WO2023249800A1 - Polyurethane products with digital functionality through use of embedded sensor devices - Google Patents

Abstract

A polyurethane product having digital functionality including a matrix of polyurethane and one or more sensor devices embedded therein is disclosed. The polyurethane product may be produced by combining a polyisocyanate compound, a compound with isocyanate-reactive hydrogen atoms and one or more sensor devices and reacting the polyisocyanate compound with the compound with isocyanate-reactive hydrogen atoms in the presence of the one or more sensor devices.

Description

POLYURETHANE PRODUCTS WITH DIGITAL FUNCTIONALITY THROUGH

USE OF EMBEDDED SENSOR DEVICES

TECHNICAL FIELD

[0001] The present disclosure generally relates to polyurethane products with digital functionality. One or more sensor devices may be integrally embedded in the polyurethane products to provide for digital functionality while retaining the physical appearance and structural integrity of the foam.

BACKGROUND

[0002] Polyurethane products are currently used worldwide as an inexpensive, easily made, and customizable material for making a variety of products. It has been proposed to place electronic devices on or in products to detect and identify the products. Such devices can be secured to an external surface or inserted into slits that are cut into the material. However, such processes typically require additional steps or specialized equipment to integrate the electronic device with the product or incorporate the electronic device in a manner which compromises the physical appearance or structural integrity of the foam.

[0003] Accordingly, there remains a need in the art for a simple method of incorporating an electronic device within a polyurethane product that is compatible with conventional manufacturing equipment and retains the physical appearance and structural integrity of the foam.

SUMMARY

[0004] The present disclosure provides components, systems and methods for providing polyurethane products with digital functionality. Digital functionality, such as sensors, sensor arrays, or sensor motes, can be used for monitoring, tracking, identification, and anticounterfeit applications.

[0005] This disclosure provides a polyurethane product having digital functionality including a matrix of polyurethane and one or more sensor devices embedded therein is disclosed. The polyurethane product may be produced by combining a polyisocyanate compound, a compound with isocyanate-reactive hydrogen atoms and one or more sensor devices and reacting the polyisocyanate compound with the compound with isocyanatereactive hydrogen atoms in the presence of the one or more sensor devices.

This disclosure provides a digitally functionalized polyurethane foam system comprising a polyurethane matrix that is a reaction product of a polyisocyanate compound and a compound with isocyanate-reactive hydrogen and one or more sensor devices embedded in the polyurethane matrix, wherein an intact portion of the polyurethane matrix surrounds the one or more sensor devices embedded therein.

DETAILED DESCRIPTION

[0006] This disclosure relates to polyurethane products with an embedded sensor device that is integral to the polyurethane in the end use article. Polyurethane with an embedded sensor device advantageously enable real time monitoring and recording of events such as the performance, use, structural integrity and curing process of polyurethane materials. For example, embedded sensor devices may be sensors that collect data regarding temperature, movement, moisture, pressure and the like during use of the product. Additionally, the sensor device may be a sensor device that collects data regarding temperature, movement, moisture and the like from a location within the polyurethane matrix during the curing process, thereby improving the process and quality control to streamline manufacturing.

[0007] This disclosure provides methods of incorporating a sensor device in a polyurethane in which the sensor device may be added to the polyurethane during the manufacture of the polyurethane from its initial chemical components. As the sensor device is present during formation of polyurethane and before the polyurethane is fully cured, no additional manufacturing step is required to impart sensor device functionality once the polyurethane is cured. Consequently, the sensor devices may be embedded in an intact portion of a matrix formed of a polyurethane , thereby providing for the functionality of embedded sensor devices while retaining the physical appearance and structural integrity of the polyurethane matrix.

[0008] Additionally, as the sensor device may be added to polyurethane during the manufacture of the polyurethane, the polyurethane matrix may securely adhere directly to a surface of the embedded sensor devices to reduce the risk of displacement, accidental loss or intentional removal of the devices from the polyurethane matrix. It is therefore an advantage of the disclosed polyurethane products and systems to provide a material which exhibits improved adhesion between the polyurethane matrix material and the embedded sensor devices.

[0009] A polyurethane product and system having digital functionality comprising a matrix of polyurethane and one or more sensor devices embedded therein may be produced by combining a polyisocyanate compound, a compound with isocyanate-reactive hydrogen atoms and one or more sensor devices and reacting the polyisocyanate compound with the compound with isocyanate-reactive hydrogen atoms in the presence of the one or more sensor devices. In some aspects, the polyurethane product and system are preferably prepared by reacting polyisocyanates with compounds having isocyanate-reactive hydrogen atoms, and optionally one or more of chain extenders and / or crosslinking agents, catalysts, surfactants, blowing agents, surfactants, propellants and other additives.

[0010] The polyisocyanate compound and the compound with isocyanate-reactive hydrogen atoms may be partially reacted prior to combining all three of a polyisocyanate compound, a compound with isocyanate-reactive hydrogen atoms and one or more sensor devices. For example, the sensor, sensor array or sensor mote may be placed into the polyurethane reaction mixture upon the onset of the reaction or held in a specific location while polyurethane is introduced. In some aspects, one of the polyisocyanate compound or the compound with isocyanate-reactive hydrogen atoms may be combined with the one or more sensor devices prior to combining all three of a polyisocyanate compound, a compound with isocyanate-reactive hydrogen atoms and one or more sensor devices.

[0011] In any case, the reaction forms a matrix of polyurethane surrounding the one or more sensor devices. As the sensor device can be added to the polyurethane during the manufacture of the polyurethane from its initial chemical components, the components of the polyurethane matrix envelopes and surrounds the sensor devices as the foam matrix expands and forms. As a result, the sensor devices are embedded in an intact foam matrix. In this context, an “intact” polyurethane matrix or a portion thereof refers to a polyurethane matrix in which the embedded sensor device is an integral part. Generally, an intact foam matrix may retain the cellular structure of the polyurethane as it was formed during the forming and/or curing process. An intact foam matrix may be free from damage by cutting, slicing, piercing or other post-forming steps that permanently damage the cellular structure of the polyurethane matrix. Preferably, an intact polyurethane matrix may have a cell structure which is undamaged.

[0012] Polyurethanes of this disclosure are understood as including any polyurethane and polyisocyanate polyaddition products known in the art. These include isocyanate and alcohol addition products, as well as modified polyurethanes which may contain isocyanurate, allophanate, urea, carbodiimide, uretonimine, biuret, and other isocyanate addition products. These polyurethanes according to the invention in particular comprise solid polyisocyanate polyaddition products, such as thermosets, and foams based on polyisocyanate polyaddition products, such as flexible foams, semi-rigid foams, rigid foams or integral foams as well as polyurethane elastomers, coatings, adhesives and binders. Polyurethanes are also to be understood as meaning polymer blends containing polyurethanes and further polymers, as well as foams from these polymer blends.

[0013] The polyisocyanate compound of this disclosure may include one or more polyisocyanates. The polyisocyanates of this disclosure are not limited and may include organic and / or modified polyisocyanates. Suitable poly isocyanates include those known in the art, such as aliphatic, cycloaliphatic and aromatic di- or polyfunctional isocyanates and any mixtures thereof. Examples are diisocyanates, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and/or octamethylene diisocyanate, 2- methylpentamethylene 1,5 -diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene

1.5 -diisocyanate, butylene 1,4-diisocyanate, l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 1,3- bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1- methylcyclohexane 2,4- and/or 2,6-diisocyanate and/or dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate, diphenylmethane 2,2'-, 2,4'- and/or 4,4'-diisocyanate (MDI), naphthylene

1.5 -diisocyanate (NDI), tolylene 2,4- and/or 2,6-diisocyanate (TDI), diphenylmethane diisocyanate, 3,3 '-dimethylbiphenyl diisocyanate, 1,2-diphenyl ethane diisocyanate and/or phenylene diisocyanate. Further possible isocyanates are given, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.2 and 3.3.2.

[0014] The polyisocyanate component may be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers are obtainable by reacting the polyisocyanates described above, with polyols to give the prepolymer. Prepolymer may be prepared, for example, at temperatures of 30 to 100 °C, preferably at about 80 °C. For the preparation of the prepolymers of the invention, 4,4'-MDI is preferably used together with uretonimine-modified MDI and commercially available polyols based on polyesters, for example, starting from adipic acid, or polyethers, for example starting from ethylene oxide and / or propylene oxide. Polyols are known to the person skilled in the art and described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1.

[0015] Ether-based prepolymers are preferably obtained by reacting polyisocyanates, more preferably 4,4'-MDI, with 2- to 3 -functional poly oxypropylene and / or polyoxypropylene-polyoxyethylene polyols. They are usually prepared by the generally known base-catalyzed addition of propylene oxide alone or in admixture with ethylene oxide to H-functional, in particular OH-functional starter substances. Examples of starter substances used are water, ethylene glycol or propylene glycol or glycerol or trimethylolpropane. Further, as catalysts, it is also possible to use multimetal cyanide compounds, so-called DMC catalysts.

[0016] When using ethylene oxide / propylene oxide mixtures, the ethylene oxide is preferably used in an amount of 10-50% by weight, based on the total amount of alkylene oxide. The incorporation of the alkylene oxides can be carried out in blocks. Particularly preferred is the incorporation of an ethylene oxide end block ("EO cap") to increase the content of more reactive primary OH end groups. The number average molecular weight of the polyols is preferably between 1750 and 4500 g / mol.

[0017] If appropriate, customary chain extenders or crosslinking agents are added to the said polyols in the preparation of the isocyanate prepolymers. Particular preference is given to using dipropylene glycol or tripropylene glycol as a chain extender or crosslinking agent.

[0018] The compound with isocyanate-reactive hydrogen atoms may include one or more compounds with isocyanate-reactive hydrogen atoms. A compound with isocyanatereactive hydrogen atoms is not limited and may include higher molecular weight compounds having at least two isocyanate-reactive hydrogen atoms, for example, polyetherols, polyesterols and / or polycarbonatediols, which are usually also grouped under the term "polyols." Suitable compounds with isocyanate-reactive hydrogen atoms may have numberaverage molecular weights of 500 to 8000, preferably 600 to 6000, in particular 800 to 4000 g / mol, and preferably an average functionality of 1.8 to 3, preferably 1.9 to 2.2, in particular 2 and mixtures thereof. Polymer compounds with isocyanate-reactive groups are known in the art and are described, for example, in "Kunststoffhandbuch, 7, Polyurethane", Carl Hanser- Verlag, 3rd edition 1993, Chapter 3.1.

[0019] Polyetherols can be prepared by known processes, for example, by anionic polymerization with alkali metal hydroxides or alkali metal alkoxides as catalysts and with the addition of at least one starter molecule containing 2 to 3 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids such as antimony pentachloride or borofluoride etherate from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical. Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 3 -propylene oxide, 1, 2 or 2,3-butylene oxide and preferably ethylene oxide and 1, 2-propylene oxide. Further, as catalysts, it is also possible to use multimetal cyanide compounds, so-called DMC catalysts. The alkylene oxides can be used individually, alternately in succession or as mixtures. Preference is given to mixtures of 1, 2-propylene oxide and ethylene oxide, wherein the ethylene oxide is used in amounts of 10 to 50% as ethylene oxide endblock ("EO-cap"), so that the resulting polyols have more than 70% of primary OH end groups.

[0020] Suitable starter molecules are water or dihydric and trihydric alcohols, such as ethylene glycol, 1, 2- and 1, 3 -propanediol, diethylene glycol, dipropylene glycol, 1, 4- butanediol, glycerol or trimethylolpropane into consideration.

[0021] The polyether polyols, preferably polyoxypropylene polyoxyethylene polyols, preferably have a functionality of up to 6, preferably from 2 to 3, and molecular weights of from 300 to 8,000, preferably from 2,000 to 6,000 g / mol.

[0022] Polyester polyols can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. Suitable dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic acid, suberic, azelaic, sebacic, decanedicarboxylic, maleic, fumaric, phthalic, isophthalic and terephthalic acids. The dicarboxylic acids can be used both individually and in admixture with each other. Instead of the free dicarboxylic acids, it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides. Dicarboxylic acid mixtures of succinic, glutaric and adipic acid in ratios of, for example, from 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid, are preferably used. Examples of dihydric and polyhydric alcohols, especially diols, are: ethanediol, di ethylene glycol, 1, 2 or 1, 3 -propanediol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, glycerol and trimethylolpropane. Preferably used are ethanediol, di ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol. Polyester polyols may also be employed from lactones, e.g. s-caprolactone or hydroxycarboxylic acids, e.g. cohydroxy caproic acid.

[0023] For the preparation of the polyester polyols, the organic, for example aromatic and preferably aliphatic polycarboxylic acids and / or derivatives and polyhydric alcohols catalyst-free or preferably in the presence of esterification catalysts, conveniently in an atmosphere of inert gas, such as nitrogen, carbon monoxide, helium, argon, inter alia the melt at temperatures of 150 to 250 °C, preferably 180 to 220 °C, optionally under reduced pressure, to the desired acid number, which is preferably less than 10, more preferably less than 2, polycondensed. According to a preferred embodiment, the esterification mixture at the abovementioned temperatures up to an acid number of 80 to 30, preferably 40 to 30, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar, polycondensed. Suitable esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of diluents and / or entrainers, such as benzene, toluene, xylene or chlorobenzene for the azeotropic distillation of the water of condensation. For the preparation of the polyester polyols, the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are advantageously polycondensed in a molar ratio of 1 : 1 to 1.8, preferably 1 : 1.05 to 1.2 polycondensed.

[0024] The polyester polyols obtained preferably have a functionality of 2 to 6, in particular of 2 to 4, and a molecular weight of 300 to 20,000, preferably 500 to 10,000, more preferably 1000 to 4,000 g / mol.

[0025] Preferably used as a compound with isocyanate-reactive hydrogen atoms are mixtures containing polyetherols and polyesterols. Also suitable as polyols are polymer- modified polyols, preferably polymer-modified polyesterols or polyetherols, particularly preferably graft polyether or graft polyesterols, in particular graft polyetherols. This is a so- called polymer polyol, which usually has a content of, preferably thermoplastic, polymers of 5 to 60 wt.%, preferably 10 to 55 wt.%, particularly preferably 30 to 55 wt.% and in particular 40 to 50% by weight. These polymer polyesterols are described, for example, in WO 05/098763 and are usually prepared by free-radical polymerization of suitable olefinic monomers, for example styrene, acrylonitrile, (meth) acrylates, (Meth) acrylic acid and / or acrylamide, produced in a serving as a grafting polyesterol. The side chains are generally formed by transferring the radicals from growing polymer chains to polyesterols or polyetherols. In addition to the graft copolymers, the polymer polyol predominantly contains the homopolymers of the olefins dispersed in unchanged polyesterol or polyetherol.

[0026] The polyurethane may be a rigid foam, flexible foam, or elastomer. Suitable polyurethane foams may be foams according to DIN 7726. In this case, flexible polyurethane foams may have a compressive stress at 10% compression or compressive strength according to DIN 53 421 / DIN ENISO 604 of 15 kPa and less, preferably 1 to 14 kPa and in particular 4 to 14 kPa. A suitable flexible foam is described in US Pat. No. 8,247,467, which is incorporated herein by reference. Polyurethane foams may include semirigid foams having a compressive stress at 10% compression according to DIN 53 421 / DIN EN ISO 604 of greater than 15 to less than 80 kPa. Polyurethane foams may also include rigid foams. [0027] A summarizing overview of the production and use of rigid polyurethane foams may be found, for example, in the Kunststoff-Handbuch, Volume 7, Polyurethane, 1st edition 1966, edited by Dr. R. Vieweg and Dr. A. Hochtlen, 2nd edition 1983, edited by Dr. Gunter Oertel, and 3rd edition 1993, edited by Dr. Gunter Oertel, Carl Hanser Verlag, Munich, Vienna, as well as WO2012163279. Further details on polyurethane flexible foams according to the invention and rigid polyurethane foams can be found in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 5. Viscoelastic polyurethane foams are described several times in patents and in the literature, such as US Pat. No. 7,022,746, for example, which is incorporated herein by reference.

[0028] The specific starting substances for the production of polyurethanes of this disclosure differ only quantitatively and qualitatively only slightly if a thermoplastic polyurethane, a flexible foam, a semi-rigid foam, a rigid foam or an integral foam is to be produced as polyurethane according to the invention. For example, no propellants are used for the production of solid polyurethanes, and predominantly strictly difunctional starting substances are used for thermoplastic polyurethane. Furthermore, the elasticity and hardness of the polyurethane according to the invention can be varied, for example, via the functionality and the chain length of the higher molecular weight compound having at least two reactive hydrogen atoms. Such modifications are known to the person skilled in the art. The process for the production of a solid polyurethane are described, for example, in EP 0989146 or EP 1460094, the process for the production of a flexible foam in PCT/EP2005/010124 and EP 1529792, the process for the production of a semi-rigid foam in the "Plastics Handbook, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd Edition 1993, Chapter 5.4, the starting materials for the production of a rigid foam in PCT/EP2005/010955 and the process for producing an integral foam in EP 364854, US 5506275 or EP 897402 described.

[0029] In some aspects, the polyurethane product and system are preferably prepared by reacting polyisocyanates with compounds having isocyanate-reactive hydrogen atoms, and optionally one or more of chain extenders and / or crosslinking agents, catalysts, blowing agents, surfactants, propellants, additives, organic fillers, inorganic fillers, flame retardants, nucleating agents, stabilizers, lubricants and mold release agents, reinforcing agents, plasticizers, colorants such as dyes and pigments, hydrolysis protectants, fungistatic and bacteriostatic substances. Such substances are known and described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.4.4 and 3.4.6 to 3.4.1 1. [0030] Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates and the hydroxyl groups of the compounds with isocyanatereactive hydrogen atoms are the tertiary amines known and customary in the prior art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanic acid esters, iron compounds such as Iron (III) acetylacetonate, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate or the like. bar. The catalysts are usually used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of polyhydroxyl compound.

[0031] In addition to the abovementioned components, it is also possible to use chain regulators, usually having a molecular weight of 31 to 499 g / mol. Such chain regulators are compounds which have only one isocyanate-reactive functional group, such as monofunctional alcohols, monofunctional amines and / or monofunctional polyols. By means of such chain regulators, a flow behavior, in particular with TPUs, can be adjusted in a targeted manner. Chain regulators can generally be used in an amount of 0 to 5, preferably 0.1 to 1, parts by weight, based on 100 parts by weight of component isocyanate-reactive compound.

[0032] As chain extenders, it is possible to use generally known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499, preferably 2-functional compounds, for example diamines and / or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular butanediol- 1, 4, hexanediol- 1, 6 and / or di- , tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols having 3 to 8 carbon atoms. Preferred corresponding oligo- and / or polypropylene glycols, wherein mixtures of the chain extenders can be used.

[0033] It is further known that polyurethanes tend to produce emissions of organic substances that can lead to odor nuisance or in the case of high concentrations to malaise. In particular, enclosed spaces, for example in the interior of buildings or vehicles, such as automobiles, are particularly affected. An example of such emissions is the emission of aldehydes. There are already different approaches to reducing aldehyde emissions. US 10,196,493, which is incorporated herein in its entirety by reference, discloses a reduced emission polyurethane that can be prepared by a process in which polyisocyanate, polymeric compounds with isocyanate-reactive groups, catalysts, a CH-acid compound, the general formula R ¹ -CH ² -R ² , wherein R ¹ and R ² independently represent an electron-withdrawing radical of the general formula -C (0) -R ³ or -CN, wherein the radical R ^{3 1S} selected from the group consisting of -NH 2 , -NH-R ⁴ -NR ⁵ R ⁶ , OR ⁷ or R ⁸ , wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently selected from the group consisting of aliphatic, araliphatic or aromatic hydrocarbons which and optionally blowing agent, chain extenders and / or crosslinking agents and auxiliaries and / or additives are mixed to form a reaction mixture and the reaction mixture is allowed to react to give the polyurethane.

[0034] Polyurethane rigid foams, semi-rigid foams and flexible polyurethane foams preferably have an open cell content according to DIN ISO 4590 of greater than 85%, particularly preferably greater than 90%. The polyurethane foam of this disclosure is preferably open-celled, but closed cells may also be included. Usually, the proportion of closed cells is at most 10, preferably at most 5%. Since the foam is open-celled, the recesses are usually filled with the atmosphere surrounding the composite element, typically air. A suitable open-cell foam structure is described in US Pat. No. 7,910,200, which is incorporated herein by reference.

[0035] The preparation of the polyurethane can be carried out by the known processes, for example with reaction extruders or the belt process according to one-shot or the prepolymer process, or batchwise according to the known prepolymer process. In general, a method for producing polyurethane foam wherein the following are mixed to form a reaction mixture: a) polyisocyanate, b) a compound with isocyanate-reactive hydrogen atoms; and c) one or more sensor devices, and optionally one or more of a catalyst, a surfactant, a blowing agent; a chain elongation; and/or cross-linking agent; and an auxiliary agent and/or additive or combinations thereof. The reaction mixture is allowed to react to form the polyurethane. Thereafter, the polyurethane foam may be allowed to fully cure while one or more sensor devices are embedded therein.

[0036] The polyurethane forming reaction can be carried out under customary code (i.e., reactive index or ratio) numbers, preferably with a code number of 60 to 130, particularly preferably with a code number of 80 to 125. The code number is defined by the ratio of the total isocyanate groups of component used in the reaction with isocyanatereactive groups of the compound with isocyanate-reactive hydrogen atoms, i.e. the active hydrogens. With a figure of 100, each isocyanate group of the polyisocyanate compound has an active hydrogen atom, i.e. an isocyanate-reactive group containing component. For ratios above 100, there are more isocyanate groups than OH groups.

[0037] The reacting components may be mixed together successively or simultaneously with the reaction starting immediately. The polyurethane products can be prepared in open or closed molds or by a continuous foaming process. A continuous foaming process generally includes continuously applying or extruding the reaction mixture to a belt line to produce a foam sheet, slab or block. In some examples, the sensor devices may also be pre-heated before being introduced to the polyisocyanate and the compound with isocyanatereactive hydrogen atoms so as to not impact the polyurethane chemistry.

[0038] Generally, due to the chemistry of the polyurethane system, the reaction takes place at a temperature above 85°C, or above 100°C, or above 115°C or above 130 °C. While most recommended operating ranges of electronic devices are 85°C or lower, we have found that the sensor devices are able to withstand the reaction temperatures with only negligible loss of function. The maximum reaction temperature is generally limited by the temperature sensitivity of the sensor devices and is preferably 185°C or less, 165°C or less, or 150°C or less.

[0039] Additionally, reaction takes place at a pressure up to 2 bar, or up to 1 bar, or up to 0.8 bar or up to 0.4 bar.

[0040] In some aspects, the reaction the polyisocyanate compound with the compound with isocyanate-reactive hydrogen atoms occurs in a mold, such as an open mold or a closed mold. If a mold is used, the sensor devices may be placed into the mold prior to, simultaneously with, or after introducing one or both of the polyisocyanate compound and isocyanate-reactive hydrogen atoms to the mold. For example, the sensor(s) may be placed into a mold, and thereafter a mixture of the poly isocyanate compound and isocyanate-reactive hydrogen atoms may be applied to the mold. Alternatively, a mixture of the polyisocyanate compound and isocyanate-reactive hydrogen atoms may be introduced into a mold and the sensor(s) may be placed onto the surface or submerged into the reaction mixture before foaming is complete or at least before curing is complete.

[0041] Advantageously, the sensor devices may be powered in an ON state and actively operating during the reaction of the polyurethane system. This enables the use of the sensor devices to directly monitor aspects of the reaction and curing process. Additionally, advantageously, potting is not required to embed the sensor devices. In other words, it is possible for the electrical connections to be directly exposed to the polyurethane reaction components without an initial potting or insulating step.

[0042] The sensor device may be held in the mold in a fixed location based on the design of the mold or placed without any fixturing, such that the flow of polyurethane filling the cavity dictates the location of the sensor. The location of the sensor device could be determined after manufacturing via the appropriate sensor functionality and software. Adjustment of position within the foam is also possible during the reaction or as the foam structure develops.

[0043] The methods and systems of this disclosure are compatible with a variety of sensor devices, including sensor motes or sensor arrays, active or passive sensors, and the like that are known in the art. As used herein, the term “sensor devices” refers to one or more devices that respond to a physical stimulus, and convert the stimulus into a signal that is conveyed to another device. For example, a sensor may include a measuring element that detects the magnitude of a physical parameter and transmits the measurement as a signal.

[0044] In preferred examples, the sensor device of this application includes, within its housing, a power unit, a communication unit, a microprocessor and/or microprocessor, a central processing unit (“CPU”), a sensing unit and an internal clock. An example of a sensing device incorporating these elements is disclosed in US Pat. No. 7,881,239, which is incorporated herein by reference.

[0045] Suitably, the power unit may be a primary or secondary battery, a supercapacitor, or an energy harvester, such as a thermoelectric energy harvester or radio wave energy harvester.

[0046] The communication unit may be wired or wireless. Generally, the communication unit includes a receiver and transmitter for respectively receiving and transmitting information. In some examples, the communication unit may include an antenna. Preferably, the sensor device is not an RFID tag and/or does not include an RFID tag device. As used herein, an “RFID tag” refers to a component of an RFID system that is largely limited to an electronic circuit (e.g., an antenna) and a small silicon-based microprocessor with a memory typically storing only identification information.

[0047] The microprocessor generally manages the reception and transmission of information. Examples of the microprocessor or microprocessor may include a digital signal processor (“DSP”). In some examples, the CPU may be integrated in a microcontroller, or provided as an independent element.

[0048] In some examples, the sensing unit is a temperature sensor, moisture sensor, humidity sensor, acceleration sensor, magnetic field sensor, orientation sensor, strain sensor, pressure sensor, light sensor, chemical (gas) sensor, bio sensor (sweat), proximity sensor, capacitive sensor, resistive sensor, accelerometer, magnetometer, seismic sensor, vibration sensor, sound sensor, altitude sensor or infrared sensor. Polyurethane products may include multiples of the same or different sensors in combination. In some examples, the sensor may be an IMU (inertial measurement unit) including an accelerometer, magnetometer and gyroscope.

[0049] An exemplary electronic system may be the Micro Inertial Measurement System (MIMSY), which is an open-source wireless sensor node for Internet of Things applications, specifically designed for a small system volume while maintaining functionality and extensibility. MIMSY is a 16mm x 16mm node with an Arm Cortex-M3 microprocessor, 802.15.4 wireless transceiver, and a 9-axis IMU. Schindler, Craig, et. al., MIMSY: The Micro Inertial Measurement System for the Internet of Things, 2019 IEEE 5th World Forum on Internet of Things (WF-IoT). The MIMSY system is fully compatible with the OpenWSN wireless sensor networking stack, which enables the straightforward implementation of standards compliant 6TiSCH mesh networks using MIMSY motes.

[0050] The devices may be wired or wireless. One or more sensor devices may also be organized as one of a plurality of nodes in a mesh network, such as a self-organizing network, with other sensors or other devices. An example of a mesh network is disclosed in US Pat. No. 7,529,217, which is incorporated herein by reference.

[0051] A mesh network may be a network that employs “full mesh” topology or “partial mesh” topology. In the full mesh topology, each node of the plurality of nodes is connected directly to each of the others. In the partial mesh topology, nodes are connected to only some, not all, of the other nodes.

[0052] Mesh networks and partial-mesh networks generally include a network infrastructure that is decentralized, avoids a central point of failure and control, is cost effective and be maintained and expanded locally. A mesh network or partial mesh network includes many-to-many connections and is capable of dynamically updating and optimizing these connections.

[0053] The mesh networks may also include embedded mesh network devices that form an “embedded mesh network.” An embedded mesh network may be a component of a larger more complex mesh network. An embedded mesh network is preferably designed to run on its own without intervention, responds to events (e.g., data collection, data transfer, etc.) in- real time and provides data to the larger more complex network. The plural network devices include one or more of a wired interface and/or a wireless interface used to connect to a mesh network or partial mesh network to provide data communications.

[0054] One or more sensor devices in a mesh network may preferably further be provided with signal generating circuitry configured to be responsive to detecting an environmental event by broadcasting a signal to other sensor devices in the mesh network and also to re-broadcast signals received from other sensor devices in the mesh network.

[0055] The sensor devices in a mesh network may be connected to a cloud platform that may, for example comprise any of a variety of network level components. The Cloud may, for example, comprise any of a variety of server systems executing applications that monitor and/or control components of the network. Such applications may also, for example, manage the collection of information from any of a large array of networked information sources, many examples of which are discussed herein. The Cloud (or a portion thereof) may also be referred to, at times, as an API. For example, Cloud (or a portion thereof) may provide one or more application programming interfaces (APIs) which other devices may use for communicating/interacting with the Cloud.

[0056] An example component of the Cloud may, for example, manage interoperability with various multi-cloud systems and architectures. Another example component (e.g., a Cloud service component) may, for example, provide various cloud services (e.g., captive portal services, authentication, authorization, and accounting (AAA) services, API Gateway services, etc.). An additional example component (e.g., a DevCenter component) may, for example, provide network monitoring and/or management functionality, manage the implementation of software updates, etc. A further example component of the Cloud may manage data storage, data analytics, data access, etc. A still further example component of the Cloud may include any of a variety of third-partly applications and services.

[0057] The Cloud may, for example, be coupled to the Backbone/Core Infrastructure of the example network via the Internet (e.g., utilizing one or more Internet Service Providers). Though the Internet is provided by example, it should be understood that scope of the present disclosure is not limited thereto.

[0058] Preferred embodiments include mesh network devices and interfaces that are compliant with all or part of standards proposed by the Institute of Electrical and Electronic Engineers (IEEE), International Telecommunications Union-Telecommunication Standardization Sector (ITU), European Telecommunications Standards Institute (ETSI), Internet Engineering Task Force (IETF), U.S. National Institute of Security Technology (NIST), American National Standard Institute (ANSI), Wireless Application Protocol (WAP) Forum, Bluetooth Forum, or the ADSL Forum. However, network devices based on other standards could also be used.

[0059] The sensor devices may be operably connected to a power source, data processor, data storage, or communication device. In some aspects, this may include a wired or wireless connection between the embedded sensor devices and a power source, data processor, data storage, or communication device. In some cases, this may include a sensor device that includes a power source, data processor, data storage, or communication device also embedded in the polyurethane matrix. For example, powering options, such as energy harvesters or wireless power transfer (i.e., wireless charging), can be embedded within the polyurethane article. In such examples, the power source, data processor, data storage, or communication device is generally selected to have heat-resistance such that it can withstand one-time exposure to typical manufacturing temperatures, which may be upwards of 130 °C, or 150 °C. However, conditions for actual use of the products typically occurs at temperatures lower than 85 °C, such as room temperature.

[0060] The polyurethane products and systems of this disclosure can be used in any applications using polyurethane in which digital functionality is desired. For example, the polyurethane products and systems may be used in padding or upholstery for furniture or automotive uses, mattresses, pillows, clothing, shoes, carpet back-foaming, cavity foaming or padding or vibration damping, helmet padding, rigid insulation foam, spray foam, sandwich/insulation panels, automotive seating, automotive interior components including an arm rest or dashboard, wheels and rollers, tires, pipeline inspection PIGs, sporting equipment such as bike seats or yoga mats, coatings, adhesives, sealants, geo-fill, thermo polyurethane plastics (TPU), wood panels, woodfiber insulation and the like and the various applications thereof.

[0061] The types and combinations of sensors used in a polyurethane product may be selected based on the desired application of the polyurethane article. Non-limiting examples of selections of sensors for various non-exclusive applications are set forth in Table 1.

[0062] In some examples, sensor devices in the form of user activatable push buttons may be integrated into automotive interior components such as armrests, dashboards, etc. Advantageously, integration of such buttons in the foam could reduce the number of required parts, streamline assembly, protect the button device from debris because the button is fully enclosed, and aid in the ability to clean surfaces.

[0063] In some examples, a mattress could be provided with digital functionality via embedded sensors. For example, a mattress may be integrated with a temperature sensor and a mechanism for cooling the mattress or other temperature control to improve comfort while in use. A mattress with digital functionality, which could be with an adjustable bed frame, may also provide feedback to adjust positioning to reduce pressure points and improve comfort. A mattress with digital functionality may also provide feedback to the end user or healthcare setting to monitor sleep quality. A mattress with digital functionality may enable remote monitoring of a patient’s movements or lack of movement to alert healthcare staff of patient needs (e.g. reduction of bed sores). Sensor devices could provide feedback to the end user or healthcare provider that the cleanliness of a mattress has been compromised.

[0064] Additionally, a function can be integrated into a sensor device system to provide tracking information. Properties of a mattress with digital functionality can be tracked over time to indicate to the end user that the mattress should be replaced before it begins to impact the health and sleep quality of the end user. Mattress use and orientation can also be tracked and feedback may be provided to the end user to rotate their mattress to achieve the maximum useful life.

[0065] In some examples, a rigid foam can be provided with digital functionality via embedded sensor devices. For example, a rigid foam may be provided with moisture sensors. As effectiveness of insulation may be impacted by the uptake of moisture, sensor information could be of value to the end user or to the manufacturer for investigation as to the presence and source of unwanted moisture. Sensor devices can also be used to determine if the foam has been damaged, such as by pressure. This could be done by monitoring for sudden impacts, strain sensors, tracking the electrical resistivity of physical contacts or of the foam, etc. Sensor devices can be embedded within a sandwich panel to monitor if failure is occurring between the foam core and panel skins. The integrity of the panel could be compromised if this is reduced below a critical threshold.

[0066] In some examples, an elastomer can be provided with digital functionality via embedded sensor devices. For example, sensor devices may detect wear, which could be of value in remote operations such as mining where replacement parts are not immediately available. Sensor devices may also detect wear in wheels, rollers, shock and vibration isolators or other equipment, which may be part of conveyer systems that cannot be shut down often for inspection or where major failure would greatly impact operations. Early detection for replacement could aid to extend overall equipment life which could be impacted by increased vibrations, shocks and impact. Smart pigs may also be used as part of specialty inspections. Miniature, low-cost sensor motes could enable more pig users to inspect their piping, which could lead to early detection of weakpoints or failure. Additional basic function could be to identify a location within a piping system in case of blockage.

[0067] In some examples, sports equipment can be provided with digital functionality via embedded sensor devices. Such sports equipment with digital functionality could assist with finding lost or stolen equipment. Additionally, sports equipment with digital functionality could be useful as a training instrument for the individual, personal trainer or healthcare provider. Sports equipment with digital functionality may provide feedback to the user, gym owner, personal trainer, equipment manager to ensure clean equipment. Additionally, data on impact could be useful for the user, coach or healthcare provider to understand the degree of impact and take proper precautions to ensure the users safety and optimal performance. Feedback provided to the user during use or during purchase to ensure that the sports equipment or protective equipment is well-fitted and can work as it was designed.

[0068] EXAMPLES: [0069] Example 1 : Shoe sole

[0070] A polyurethane reaction mixture was prepared from the materials provided in

Table 2.

[0071] The polyurethane reaction mixture according to Table 2 was placed into mold of a shoe sole. MIMSY sensor motes were placed into to the polyurethane reaction mixture as the reaction occurred and foam structure developed. Additionally, the use of a high temperature battery (secondary (i.e., rechargeable)) was embedded with the sensor mote. The sensor mote retained function of its 9-axis IMU - Inertial measurement unit (3-axis accelerometer, 3-axis gyroscope, 3-axis magnetometer) and temperature sensor. Data was transmitted wirelessly via OpenWSN protocol. Wireless power transfer was also demonstrated to be embedded in polyurethane.

[0072] Example 2: Pillow Foam

[0073] A polyurethane reaction mixture was prepared from the materials provided in Table 3.

[0074] The polyurethane reaction mixture according to Table 3 was placed into mold of a pillow. MIMSY sensor motes were placed into the polyurethane reaction mixture as the reaction occurred and foam structure developed. The sensor mote retained function of its 9- axis IMU - Inertial measurement unit (3-axis accelerometer, 3-axis gyroscope, 3-axis magnetometer) and temperature sensor. A battery power source was connected externally. [0075] Example 3: Viscoelastic foam

[0076] A polyurethane reaction mixture was prepared from the materials provided in Table 4.

*pph = parts per hundred parts polyol

[0077] Four MIMSY sensor motes were placed into to the polyurethane reaction mixture according to Table 4 as the reaction occurred and foam structure developed. Additionally, the use of a high temperature battery (secondary (i.e.. rechargeable)) was embedded with each of the sensor motes. The sensor motes retained function of its 9-axis IMU - Inertial measurement unit (3-axis accelerometer, 3-axis gyroscope, 3-axis magnetometer) and temperature sensor. Data was transmitted wirelessly via OpenWSN protocol. Motion and temperature was tracked using the MIMSY sensor during the manufacture of the foam block.

[0078] Example 4: HYPERSOFT™ Foam

[0079] A polyurethane reaction mixture was prepared from the materials provided in

Table 5.

*pph = parts per hundred polyol

[0080] Four MIMSY sensor motes were placed into to the polyurethane reaction mixture according to Table 5 as the reaction occurred and foam structure developed. Additionally, the use of a high temperature battery (secondary (i.e., rechargeable)) was embedded with each sensor mote. The sensor motes retained function of its 9-axis IMU - Inertial measurement unit (3-axis accelerometer, 3-axis gyroscope, 3-axis magnetometer) and temperature sensor.

[0081] Additionally, a capacitive sensor array was embedded in this foam. The array was a grid of printed sensors on a film. The array was attached to an Arduino and then to a computer (both wired connections) for data logging and display. The array served to map pressure at different locations in the x-y plane on the foam block.

[0082] Example 5: High Resiliency foam

[0083] A polyurethane reaction mixture was prepared from the materials provided in Table 6.

*pph = parts per hundred polyol

[0084] Four MIMSY sensor motes were placed into to the polyurethane reaction mixture according to Table 6 as the reaction occurred and foam structure developed. Additionally, the use of a high temperature battery (secondary (i.e., rechargeable)) was embedded with the sensor mote. The sensor mote retained function of its 9-axis IMU - Inertial measurement unit (3-axis accelerometer, 3-axis gyroscope, 3-axis magnetometer) and temperature sensor. Data was transmitted wirelessly via OpenWSN protocol.

[0085] Example 6: Viscoelastic foam

[0086] A viscoelastic elastomeric polyurethane foam was obtained according to the materials and methods disclosed in WO2021259832. MIMSY sensor motes were placed into to the polyurethane reaction mixture as the reaction occurred and foam structure developed. A battery power source was connected externally. Temperature was measured by MIMSY during manufacturing of the foam sample.

Claims

What is claimed is:

1. A process for producing a polyurethane product having digital functionality comprising a matrix of polyurethane and one or more sensor devices embedded therein, comprising: a) combining a polyisocyanate compound, a compound with isocyanate-reactive hydrogen atoms and one or more sensor devices; and b) reacting the polyisocyanate compound with the compound with isocyanate-reactive hydrogen atoms in the presence of the one or more sensor devices.

2. The process according to claim 1, wherein the polyisocyanate compound and the compound with isocyanate-reactive hydrogen atoms are partially reacted prior to step a).

3. The process according to claim 1, wherein one of the polyisocyanate compound or the compound with isocyanate-reactive hydrogen atoms is combined with the one or more sensor devices prior to step a).

4. The process according to claim 1, wherein step b) forms an intact matrix of polyurethane surrounding the one or more sensor devices embedded therein.

5. The process according to claim 1, further comprising adding at least one of a chain extender, a surfactant, a crosslinking agent, a filler, a colorant, a catalyst, and a blowing agent.

6. The process according to claim 1, wherein step b) occurs in a mold.

7. The process according to claim 1, wherein step b) comprises a continuous foaming step.

8. The process according to claim 1, wherein the one or more sensor devices is/are placed in a mold prior to step a).

9. The process according to claim 1, further comprising embedding a power source, data processor, data storage, or communication device operably connected to the sensor or sensor array in the matrix.

10. The process according to claim 1, wherein the polyurethane is a rigid foam, flexible foam, or elastomer.

11. The process according to claim 1, wherein step b) occurs at a temperature above 85°C.

12. The process according to claim 1, wherein the one or more sensor devices are in an ON state during step b).

13. A digitally functionalized polyurethane system comprising: a) a polyurethane matrix that is a reaction product of a polyisocyanate compound and a compound with isocyanate-reactive hydrogen; and b) one or more sensor devices embedded in the polyurethane matrix, wherein an intact portion of the polyurethane matrix surrounds the one or more sensor devices embedded therein.

14. The polyurethane system according to claim 13, wherein the polyurethane matrix is further a reaction product of at least one of a chain extender, a surfactant, a crosslinking agent, a catalyst, and a blowing agent.

15. The polyurethane system according to claim 13, wherein the polyurethane system is a molded polyurethane matrix.

16. The polyurethane system according to claim 13, wherein the one or more sensor devices comprises a temperature sensor, moisture sensor, humidity sensor, acceleration sensor, magnetic field sensor, orientation sensor, strain sensor, pressure sensor, light sensor, chemical sensor, bio sensor, proximity sensor, capacitive sensor, resistive sensor, accelerometer, magnetometer, seismic sensor, vibration sensor, sound sensor, altitude sensor or infrared sensor.

17. The polyurethane system according to claim 13, wherein the sensor is operably connected to a power source, data processor, data storage, or communication device.

18. The polyurethane system according to claim 17, wherein the power source, data processor, data storage, or communication device is embedded in the polyurethane matrix.

19. The polyurethane system according to claim 13, wherein the polyurethane is a rigid foam, flexible foam, or elastomer.

20. The polyurethane system according to claim 13, wherein the polyurethane system is a mattress, a shoe sole, a pillow, helmet padding, carpet back-foaming, cavity foaming or padding, vibration damping foam, insulation foam, spray foam, a sandwich panel, automotive seating, automotive interior components, a wheel, a roller, a tire, a pipeline inspection PIG, sporting equipment, geo-fill, thermo polyurethane plastics (TPU), wood panels, or woodfiber insulation.

21. The polyurethane system according to claim 13, wherein the one or more sensor devices are wireless.

22. The polyurethane system according to claim 13, wherein the one or more or more sensor devices are organized in a mesh network.

23. The polyurethane system according to claim 13, wherein the one or more or more sensor devices are connected to a cloud platform.