol, 0.5g butylated hydroxytoluene, and 0.004g of Tris(2,4-di-tert-butylphenyl) phosphite. The solution was further allowed to stir at 185 C and for 15min to make a polyurethane reaction solution. Once the solution was homogenous it was cooled to ambient temperature before adding 3m1 of a 10%w/v dibutyltin dilaurate catalyst solution and further stirred for 15 min. Prearranged arrays of glass bottles and flat glass slides were lowered into a wide container to dip coat with the polyurethane solution at this time. The bottles or slides were submerged in the solution for 1 Os before they were allowed to air dry for 30min at room temperature before a stepwise heat curing program. The curing started at 85 C
for 20min, then 100 C for 20 min, then 125 C for 60min, and finally 170 C for 30min. Once cured, the thickness of the polyurethane film was 73 gm, and had a hardness of 50 on the Vicker's Hardness scale, a peel score of 5 under the ASTM D3359-17, and full transparency. The coating was stable after being dry heat challenged at 250 C for at least 60min, and compatible with moist heat sterilization at 121 C between 15-18psi for at least 30min.

Date Recue/Date Received 2021-07-06 Example 6: Polyurethane: [(2R,3R,4R,5R)-1,2,3,4,5,6-Hexanehexol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]

[00121] 0.1518g mannitol, 0.1902g propylene glycol, 0.2204g butylated hydroxytoluene, 1.4429g 4,4'-methylenebis(cyclohexyl isocyanate) and 0.002g tris(2,4-di-tert-butylphenyl) phosphite were mixed in 1.8 ml N,N-dimethylformamide. The solution was further allowed to stir at 185 C and for 30min to make a polyurethane reaction solution. Once the solution was homogenous it was cooled to ambient temperature before adding 0.1 ml of a 10%w/v dibutyltin dilaurate catalyst solution and further stirred for 15 min. Then polyurethane composition was cast onto a flat glass slide by spreading. The curing started at 85 C for 20min, then 100 C for 20 min, then 125 C for 60min, and finally 170 C for 30min. Once cured, the thickness of the polyurethane film was 73 gm, and had a hardness of 50 on the Vicker's Hardness scale, a peel score of 5 under the ASTM D3359-17, and full transparency. The coating was stable after being dry heat challenged at 250 C
for at least 60min, and compatible with moist heat sterilization at 121 C between 15-18psi for at least 30min.
Example 7: Polyurethane with antimicrobial components: [2-(2-hydroxypropoxy)propan-1 -ol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Poly(dimethylsiloxane)-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[dodecyl-bis(2-hydroxyethyl)-methylazanium;bromide-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane];N-(3-trimethoxysilylpropyl)butan-1-amine

[00122] 18g N,N-bis(2-hydroxyethyl)-N-methyldodecan- 1 -aminium bromide was first dissolved in 210 ml N,N-dimethylformamide at 60 C by stifling at 600rpm for 10min. The solution was then mixed with 98.8g 4,4'-methylenebis(cyclohexyl isocyanate), 110.3g polypropylene glycol and 37.5g polydimethylsiloxane. 6m1 of a 4%w/v dibutyltin dilaurate (in acetone) catalyst solution was then added to the mixture. The mixture was further allowed to stir at 60 C and for lh to result in a polyurethane reaction solution. The solution was cooled to ambient temperature, 86.6g n-butylaminopropyltrimethoxysilane was added, and the solution was further stifled for 15 min at 30 C. The antimicrobial polyurethane Date Recue/Date Received 2021-07-06 composition was cast onto a stainless steel #304 panel using a spray nozzle.
The curing started room temperature, with the temperature ramp increasing at 15 C/min until 80 C
was maintained for 4 hours. Once cured, the thickness of the polyurethane film was 40 m, and had a peel score of 2 under the ASTM D3359-17, and full transparency. The formed coating as smooth visually and to the touch, and was not susceptible to contact with water for 2-5 minutes at a time.
Example 8: Same as Example 7 but the stainless steel #304 panel is first treated with a surface modification solution. Preparation of the surface modification solution is provided.

[00123] Surface modification solution: A 42% w/w solution (although an acceptable range is from about 40-62% w/w) of dimethyloctadecy13-(trimethoxysilyl)propylammonium chloride is made with methanol as the solvent. The dimethyloctadecy13-(trimethoxysilyl)propylammonium chloride solution was then mixed at a ratio of 1:1 v/v (although an acceptable range is from about 2:3 to 3:2 v/v) to a 97% bis(3-trimethoxysilylpropyl)amine solution. The mixture was stirred at 400 rpm at ambient temperature (although an acceptable range is from about 13-30 C) for 15 minutes (although an acceptable range is from about 5-30 minutes) to ensure homogeneity. This surface modification solution was sprayed onto the surface of a stainless steel #304 panel prior to treating the panel with the antimicrobial polyurethane solution of Example 7 and below.

[00124] Antimicrobial polyurethane solution: 18g N,N-bis(2-hydroxyethyl)-N-methyldodecan-1-aminium bromide was first dissolved in 210 ml N,N-dimethylformamide at 60 C by stirring at 600rpm for 10min. The solution was then mixed with 98.8g 4,4'-methylenebis(cyclohexyl isocyanate), 110.3g polypropylene glycol and 37.5g polydimethylsiloxane. 6m1 of a 4%w/v dibutyltin dilaurate (in acetone) catalyst solution was then added to the mixture. The mixture was further allowed to stir at 60 C
and for lh to result in a polyurethane reaction solution. The solution was cooled to ambient temperature, 86.6g n-butylaminopropyltrimethoxysilane was added, and the solution was further stirred for 15 min at 30 C. The antimicrobial polyurethane composition was sprayed onto the stainless steel #304 panel which was pre-treated with the surface modification solution. The curing started room temperature, with the temperature ramp Date Recue/Date Received 2021-07-06 increasing at 15 C/min until 80 C was maintained for 2 hours. Once cured, the thickness of the polyurethane film was 40 gm, and had a peel score of 4 under the ASTM
D3359-17, and full transparency. The formed coating as smooth visually and to the touch.
The coating was not susceptible to contact with water, ethanol, saline solution, or common cleaning solutions such as Lysol when exposed for 10-20 minutes at a time.

[00125] Pathogen elimination studies of coatings formed from this example are illustrated in FIG. 13 and 14.
Example 9: UV-curable polyurethane with antimicrobial components: polyurethane with antimicrobial additives: [2-(2-hydroxypropoxy)propan-1-ol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Poly(dimethylsiloxane)-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[dodecyl-bis(2-hydroxyethyl)-methylazanium;bromide-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane];2-hydroxyethyl prop-2-enoate

[00126] 9g N,N-bis(2-hydroxyethyl)-N-methyldodecan-1-aminium bromide was first dissolved in 120 ml N,N-dimethylformamide at 60 C for 10min. The solution was then mixed with 48.9g 4,41-methylenebis(cyclohexyl isocyanate), 54.6g polypropylene glycol and 18.6g polydimethylsiloxane. 3m1 of a 4%w/v dibutyltin dilaurate (in acetone) catalyst solution was then added to the mixture. The solution was further allowed to stir at 55 C
and for 1 hour to make a polyurethane reaction solution. Once the prepolymer was made, 57.6g 2-hydroxyethyl acrylate was added and the reaction continued for 1 hour at 60 C.

[00127] 10% w/v ethylene glycol dimethacrylate and 2% w/v of 2,2-dimethoxy-2-phenylacetophenone are added when the prepolymer is ready to be applied to the substrate surface, such as stainless steel #304 in this case. The addition of the two compounds enables the solution to be cured by UV-irradiation at 254nm with and intensity of 0.57W/m2 within 4 hours at 26 C.

Date Recue/Date Received 2021-07-06

Claims

CLAIMS:
I. A polyurethane composition comprising:
a. At least one polyfunctional isocyanate with three or more backbone carbons;
b. At least one polyol with at least two hydroxyl groups; and Optionally at least one of c. At least one additive;
d. At least one catalyst;
e. At least one surface modification agent; and combinations thereof.
2. The polyurethane composition of claim 1 wherein said at least one polyfunctional isocyanate is selected from the group consisting of aromatic, aliphatic, cycloaliphatic, polycyclic, and combinations thereof.
3. The polyurethane composition of claim 1 or 2 wherein said at least one polyol is selected from the group consisting of 1,4-butanediol, 1, 6 hexanediol, triethylene glycol, glycerol, polyethylene terephthlate, polyethylene succinate, tris(hydroxymethyl)propane, 1,1,1-tri(hydroxymethyl)propane, ethylene glycol, propylene glycol, xylitol, mannitol, 2,3-butanedil, 4,4'-isopropylidenedicyclohexanol, a derivative of the above and combinations thereof.
4. The polyurethane composition of any one of claims 2 or 3, wherein the polyfunctional isocyanate is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 3-triehtoxysily0propyl isocyanate, a derivative of the above and combinations thereof.
5. The polyurethane composition of any one of claims 1-4, with a molar ratio of isocyanate functional groups of the polyfunctional isocyanate to hydroxyl groups of the polyol is selected from 1:1, 1:1.1, 1:1.05, 1:1.01, 1.01:1, 1.05:1 and 1.1:1.
6. The polyurethane composition of any one of claims 1-5, with said at least one additive being from 0 to about 10% by molar weight of total reagents excluding solvents.

Date Recue/Date Received 2021-07-06 7. The polyurethane composition of claim 6 wherein the molar weight is between about 0.1 to about 2%.
8. The polyurethane composition of any one of claims 1-7 wherein the at least one additive is selected from the group consisting of a reactive additive, non-reactive additive and combinations thereof.
9. The polyurethane composition of claim 8 wherein the reactive additive contains at least one terminal reactive group, wherein said reactive group reacts with i) at least one hydroxyl group of said polyol; ii) an isocyanate group of said multifunctional isocyanate;
and combinations thereof.
10. The polyurethane composition of claim 9 wherein said reactive additive is selected from the group consisting of water, 2,6-di-tert-buty1-4-methylphenol, monohydroxy-tenninated poly(dimethyl siloxane), bishydroxy-tenninated poly(dimethylsiloxane), poly(ethylene glycol) diglycidyl ether, octafluoro-pentanol, polyethylene terephthalate, polyetheylene succinate, bis-(2-hydroxy-ethyl)-methyl-tetradecyl-ammonium chloride and derivatives thereof.
11. The polyurethane composition of claim 8 wherein the non-reactive additive is selected from the group consisting of a metal oxide, a cationic metal, a phosphite compound, a calcium compound, 2-(4,6-dipheny1-1,3,5-triazin-2-y1)-5-[(hexyl)oxy]-phenol, and a derivative of any of the above.
12. The polyurethane composition of claim 11 wherein the metal oxide is selected from titanium oxide and silicon oxide; the cationic metal is selected from silver and copper; the phosphite compound is tris(2,4-di-tert-butylphenyl)phosphite; and the calcium compound is selected from calcium carbonate and calcium hydroxide.
13. The polyurethane composition of any one of claims 1-12, wherein the at least one additive further comprises at least one of an antioxidant, a dye, an antimicrobial, a coloured compound, an ultra-violet resistant compound, an ultra-violet sensitive compound, an infrared sensitive compound, a surface smoothness increasing compound, a surface hardness increasing compound, a surface scratch resistance increasing Date Recue/Date Received 2021-07-06 compound, a ware repellent increasing compound, a solvent resistance increasing compound and combinations thereof.
14. The polyurethane composition of any one of claims 1-13, wherein the at least one catalyst is selected from the group consisting of triethyl amine, dibutyltin dilaurate, 1,4-diazabicyclo [2.2.2] octane, tin (II) 2-ethylhexanoate, (neodecanoate-0)phenyl mercury, and combinations thereof.
15. The polyurethane composition of claim 14, wherein said at least one catalyst is in solid powder or liquid solution.
16. The polyurethane composition of claim 15, wherein when said catalyst is in liquid solution, said catalyst is dissolved in a solvent selected from the group consisting of water, dimethylformamide, acetone, acetonitrile, ethanol, dimethyl sulfoxide, Cyrenee, chloroform, diethyl carbonate, dimethyl carbonate, tetrahydrofuran, and combinations thereof.
17. The polyurethane composition of any one of claims 1-16 selected from the group consisting of: [hexane-1,6-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane], [1,2,3-propaetriol-alt-1-isocyanato-4[(4-isocyanatocyclohexyl)methyl]cyclohexane] [2-(hydroxymthyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane], [1,2,3-propaetriol-alt-1-isocyanato-isocyanatocyclohexyl)methyl]cyclohexane]-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate], [(2R,3R,4S)-Pentane-1,2,3,4,5-pentol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Ethane-1,2-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane], and [(2R,3R,4R,5R)-1,2,3,4,5,6-}lexanehexol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane].

Date Recue/Date Received 2021-07-06 18. The polyurethane composition of any one of claims 1-17, wherein said polyurethane composition has a density of about 1.17 to about 1.27 g/cm2.
19. Use of a polyurethane composition of any one of claims 1-18 as a heat resistant coating on a substrate.
20. Use of claim 19 wherein said substrate is selected from the group consisting of ceramic, glass, plastic, metal, wood, rubber and cement.
21. A coating for a substrate comprising a polyurethane composition of any one of claims 1-18.
22. The coating of claim 21, wherein said substrate is selected from the group consisting of ceramic, glass, plastic, metal, wood, rubber and cement.
23. The coating of claim 21 or 22, wherein said coating has a density of about 1.17 to about 1.27 g/cm2.
24. The coating of any one of claims 21-23, wherein said coating has a thickness of about 10 to 200 gm, and preferably of about 50 to 100 gm.
25. The coating of any one of claims 21-24, wherein said coating has a hardness of from 30-55 Hv.
26. The coating of any one of claims 21-25, wherein said coating has an adhesion value of about 4-5 according to ATSM D33359-17.
27. The coating of any one of claims 21-26, wherein said coating has a thermal conductance of about 0.017 to 0.038 and preferably 0.025 W/mK.
28. The coating of any one of claims 21-27, wherein said coating has a static coefficient of friction of about 0.6 to 0.8 and preferably 0.63g.
Date Recue/Date Received 2021-07-06 29. The coating of any one of claims 21-28, wherein said coating maintains i) structural integrity including visual appearance and transparency; ii) chemical stability (no chemical degradation) and iii) hardness value, adhesion value, thermal conductance and coefficient of friction; at dry heat up to 260 C for about 60 minutes.
30. The coating of any one of claims 21-29, wherein said coating tolerates water vapour at 121C at 15-18 psi for at least 30 minutes.
31. The coating of any one of claims 21-30, wherein the % light transmittance through said coating after heating at 250 C for at least 30 minutes is at least 95% at a wavelength of from 370 nm to 800 nm.
32. A process to manufacture a polyurethane composition [hexane-1,6-diol-alt-l-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. mix 4,4'-methylenebis(cyclohexyl isocyanate), glycerol, and 1,6-hexanediol into N,N-dimethylformamide and allow to stir;
b. add dibutyltin dilaurate.
33. A process to manufacture a polyurethane composition [1,2,3-Propanetriol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. mix 4,4'-methylenebis(cyclohexyl isocyanate), glycerol and butylated hydroxytoluene into N,N-dimethylfonnamide and allow to stir;
b. add dibutyltin dilaurate in acetone.
34. A process to manufacture a polyurethane composition [2-(hydroxymethyl)-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. mix 4,4'-methylenebis(cyclohexyl isocyanate), tris(hydroxymethyl)propane, and poly(dimethylsiloxane) into N,N-dimethylfonnamide and allow to stir to make a polyurethane reaction solution;

Date Recue/Date Received 2021-07-06 b. dissolve dibutyltin dilaurate in acetone and add into the polyurethane reaction solution.
35. A process to manufacture a polyurethane composition [1,2,3-Propanetriol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-2-(hydroxymethyl)-2-ethylpropane-1,3-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[polydimethylsiloxane] blended with [ethyl prop-2-enoate-ran-methyl 2-methylprop-2-enoate]: said process comprising:
a. dissolve polymethyl methacrylate-co-ethyl acrylate, tris(hydroxymethyl)propane, glycerol, 1,4-butanediol, and 4,4'-Methylenebis(cyclohexyl isocyanate) in tetrahydrofuran and allowed to stir to make a polyurethane reaction solution;
b. add a dibutyltin dilaurate solution into the polyuerethane reaction solution.
36. A process to manufacture a polyurethane composition [(2R,3R,4S)-Pentane-1,2,3,4,5-pentol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[Ethane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane]: said process comprising:
a. dissolve xylitol in N,N-dimethylfomiamide to form a solution;
b. mix the solution with 4,4'-methylenebis(cyclohexyl isocyanate), ethylene glycol, 2-(4,6-dipheny1-1,3,5-triazin-2-y1)-5-[(hexyl)oxy]-phenol, butylated hydroxytoluene, and Tris(2,4-di-tert-butylphenyl) phosphite and allow to stir to make a homogeneous polyurethane reaction solution;
c. cool to ambient temperature and add dibutyltin dilaurate catalyst solution.

Date Recue/Date Received 2021-07-06 37. A process to manufacture a polyurethane composition [(2R,3R,4R,5R)-1,2,3,4,5,6-}lexanehexol-alt-1-isocyanato-444-isocyanatocyclohexyl)methyl]cyclohexane]-ran-[propane-1,2-diol-alt-1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexanet said process comprising:
a. mix mannitol, propylene glycol, butylated hydroxytoluene, 4,4'-methylenebis(cyclohexyl isocyanate) and tris(2,4-di-tert-butylphenyl) phosphite in N,N-dimethylfonnamide and allow to stir to make a homogeneous polyurethane reaction solution;
b. cool the solution to ambient temperature and add dibutyltin dilaurate solution.
38. A process to manufacture a polyurethane composition with quaternary ammonium compounds as antimicrobial additives of any of claims 33-37, said process comprising:
a. add an polyfunctional isocyanate with at least one functional group, a quaternary ammonium compound with at least one optional tenninal hydroxyl group, and a polyol with at least two tenninal hydroxyl groups selected for polyurethane formation into N,N-dimethylfomiamide wherein the isocyanate functional groups of the polyfunctional isocyanate to the sum of i) the terminal hydroxyl groups on the polyol and ii) the optional tenninal hydroxyl groups of the quaternary ammonium compound and iii) the amino groups of the quaternary ammonium compound has a molar ratio of from 1:1 to 1.1:1, and mix until solution becomes homogenous;
b. add dibutyltin dilaurate;
c. wherein said quaternary ammonium compound is present in the polyurethane composition at a final concentration of between 1.5-8% w/w.
39. Use of claims 19 and 20, wherein said glass substrate includes primary pharmaceutical packaging, digital display, architectural window glass; said plastic substrate includes vehicle interior; and said metal substrate include metal containers.

Date Recue/Date Received 2021-07-06 40. A polyurethane composition of any one of claims 1-19 wherein said composition is heat tolerable, maintains hardness, adhesion and coefficient of friction under the dotted curve of the following graph:
Time-temperature combinations of polyurethane compositions 300 ..................

so mum .111111111--too -0 ___________________________________________________________________________ Time (min) 5 41.
The process of claims 32 and 33, wherein said allow to stir is at 100-400 rotations per minute (rpm) at 15 - 60 C for 2-20 minutes.
42. The process of claim 34, wherein said allow to stir is at 100-400 rpm at 15 - 60 C for 2-4 hours.
43. The process of claim 35, wherein said allow to stir is at 100-400 rpm at 15 - 60 C for 30-60 minutes.
44. The process of claims 36 and 37, wherein said allow to stir is at 100-400 rpm at 140 -190 C for 10-20 minutes.

Date Recue/Date Received 2021-07-06