High Temperature Stable Sandwich Panel

Abstract

The present disclosure provides a reaction mixture for producing a polyurethane / polyisocyanurate sandwich panel having high temperature stability up to about 230° C. The polyurethane / polyisocyanurate sandwich panel may be used in connection with the production of automotive structural components. The present disclosure also provides a process for the production of polyurethane / polyisocyanurate molded articles exhibiting high temperature stability.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 340,210, filed May 10, 2022, the contents of which are expressly incorporated by reference in their entirety herein.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT N / A

[0003] The present disclosure generally relates to reaction mixtures for producing polyurethane / polyisocyanurate sandwich panels, processes for producing polyurethane / polyisocyanurate sandwich panels, and structures including polyurethane / polyisocyanurate sandwich panels that can be used in a variety of applications, including, but not limited to, automotive applications. [Background technology]

[0004] Polyurethane-based sandwich panels are widely adopted for use in automotive applications due to their light weight and rigidity. These sandwich panels generally include a core made of thermosetting or thermoplastic foam, or paper, thermoplastics, or metal in a honeycomb / cylindrical structure, located between two skin layers made of fiber-reinforced polymer. The fiber reinforcement can be in the form of glass fiber mat, carbon fiber mat, natural fiber mat, or polymer fiber mat in chopped, continuous, sewn, or needling form. A polyurethane-forming reaction mixture is applied to at least one side of the semi-finished sandwich panel, preferably via spray application. The semi-finished sandwich panel is then placed in a mold and obtains a specific shape by compression in a hot compression process to harden the polyurethane reaction mixture.

[0005] One of the drawbacks of current polyurethane-based sandwich panels is that they do not have the ability to withstand exposure to high temperatures, and therefore have limited use in the production of automotive trunk floors. Specifically, polyurethane-based sandwich panels can exhibit defects upon exposure to high temperatures, evidenced by irreversible expansion or surface blistering in areas of high resin content.

[0006] There is a need for improvements to current polyurethane-based sandwich panels so that they can be used in the production of other semi-structural automotive parts that are exposed to high temperatures, such as roof modules, hoods, side panels, and liftgates. Summary of the Invention

[0007] The present disclosure describes a reaction mixture for use in the production of polyurethane / polyisocyanurate sandwich panels exhibiting high temperature stability, the reaction mixture comprising (i) a polyol, (ii) a polyisocyanate, (iii) a catalyst, (iv) a blowing agent, and optionally (v) at least one chain extender or crosslinker, and optionally (vi) additives, the reaction mixture having an Isocyanate Index greater than 200.

[0008] A process is also provided for the production of polyurethane / polyisocyanurate molded articles exhibiting high temperature stability, the process comprising: a) applying a first fibrous material having a first surface and a second surface to a first surface of a core material; b) applying a second fibrous material having a first surface and a second surface to a second surface of the core material to form a sandwich structure having a first surface and a second surface, where the first fibrous material and the second fibrous material can be the same or different; c) applying the reaction mixture of claim 1 to a first surface and a second surface of a sandwich structure to form a reaction mixture-coated sandwich structure; d) placing the reactive mixture coated sandwich structure into a mold; e) shaping the reaction mixture coated sandwich structure in a mold at a temperature in the range of about 100° C. to about 160° C. while curing the reaction mixture to form a polyurethane / polyisocyanurate molded article; f) removing the polyurethane / polyisocyanurate molding from the mold; e) optionally post-treating the polyurethane / polyisocyanurate molded article; Includes. [Brief description of the drawings]

[0009] [Figure 1A] 1 is an illustration of the process of the present disclosure. [Figure 1B] FIG. 1B is a close-up of the sandwich structure of the process shown in FIG. 1A. [Figure 1C] FIG. 1B is a close-up view of the molded product of the process shown in FIG. 1A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present disclosure provides a reaction mixture for use in the production of polyurethane / polyisocyanurate sandwich panels exhibiting high temperature stability, the reaction mixture comprising (i) a polyol, (ii) a polyisocyanate, (iii) a catalyst, (iv) a blowing agent, and optionally (v) at least one chain extender or crosslinker, and optionally (vi) additives, the reaction mixture having an isocyanate index greater than 200. By applying a combination of modifications to modern reaction mixtures used in the production of rigid foams, including modifying the components of the reaction mixture, increasing the isocyanate index, and optimizing the mold temperature, polyurethane / polyisocyanurate sandwich panels can be molded within current processing windows and achieve high temperature stability of up to about 210° C. or in other embodiments up to about 230° C. (i.e., do not exhibit thermal and dimensional instability after exposure to temperatures of up to about 210° C. or up to about 230° C. for extended periods of time). Such panels can then be efficiently used thereafter during primary assembly on a vehicle production line in connection with the production of various automotive structural components, including, but not limited to, roofs, hoods, door panels, liftgates, and floors.

[0011] As used herein, the term "comprising" and its derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is disclosed herein. For the avoidance of doubt, all compositions claimed herein through the use of the term "comprising" may include any additional additive, adjuvant, or compound, unless stated to the contrary. In contrast, "consisting essentially of" may be used to describe any composition that is not specifically claimed. The term "essentially of," as used herein, excludes any other component, step, or procedure from the scope of any succeeding recitation, except those that are not essential to operability. The term "consisting of," when used, excludes any component, step, or procedure not specifically recited or listed. The terms "or" and "and / or" refer to the listed members individually or in any combination, unless otherwise stated. For example, the phrase A and / or B refers to A alone, B alone, or both A and B.

[0012] The articles "a" and "an" are used herein to refer to one or more (i.e., at least one) of the grammatical object of the article. By way of example, "a polyol" means one polyol or multiple polyols. The phrases "in one embodiment," "according to one embodiment," and the like generally mean that the feature, structure, or characteristic that follows the phrase is included in at least one embodiment of the disclosure and may also be included in multiple embodiments of the disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. When a statement is made herein that an ingredient or feature "may," "can," "could," or "might" be included or have a characteristic, it does not require that the ingredient or feature be included or have that characteristic.

[0013] The terms "preferred" and "preferably" refer to embodiments that may provide certain benefits, under certain circumstances, while other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present disclosure.

[0014] The term "about," as used herein, allows for a certain degree of variation in a value or range, for example, the degree of variation may be within 10%, within 5%, or within 1% of a stated value or a stated range limit.

[0015] Values ​​expressed in range format are to be interpreted in a flexible manner to include not only the numbers expressly recited as the limits of the range, but also all of the individual numbers or subranges subsumed within that range, as if each number and subrange were expressly recited. For example, a range (such as 1 to 6) shall be considered to have specifically disclosed subranges (such as 1 to 3, 2 to 4, 3 to 6, etc.) as well as individual numbers within that range (e.g., 1, 2, 3, 4, 5, and 6). This applies regardless of the breadth of the range.

[0016] The term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes cases where the event or circumstance occurs and cases where it does not occur.

[0017] The term "extended period of time," as used herein, refers to any period of time that one of ordinary skill in the art would consider to be long with respect to the assembly of a structure (such as a vehicle) using the molded part, specifically, a period of time such as at least about 5 minutes, or at least about 10 minutes, or at least about 15 minutes, or at least about 30 minutes.

[0018] "Isocyanate Index" or "NCO Index" or "Index" refers to the ratio of NCO groups to isocyanate-reactive hydrogen atoms present in a formulation, this ratio being given as a percentage: [NCO] x 100 / [active hydrogen] (%).

[0019] The term "hydroxyl number" refers to the concentration of hydroxyl groups capable of reacting with --NCO groups per unit weight of polyol. Hydroxyl number is reported as mg KOH / g and can be measured according to standard ASTM D1638.

[0020] The term "average functionality" or "average hydroxyl functionality" of a polyol refers to the number of OH groups per molecule on average. The average functionality of an isocyanate refers to the number of OH groups per molecule on average. This refers to the number of -NCO groups.

[0021] The term "reaction mixture," as used herein, may be used when two or more components of the mixture are combined, or may be used to refer to all of the components of the mixture before they are combined, and does not necessarily require that all of the components are present at the same time at all times.

[0022] The term "substantially free" refers to the amount of a particular component or part present in a composition that does not significantly affect the overall composition.In some embodiments, "substantially free" can refer to the amount of a particular component or part present in a composition being less than about 5% by weight, or less than about 4% by weight, or less than about 3% by weight, or less than about 2% by weight, or less than about 1% by weight, or less than about 0.5% by weight, or less than about 0.1% by weight, or less than about 0.05% by weight, or even less than about 0.01% by weight, based on the total weight of the composition, or the amount of that particular component or part present in each composition is zero.

[0023] Thus, the present disclosure provides a reaction mixture for producing polyurethane / polyisocyanurate sandwich panels that exhibit high temperature stability up to about 210° C. or in some embodiments up to about 230° C. In one embodiment, the reaction mixture includes (i) a polyol having at least two isocyanate-reactive moieties per compound. For example, the polyol or mixture thereof can be liquid at 25° C. and have a molecular weight in the range of 60 Daltons to 10,000 Daltons (e.g., 300 Daltons to 10,000 Daltons or less than 5,000 Daltons), a nominal hydroxyl functionality that is at least 2, and a hydroxyl equivalent weight of 30 to 2000 (e.g., 30 to 1,500 or 30 to 800). Examples of polyols that can be used include polyether polyols (such as those prepared by the addition of alkylene oxides to an initiator) that contain 2 to 8 active hydrogen atoms per compound. In some embodiments, the initiators include glycols, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, ethylenediamine, ethanolamine, diethanolamine, aniline, toluenediamine (e.g., 2,4 toluenediamine and 2,6 toluenediamine), polymethylene polyphenylene polyamines, N-alkylphenylene-diamines, o-chloro-aniline, p-aminoaniline, diaminonaphthalene, or combinations thereof. Suitable alkylene oxides that may be used to form the polyether polyols include ethylene oxide, propylene oxide, and butylene oxide, or combinations thereof.

[0024] Other suitable polyols include Mannich polyols having a nominal hydroxyl functionality of at least 2 and at least one secondary or tertiary amine nitrogen atom per molecule. In some embodiments, the Mannich polyol is a condensation product of an aromatic compound, an aldehyde, and an alkanolamine. For example, the Mannich condensation product may be produced by the condensation of one or both of a phenol and an alkylphenol with formaldehyde and one or more of monoethanolamine, diethanolamine, and diisopronolamine. In some embodiments, the Mannich condensation product includes the reaction product of a phenol or nonylphenol with formaldehyde and diethanolamine. The Mannich condensation product may be prepared by any known process. In some embodiments, the Mannich condensation product may act as an initiator for alkoxylation. Any alkylene oxide (e.g., the alkylene oxides described above) may be used in the alkoxylation of one or more Mannich condensation products. Once polymerization is complete, the Mannich polyols contain primary and / or secondary hydroxyl groups attached to aliphatic carbon atoms.

[0025] In certain embodiments, the polyols used are polyether polyols containing propylene oxide ("PO"), ethylene oxide ("EO"), or a combination of PO and EO groups or PO and EO moieties in the polymer structure of the polyol. Such PO and EO units may be randomly arranged throughout the polymer structure or arranged in block sections. In certain embodiments, the EO content of the polyol ranges from 0% to 100% by weight based on the total weight of the polyol (e.g., 0% to about 50% by weight or about 50% to 100% by weight based on the total weight of the polyol). In some embodiments, the PO content of the polyol ranges from 100% to 0% by weight based on the total weight of the polyol (e.g., 100% to about 50% by weight or about 50% to 0% by weight based on the total weight of the polyol). Thus, in some embodiments, the EO content of the polyol may range from about 99% to about 33% by weight of the polyol, while the PO content may range from about 1% to 67% by weight of the polyol. In other embodiments, the PO content of the polyol may range from about 99% to about 33% by weight, and the EO content may range from about 1% to about 67% by weight of the polyol. Furthermore, in some embodiments, the EO and / or PO units may be located at the terminals on the polymer structure of the polyol or within an internal section of the polymer backbone structure of the polyol. Suitable polyether polyols include poly(oxyethylene) diols and triols obtained by the addition of ethylene oxide to di- or trifunctional initiators known in the art, poly(oxypropylylene) diols and triols obtained by the addition of propylene oxide to di- or trifunctional initiators known in the art, and poly(oxyethylene) and poly(oxypropylene) diols and triols obtained by the sequential addition of propylene and ethylene oxide to di- or trifunctional initiators known in the art. In certain embodiments, the polyol comprises the aforementioned diols or alone, or alternatively, the polyol comprises a mixture of these diols and triols.

[0026] The aforementioned polyether polyols also include the reaction products obtained by polymerization of ethylene oxide with another cyclic oxide (e.g., propylene oxide) in the presence of a multifunctional initiator (such as water and a low molecular weight polyol). Suitable low molecular weight polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, or combinations thereof.

[0027] In another embodiment, the polyol may include polyester polyols. Polyester polyols include polyesters having a linear polymer structure and a number average molecular weight ranging from about 500 Daltons to about 10,000 Daltons (e.g., preferably from about 700 Daltons to about 5,000 Daltons or from about 700 Daltons to about 4,000 Daltons), and an acid number generally less than 1.3 (e.g., less than 0.8). The molecular weight is determined by assaying the terminal functional groups and is related to the number average molecular weight. Polyester polymers can be obtained using techniques known in the art, such as (1) esterification of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) transesterification (i.e., reaction of one or more glycols with an ester of a dicarboxylic acid). A molar ratio of glycol to acid in excess of greater than 1 is generally preferred to obtain linear polymer chains with terminal hydroxyl groups. Suitable polyester polyols also include various lactones that are typically prepared from caprolactone and a difunctional initiator, such as diethylene glycol. The dicarboxylic acids of the desired polyesters can be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suitable dicarboxylic acids, which may be used alone or in mixtures, generally have a total of 4 to 15 carbon atoms, such as Dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, or combinations thereof. Anhydrides of the aforementioned dicarboxylic acids (e.g., phthalic anhydride, tetrahydrophthalic anhydride, or combinations thereof) may also be used. In some embodiments, adipic acid is the preferred acid. Glycols used in forming suitable polyester polyols may include aliphatic and aromatic glycols having a total of 2 to 12 carbon atoms. Examples of such glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, or combinations thereof.

[0028] Additional examples of suitable polyols include hydroxyl-terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins, and polysiloxanes, and in some embodiments, a polyol may be combined with another isocyanate-reactive material, such as, but not limited to, a polyamine or a polythiol. Suitable polyamines include primary and secondary amine-terminated polyethers, aromatic diamines (such as diethyltoluenediamine), aromatic polyamines, and combinations thereof.

[0029] In one embodiment, the amount of polyol present in the reaction mixture is at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, based on the total weight of components (i), (iii), (iv), (v), and (vi) above. In other embodiments, the amount of polyol present in the reaction mixture is in the range of about 50% to 95% by weight, or about 55% to about 90% by weight, or about 60% to about 85% by weight, based on the total weight of components (i), (iii), (iv), (v), and (vi) above. In yet another embodiment, the amount of polyol present in the reaction is less than 50% by weight, or less than about 45% by weight, or less than about 40% by weight, based on the total weight of components (i), (iii), (iv), (v), and (vi) above.

[0030] The reaction mixture also includes (ii) a polyisocyanate. The polyisocyanate may be selected from the group consisting of (1) diphenylmethane diisocyanate containing at least 40%, preferably at least 50% or at least 60%, and most preferably at least 85% by weight of 4,4'-diphenylmethane diisocyanate (4,4'-MDI); (2) carbodiimide and / or uretonimine modified variants of diphenylmethane diisocyanate (1) having an NCO value of 20% by weight or more; (3) urethane modified variants of diphenylene diisocyanate (1) having an NCO value of 20% by weight or more, which are reaction products of an excess of diphenylmethane diisocyanate (1) with a polyol having an average nominal hydroxyl functionality of 2 to 4 and an average molecular weight of up to 100; (4) an excess of any of the aforementioned polyisocyanates (1) to (3) with a polyol having an average nominal hydroxyl functionality of 2 to 6, an average molecular weight of 2000 to 12000, and preferably an average molecular weight of 15 to 60 mg / kg. and (4) a prepolymer having an NCO value of 20% by weight or more, which is the reaction product of a polyol having a hydroxyl value of 15-60 mg KOH / g, such as petroleum-based polyester polyols and polyether polyols, in particular those derived from polyoxyethylene polyoxypropylene polyols having an average nominal hydroxyl functionality of 2-4, an average molecular weight of 2500-8000, and preferably a hydroxyl value of 15-60 mg KOH / g, and preferably an oxyethylene content of 5-25% by weight, the oxyethylene being preferably located at the ends of the polymer chain, or an oxyethylene content of 50-90% by weight, the oxyethylene being preferably randomly distributed along the polymer chain; For example, MDI containing 30% to 80% w / w of 4,4'-MDI, with the remainder including MDI oligomers and MDI homologues, (6) 2,4-MDI, or (7) a mixture of any of the aforementioned polyisocyanates. In some embodiments, polyisocyanates (1) and (2) and mixtures thereof may be preferred as the polyisocyanate.

[0031] In other embodiments, the polyisocyanate can be toluene diisocyanate ("TDI") (e.g., 2,4TDI, 2,6TDI, or combinations thereof), hexamethylene diisocyanate ("HMDI" or "HDI"), isophorone diisocyanate ("IPDI"), butylene diisocyanate, trimethylhexamethylene diisocyanate, di(isocyanatocyclohexyl)methane (e.g., 4,4'-diisocyanatodicyclohexylmethane), isocyanatomethyl-1,8-octane diisocyanate, tetramethylxylene diisocyanate ("TMXDI"), 1,5-naphthalene diisocyanate ("NDP"), p-phenylene diisocyanate ("PPDI"), 1,4-cyclohexane diisocyanate ("CDI"), tolidine diisocyanate ("TODI"), or combinations thereof.

[0032] The mixture of polyisocyanates can be obtained according to any method known in the art. The isomer content of diphenylmethane diisocyanate can be adjusted to the required range by methods well known in the art, if necessary. For example, one method for changing the isomer content is to add monomeric MDI (e.g., 2,4-MDI) to a mixture of MDI that contains a higher amount of polymeric MDI than desired.

[0033] The reaction mixture also includes (iii) a catalyst. According to one embodiment, the catalyst includes a trimerization catalyst. Examples of trimerization catalysts include, but are not limited to, tris(dialkylaminoalkyl)-s-hexahydrotriazines (such as 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine), potassium salts of carboxylic acids (e.g., potassium acetate, potassium pivalate, potassium octanoate, potassium triethylacetate, potassium neoheptanoate, potassium neooctanoate, potassium ethylhexanoate), tetraalkylammonium hydroxides (such as tetramethylammonium hydroxide), alkali metal hydroxides (such as sodium hydroxide), alkali metal alkoxides (such as tetramethylammonium hydroxide), and the like. Examples of suitable ammonium salts include alkoxides (such as sodium methoxide and potassium isopropoxide), alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and, in some embodiments, pendant hydroxyl groups, quaternary ammonium carboxylates (e.g., (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate ("TMR"), (2-hydroxypropyl)trimethylammonium formate ("TMR-2"), tetramethylammonium pivalate, tetramethylammonium triethylacetate), and combinations thereof.

[0034] The trimerization catalyst may be one or more organometallic salts, preferably alkali metal salts or alkaline earth metal salts, as well as -CO-NH 2 and / or one or more compounds selected from compounds containing a carboxamide group having the structure: -CO-NH-CO- (described in paragraphs

[0039] to

[0052] of EP2830761B1, the contents of which are incorporated herein by reference).

[0035] The amount of trimerization catalyst present in the reaction mixture can be in the range of about 0.01 to 5 weight percent based on the weight of (i) polyol and (ii) polyisocyanate, or in some embodiments, in the range of about 0.05 to 3 weight percent based on the total weight of (i) polyol and (ii) polyisocyanate.

[0036] The catalyst may be an amine catalyst compound containing at least one tertiary amine group, a non-amine catalyst compound, It may also include a mixture thereof.

[0037] Examples of amine catalyst compounds containing at least one tertiary group include, but are not limited to, bis-(2-dimethylaminoethyl)ether (e.g., JEFFCAT® ZF-20 catalyst), N,N,N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether (e.g., JEFFCAT® ZF-10 catalyst), N-(3-dimethylaminopropyl)-N,N-diisopropanolamine (e.g., JEFFCAT® DPA catalyst), N,N-dimethylethanolamine (e.g., JEFFCAT® 10 catalyst), N ... DMEA catalyst), mixtures of N,N-dimethylethanolamine and ethylenediamine (e.g., JEFFCAT® TD-20 catalyst), N,N-dimethylcyclohexylamine (e.g., JEFFCAT® DMCHA catalyst), N-methyldicyclohexylamine (e.g., POLYCAT® 12 catalyst), benzyldimethylamine (e.g., JEFFCAT® BDMA catalyst), diethyltoluenediamine, pentamethyldiethylenetriamine (e.g., JEFFCAT® ... ) PMDETA catalyst), N,N,N',N'',N''-pentamethyldipropylenetriamine (e.g., JEFFCAT® ZR-40 catalyst), N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine (e.g., JEFFCAT® ZR-50 catalyst), N'-(3-(dimethylamino)propyl-N,N-dimethyl-1,3-propanediamine (e.g., JEFFCAT® Z-130 catalyst), 2-(2-dimethylaminoethoxy)ethanol (e.g., JEFFCAT® Z-20 catalyst), JEFFCAT® ZR-70 catalyst), N,N,N'-trimethylaminoethyl-ethanolamine (e.g., JEFFCAT® Z-110 catalyst), N-ethylmorpholine (e.g., JEFFCAT® NEM catalyst), N-methylmorpholine (e.g., JEFFCAT® NMM catalyst), 4-methoxyethylmorpholine, N,N'-dimethylpiperazine (e.g., JEFFCAT® DMP catalyst), 2,2'-dimorpholinodiethyl ether (e.g., JEFFCAT® DMDEE catalyst), 1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine (e.g., JEFFCAT® TR-90 catalyst), 1-propanamine, 3-(2-(dimethylamino)ethoxy), substituted imidazoles (e.g., 1-methylimidazole, 1,2-dimethylimidazole (e.g., DABCO® 2040 catalyst and TOYOCAT® DM70 catalyst), 1-methyl-2-hydroxyethylimidazole, N-(3-aminopropyl)imidazole, 1-n-butyl- 2-Methylimidazole, 1-iso-butyl-2-methylimidazole, N,N'-dimethylpiperazine, bis-substituted piperazines (e.g., aminoethylpiperazine, N,N',N'-trimethylaminoethylpiperazine or bis-(N-methylpiperazine)urea), N-methylpyrrolidine and substituted methylpyrrolidines (e.g., 2-aminoethyl-N-methylpyrrolidine or bis-(N-methylpyrrolidine)ethylurea), 3-dimethylaminopropylamine, N,N,N'',N''-tetramethyldiphenylamine, Propylenetriamine, tetramethylguanidine, and 1,2-bis-diisopropanol. Other examples of amine catalysts include N-butylmorpholine, dimorpholinodiethyl ether, N,N'-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol, bis-(dimethylaminopropyl)-amino-2-propanol, bis-(dimethylamino)-2-propanol, bis-(N,N-dimethylamino)ethyl ether, N,N,N'-trimethyl-N'hydroxyethyl- Bis-(aminoethyl)ether, N,N-dimethylaminoethyl-N-methylaminoethanol, tetramethyliminobispropylamine, N,N-dimethyl-p-toluidine, diethyltoluenediamine, 3,5-dimethylthio-2,4-toluenediamine; poly(oxypropylene)triamine (JEFF Amine® T-5000 amine), reactive acid block catalysts (e.g., phenolate of 1,8-diazabicyclo(5,4,0)undecene-7), and combinations thereof.

[0038] Non-amine catalyst compounds include organometallic compounds (e.g., organic salts of transition metals (e.g., titanium, iron, nickel, etc.)), post-transition metals (e.g., zinc, tin, and bismuth), alkali metals (e.g., lithium, sodium, and potassium), alkaline earth metals (e.g., magnesium and calcium), or combinations thereof. Other suitable non-amine catalyst compounds include ferric chloride, ferric acetylacetonate, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, stannous chloride, stannic chloride, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids, tin(II) 2-ethylhexanoate, dibutyltin dilaurate, dimethyltin dimercaptide, bismuth(III) carboxylates (e.g., bismuth(2-ethylhexanoate)), bismuth neodecanoate, bismuth pivalate, bismuth-based catalysts, 1,1',1'',1''''-(1,2-ethanediyldinitrilo)tetrakis[2-propanol] neodecanoate complex, 2,2',2'',2''''-(1,2-ethanediyldinitrilo)tetrakis[ethanol] neodecanoate complex, K-KAT XC-C 227 Included are bismuth salts (available from King Industries), sodium acetate, sodium N-(2-hydroxy-5-nonylphenol) methyl-N-methylglycinate (JEFFCAT® TR52), bismuth (2-ethylhexanoate), and combinations thereof.

[0039] The amount of amine catalyzed compound and non-amine catalyzed compound present in the reaction mixture can be in the range of about 0.01 to 4 weight percent, or about 0.2 to 3.7 weight percent, or about 0.5 to 3.5 weight percent, based on the total weight of (i) polyol and (ii) polyisocyanate.

[0040] The reaction mixture also includes (iv) a blowing agent. In one embodiment, the blowing agent includes water. For purposes of this disclosure, water shall be considered a component separate from component (i). In other words, the reaction mixture disclosed herein includes not only component (i) but also water.

[0041] Any type of water may be used, including purified water that has been filtered or treated to remove impurities. Other suitable types of water include distilled water and water that has been purified via one or more of the following processes: capacitive deionization, reverse osmosis, carbon filtration, microfiltration, ultrafiltration, ultraviolet oxidation, and / or electrodeionization.

[0042] The amount of blowing agent present in the reaction mixture can be in the range of about 0.1 to 2.5 weight percent or about 0.2 to 1.5 weight percent, based on the total weight of (i) the polyol.

[0043] The reaction mixture may also optionally include (v) at least one chain extender or crosslinker. Chain extenders are generally classified as having a functionality equal to 2, and include diols, diamines, and combinations thereof. The chain extender may have a molecular weight of up to about 500 Daltons or up to about 300 Daltons, such as at least about 35-500 Daltons.

[0044] One or more short chain polyols having 2 to 20 or 2 to 12 or 2 to 10 or 2 to 8 carbon atoms can be used as chain extenders in the reaction system to increase the molecular weight of the thermoplastic polyurethane. Examples of chain extenders include, but are not limited to, lower aliphatic polyols and short chain aromatic glycols having a molecular weight of less than 500 Daltons or less than 300 Daltons. Suitable chain extenders include organic diols (including glycols) having a total of 2 to about 20 carbon atoms, such as alkane diols, cycloaliphatic diols, alkylaryl diols, and the like. Examples of alkane diols include ethylene glycol, diethylene glycol, 1,3-propane diol, 1,3-butane diol, 1,4-butane diol, (BDO), 1,5-pentane diol, 2,2-dimethyl-1,3-propane diol, propylene glycol, dipropylene glycol, 1,6-hexane diol, 1,7-heptane diol, 1,9-nonane diol, 1,6-hexane diol, 1,7-heptane diol, 1,9-nonane diol, 1,7-nonane diol, 1,8-nonane diol, 1,9 ... Diols include 1,10-decanediol, 1,12-dodecanediol, tripropylene glycol, triethylene glycol, and 3-methyl-1,5-pentanediol. Examples of suitable cycloaliphatic diols include 1,2-cyclopentanediol and 1,4-cyclohexanedimethanol (CHDM). Examples of suitable aryl diols and alkylaryl diols include hydroquinone di(1,3-hydroxyethyl)ether (HQEE), 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2-di(hydroxymethyl)benzene, 1,4-di(hydroxymethyl)benzene, 1,3-di(2-hydroxyethyl)benzene, 1,2-di(2-hydroxyethoxy)benzene, 1,4-di-(2-hydroxyethoxy)benzene, bisethoxybiphenol, 2,2-di(4-hydroxyphenyl)propane (i.e., bisphenol A), bisphenol A ethoxylate, bisphenol F ethoxylate, 4,4-isopropylidenediphenol, 2,2-di[4-(2-hydroxyethoxy)phenyl]propane (HEPP), and mixtures thereof. In another embodiment, the chain extender is a sucrose-based polyol, such as sorbitol.

[0045] In another embodiment, the chain extender is (HO) x Q(COOH) ywhere Q is a straight or branched chain hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are each an integer between 1 and 3. In certain embodiments, the chain extender comprises a diol carboxylic acid. In other embodiments, the chain extender comprises a bis(hydroxyl alkyl) alkanoic acid. In certain embodiments, the chain extender comprises a bis(hydroxyl methyl) alkanoic acid. In certain embodiments, the diol carboxylic acid is selected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoic acid (dimethylol propionic acid, DMPA), 2,2-bis(hydroxymethyl) butanoic acid (dimethylol butanoic acid, DMBA), dihydroxy succinic acid (tartaric acid), and 4,4'-bis(hydroxyphenyl) valeric acid. In certain embodiments, the chain extender comprises an N,N-bis(2-hydroxy alkyl) carboxylic acid.

[0046] Crosslinkers are generally classified as having a functionality equal to or greater than 3. Crosslinkers are also typically represented by relatively short chain or low molecular weight molecules, such as glycerin, ethanolamine, diethanolamine, trimethylolpropane (TMP), 1,2,6-hexanetriol, triethanol-amine, pentaerythritol, N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine, diethyl-toluenediamine, dimethylthiotoluenediamine, and combinations thereof.

[0047] In one embodiment, the amount of (v) chain extender or crosslinker or mixtures thereof present in the reaction mixture may be in the range of about 0.1-15 wt %, based on the total weight of (i) polyol, hi another embodiment, the amount of chain extender or crosslinker or mixtures thereof present in the reaction mixture may be in the range of about 0.5-12 wt %, or about 1-10 wt %, based on the total weight of (i) polyol.

[0048] The reactive system may also optionally include (vi) one or more known additives, including, but not limited to, surfactants, silane adhesion promoters, antioxidants, waxes, colorants, flame retardants, microbial inhibitors, fillers, mold release agents, viscosity reducers; carbon black, titanium dioxide, and metal flake infra-red opacifiers, inert and insoluble fluorinated compounds, and perfluorinated cell size reducing compounds, calcium carbonate filler, glass fibers, and / or ground foam waste reinforcements; zinc stearate, butylated hydroxytoluene antioxidants, dyes, and pigments.

[0049] In certain embodiments, the surfactant is one or more silicone-based or non-silicone based surfactants. Suitable silicone surfactants that may be disclosed herein include polyorganosiloxane polyether copolymers and polysiloxane polyoxyalkylene block copolymers.

[0050] Non-silicone surfactants that may be used in the polyurethane insulating foam compositions disclosed herein include nonionic, anionic, cationic, amphoteric, semi-polar, and zwitterionic organic surfactants. Suitable nonionic surfactants include phenol alkoxylates and alkylphenol alkoxylates (e.g., ethoxylated phenol and ethoxylated nonylphenol, respectively).

[0051] When present, such additional additives may be used in amounts of about 0.01 to 15 weight percent, or about 0.1 to 10 weight percent, or about 0.5 to 5 weight percent, based on the total weight of the reaction mixture. These ranges may apply individually to each additional additive present in the reaction mixture or to the sum of all additional additives present.

[0052] In some embodiments, the reaction mixture may have a hydroxyl number in the range of about 150-700 mg KOH / g, or about 200-600 mg KOH / g, or about 350-500 mg KOH / g. In another embodiment, the reaction mixture may have an isocyanate index greater than about 201, or greater than about 203, or greater than about 205, or greater than about 207, or greater than about 210. In other embodiments, the reaction mixture may have an isocyanate index less than about 10,000, or less than about 1000, or less than about 500. In yet other embodiments, the reaction mixture may have an isocyanate index in the range of greater than about 200 to less than 500, or about 201-350.

[0053] According to another embodiment, a process for the production of polyurethane / polyisocyanurate molded articles is provided, the process comprising: a) applying a first fibrous material having a first surface and a second surface to a first surface of a core material; b) applying a second fibrous material having a first surface and a second surface to a second surface of the core material to form a sandwich structure having a first surface and a second surface, where the first fibrous material and the second fibrous material can be the same or different; c) applying a reaction mixture of the present disclosure to a first surface and a second surface of the sandwich structure to form a reaction mixture coated sandwich structure; d) placing the reactive mixture coated sandwich structure into a mold; e) shaping the reaction mixture coated sandwich structure in a mold at a temperature of about 100° C. to about 200° C. while curing the reaction mixture to form a polyurethane / polyisocyanurate molded article; f) removing the polyurethane / polyisocyanurate molding from the mold; e) optionally post-treating the polyurethane / polyisocyanurate molded article; Includes.

[0054] According to steps a) and b), a first fibrous material and a second fibrous material are applied to a first surface and a second surface of a core material to form a sandwich structure having a first surface and a second surface. The first fibrous material and the second fibrous material can be the same or different, and the first fibrous material and the second fibrous material can include woven fiber mats, non-woven fiber mats, continuous strand fibers, fiber random structures, fiber textures, chopped fibers, milled fibers, knitted fabrics, reinforced fiber mats, or any combination thereof. Preferred fibers are carbon fibers, polymeric fibers (e.g., KEVLAR™ fibers or aramid fibers), mineral fibers, glass fibers, and the like. , natural fibers (kenaf, hemp, coconut, etc.), and mixtures thereof. In one embodiment, the fibrous material is a fiberglass mat, a nonwoven fiberglass fabric, randomly laid fiberglass, a woven fiberglass fabric, or chopped or ground glass.

[0055] Core materials may include honeycomb paperboard, plastic honeycomb, aluminum honeycomb, balsa wood, rigid foam, compressed or uncompressed cotton fiber, compressed or uncompressed natural fiber, or compressed or uncompressed plastic fiber (such as polyethylene terephthalate (PET)).

[0056] The reactive mixture is then applied to the first and second surfaces of the sandwich structure to form a reactive mixture-coated sandwich structure, which is then placed in a mold in steps c) and d). Concurrently with the application of the reactive mixture, chopped fibers can be optionally applied onto the whole or part of one or both of the surfaces of the sandwich structure. For example, if a reinforcing fiber mat is used in steps a) and / or b), the mat can be first selected and the reactive mixture can be impregnated into the mat in a conventional manner, and then one or more types of chopped fibers can be additionally applied onto the whole or part of the surface(s) at the same time. Bonding of such additionally applied reactive mixture-wet chopped fibers occurs. The application of the reactive mixture to the fibrous material can be affected by conventional methods, such as spray application, knife coating, or roll application. The application can be affected at an elevated temperature, for example, between 20° C. and 50° C., preferably between 23° C. and 45° C. The amount applied can be up to 150 g / m 2 . 2 ~5000g / m 2 , particularly preferably 200 g / m 2 ~2000g / m 2 , more preferably 400 g / m 2 ~1000g / m 2 , especially 425g / m 2 ~500g / m 2 This results in a reactive mixture coated sandwich structure having a core material and two reactive mixture-containing fiber materials, which are then placed into a mold.

[0057] The reactive mixture coated sandwich structure is then shaped and cured in a mold. The mold temperature can be in the range of about 0-180°C or about 100-160°C or about 130-150°C. The core material and the fiber material can be optionally compressed together with one or more of the outer or decorative layers. In this case, the outer or decorative layer can be applied to one or both sides of the reactive mixture coated sandwich structure or can be placed in the mold. Alternatively, the outer or decorative layer can be applied in a further work step after demolding of the polyurethane / polyisocyanurate molding.

[0058] In this context, the decorative material may be carpet, textiles not impregnated with polyurethane, high density or foamed plastic films, and sprayed or RIM skins of polyurethane. Metal foils or sheets (e.g. aluminum or steel) may also be used as outer layers, as well as preformed materials suitable for external application, such as high density thermoplastic composites of PMMA (polymethyl methacrylate), ASA (acrylic acid ester modified styrene-acrylonitrile terpolymer), PC (polycarbonate), PA (polyamide), PBT (polybutylene terephthalate), and / or PPO (polyphenylene oxide) in painted, paintable prepared, or pigmented form, glass reinforced composite sheets (e.g. sheet molding compounds, polyurethane), in-mold coatings, and combinations thereof. Similarly, continuous or batch produced outer layers based on melamine-phenolic resins, phenol-formaldehyde resins, epoxy resins, or unsaturated polyester resins may also be used as outer layers.

[0059] During compression, the core material undergoes compression in at least some regions of the core material. Compression can vary over a wide range, ranging from tens of millimeters to a compression of less than 10% of the original thickness of the core material. When compressing the reactive mixture sandwich structure, the core material is preferably compressed to different degrees in different regions. Alternatively, the reactive mixture can be It may be applied to one or both sides of the first or second fibrous material or both fibrous materials. The fibrous material containing the reaction mixture is then applied onto the core material.

[0060] In an alternative embodiment to the above embodiment, a process for the production of polyurethane / polyisocyanurate molded articles is provided, the process comprising: a) placing a substrate (such as a textile or carpet) into a mold; b) applying a reaction mixture of the present disclosure to a surface of a substrate; c) applying a first fibrous material having a first surface and a second surface to the first surface of the core material; d) applying a second fibrous material having a first surface and a second surface to a second surface of the core material to form a sandwich structure having a first surface and a second surface, where the first fibrous material and the second fibrous material can be the same or different; e) placing the sandwich structure in a mold such that a first surface of the sandwich structure is adjacent to the reaction mixture; f) applying a reaction mixture of the present disclosure to a second surface of the sandwich structure by spray application to form a reaction mixture coated sandwich structure; g) forming a polyurethane / polyisocyanurate molded article by shaping the reaction mixture coated sandwich structure in a mold at a temperature of about 100° C. to about 200° C. while curing the reaction mixture; f) removing the polyurethane / polyisocyanurate molding from the mold; e) optionally post-treating the polyurethane / polyisocyanurate molded article; Includes.

[0061] In some embodiments, the sandwich structure can be pre-formed and therefore steps c) and d) can be omitted and instead of steps e) and f), e) placing the preformed sandwich structure in the mold such that a first surface of the preformed sandwich structure is adjacent to the reaction mixture; f) applying a reaction mixture of the present disclosure to a second surface of the preformed sandwich structure by spray application to form a reaction mixture coated sandwich structure; can be carried out.

[0062] In some embodiments, the substrate can also be a metal foil, a metal sheet, a painted, paintable formulation, or pigmented form of polymethyl methacrylate, an acrylate-modified styrene-acrylonitrile terpolymer, a thermoplastic composite of polycarbonate, polyamide, polybutylene terephthalate, and / or polyphenylene oxide, a glass-reinforced composite sheet, an in-mold coating, and combinations thereof.

[0063] 1A-1C, the process of the present disclosure includes first applying a first fibrous material 10 having a first surface 11 and a second surface 12 to a first surface 31 of a core material 30. Simultaneously or sequentially, a second fibrous material 20 having a first surface 21 and a second surface 22 is applied to a second surface 32 of the core material 30 to form a sandwich structure 40 having a first surface 41 and a second surface 42, where the first fibrous material 10 and the second fibrous material 20 can be the same or different. A low or high pressure dispenser 50 can be used to spray the reaction mixture of the present disclosure from a mix head 53. The mix head 53 is fed from an A-side tank 51 containing a polyisocyanate and a B-side tank 52 containing a polyol. Components (iii), (iv), (v), and (vi) of the reaction mixture can be individually contained in either the A-side tank or the B-side tank. The contents of the A-side tank and the B-side tank are mixed in the mix head 53, which mixes the contents of the A-side tank and the B-side tank on sides 41 and 42, respectively, of the sandwich structure 40. The mixture is sprayed onto the sandwich structure 40 via a spray nozzle 54. The reaction mixture from the mix head 53 can be applied to the sandwich structure 40 in a vertical position (not shown in Figs. 1A-1C) or preferably in a horizontal position (shown in Fig. 1A). The reaction mixture 55 is applied to the first surface 41 and the second surface 42 of the sandwich structure 40. Preferably, the (fixed) sandwich structure can be moved, preferably by a robot, in both X- and Y-directions (vertical and horizontal) under the dispenser so that an evenly distributed coating can be applied over the entire surface of the sandwich structure 40. Preferably, the sandwich structure 40 rotates, preferably fixed, and rotates under robotic control so that each of the sides 41 and 42 can receive a spray of 55.

[0064] The sandwich structure 40 is then coated with the reactive mixture and placed into a mold 60 having a mold cavity defined by a top mold half 61 and a bottom mold half 62 (or alternatively, the sandwich structure 40 is placed into the mold 60 and coated with the reactive mixture), which mold 60 is capable of shaping the reactive mixture coated sandwich structure 40 into a desired molded article shape. Preferably, the mold 60 is temperature controlled. The mold is closed (70) and the reactive mixture coated sandwich structure is shaped during a molding and curing step 80. Preferably, the mold temperature is in the range of about 100° C. to about 160° C. or about 130° C. to about 150° C. While the mold is closed and during / after shaping, the reactive mixture cures (80) to form a molded polyurethane / polyisocyanurate coated sandwich structure or molded polyurethane article 100. The mold 60 is opened and the molded polyurethane article 100 is removed (90) from the mold 50. Optionally, the molded polyurethane article can be post-treated with one or more treatments, for example, carpet can be applied, it can be painted, a decorative skin can be applied, it can be trimmed into a desired shape, etc. In some embodiments, one or more outer layers or decorative materials can be applied to the reactive mixture coated sandwich structure before the mold 60 is closed and the reactive mixture is cured.

[0065] In one embodiment, the mold 60 is designed so that when the reactive mixture coated sandwich structure is shaped, some or all of the outer edges of the final molded part are shaped so that the inner core material is not visible or exposed, in other words, as shown in FIG. 1B, the cured polyurethane / polyisocyanurate coated fiber surfaces 101 and 102 cover or hide the core material and / or contact each other (103).

[0066] The polyurethane / polyisocyanurate sandwich panels produced by the process according to the present disclosure may be used, for example, as structural parts or fittings, especially in the automotive, furniture, or construction industries.

[0067] Molded articles produced according to the present disclosure can be used as structural or interior lining / covering parts, particularly for the automotive industry, such as luggage compartment floors, lower soundproofing shields, sound absorbing belly pans, aero shields, splash shields, vehicle bottom panels, chassis shields, door modules, rear packages, leaf springs, roofs, or hoods, in the furniture industry and in the building and construction industry, such as door or window frames and facades.

[0068] The following examples are offered to illustrate the disclosure but are not intended to limit its scope. EXAMPLES

[0069] Honeycomb sandwich panels obtained using different reaction mixtures Honeycomb core (cell size 6mm) with 450g / m 2 The raw sandwich structure was covered with 400 ml of randomly chopped glass mat. 50g / m 2 Then spray with 450 g / m 2The outer edges were sprayed with 100% ethyl alcohol. The coated sandwich structure was then placed in a mold for 60 seconds, cured, and removed from the mold. Each molded part was then exposed to temperatures approaching 210°C for a minimum of 30 minutes, and the molded parts were examined to determine if any defects were present in the molded parts. [Table 1] Polyol 1-PO based polyol, hydroxyl number 650 Polyol 2-PO based polyol, hydroxyl number 240 Crosslinker - Glycerin Catalyst 1-Diethyltoluenediamine Catalyst 2-acid blocked tertiary amine Diethylene glycol containing catalyst potassium 3-octanoate

[0070] Comparative Example 1 was a comparative reaction mixture formulated to an index number of 205, which was used to obtain molded parts at mold temperatures of 130° C., 140° C., and 150° C. These molded parts were exposed to a temperature of 210° C. for the times discussed above and showed severe blistering and defects on each of their surfaces.

[0071] Examples 1 and 2 are extensions of Comparative Example 1, and were formulated with increased index numbers of 255 and 305, respectively. Both parts of Example 1 and Example 2 molded at a mold temperature of 130° C. and then exposed to a temperature of 210° C. still showed defects, whereas when the mold temperature was increased to 140° C. and 150° C., the molded parts showed no defects after exposure to temperatures of 210° C.

[0072] Examples 3-5 reflect changes in the formulation with the introduction of a crosslinker while maintaining the same B-side hydroxyl number. For Example 3, parts molded at 130°C and 140°C mold temperatures and exposed to a temperature of 210°C showed defects, but parts molded at 150°C mold temperature and exposed to a temperature of 210°C showed no defects. Similar findings were observed for Example 4. Surprisingly, parts from Example 5 showed no defects after molding at 130°C, 140°C, or 150°C mold temperatures and exposed to a temperature of 210°C. It is noted that the molecular weight between crosslinks (Mc) and onset of glass transition (DMA G') are similar for the two B-side variations (Comparative Example 1 / Example 1 / Example 2 vs. Example 3 / Example 4 / Example 5), which may suggest that the crosslinker plays a role beyond crosslink density to improve thermal stability.

[0073] In Example 6, the A-side isocyanate was switched from a 4,4'-MDI based prepolymer to a uretonomine modified 4,4'-diphenylmethane diisocyanate. Parts molded at a temperature of 140°C did not show any defects after exposure to a temperature of 210°C. [Table 2]

[0074] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, which is determined by the claims that follow.

Claims

1. 1. A reaction mixture for use in the production of a polyurethane / polyisocyanurate sandwich panel exhibiting high temperature stability, said reaction mixture comprising: (i) a polyol; (ii) a polyisocyanate; (iii) a catalyst; (iv) a blowing agent; and optionally (v) at least one chain extender or crosslinker; and optionally (vi) additives, said reaction mixture having an Isocyanate Index greater than 200.

2. 10. The reaction mixture of claim 1, wherein the polyol comprises a polyether polyol.

3. 3. The reaction mixture of claim 2, wherein the polyether polyol is a poly(oxypropylene) diol or poly(oxypropylene) triol obtained by addition of propylene oxide to a difunctional or trifunctional initiator.

4. 2. The reaction mixture of claim 1, wherein the polyisocyanate is selected from (1) diphenylmethane diisocyanate comprising at least 40 weight percent 4,4'-diphenylmethane diisocyanate (4,4'-MDI), based on the total weight of diphenylmethane diisocyanate, (2) carbodiimide and / or uretonimine modified variants of diphenylmethane diisocyanate (1) having NCO values ​​of 20 weight percent or greater, and (3) mixtures thereof.

5. 2. The reaction mixture of claim 1, wherein the catalyst comprises a trimerization catalyst.

6. 2. The reaction mixture of claim 1, wherein the chain extender or crosslinker comprises ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, (BDO), 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, propylene glycol, dipropylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, tripropylene glycol, triethylene glycol, or 3-methyl-1,5-pentanediol, glycerin, sorbitol, or mixtures thereof.

7. 10. The reaction mixture of claim 1, wherein the one or more additives comprises a surfactant.

8. 1. A process for the production of polyurethane / polyisocyanurate molded articles exhibiting high temperature stability, comprising: a) applying a first fibrous material having a first surface and a second surface to a first surface of a core material; b) applying a second fibrous material having a first surface and a second surface to a second surface of the core material to form a sandwich structure having a first surface and a second surface, the first fibrous material and the second fibrous material can be the same or different; c) applying the reaction mixture of claim 1 to the first surface and the second surface of the sandwich structure to form a reaction mixture-coated sandwich structure; d) placing the reaction mixture coated sandwich structure into a mold; e) shaping the reaction mixture coated sandwich structure in the mold at a temperature in the range of about 100° C. to about 160° C. while curing the reaction mixture to form the polyurethane / polyisocyanurate molded article; f) removing the polyurethane / polyisocyanurate molded article from the mold; e) optionally post-treating the polyurethane / polyisocyanurate molded article; The process comprising:

9. 9. The process of claim 8, wherein e) shaping the reaction mixture coated sandwich structure in the mold is performed at a temperature in the range of about 130°C to about 150°C.

10. 9. The process of claim 8, wherein the first fibrous material and the second fibrous material individually comprise a woven fibrous mat, a nonwoven fibrous mat, continuous strand fibers, a fibrous random structure, a fibrous texture, chopped fibers, milled fibers, a knitted fabric, a reinforced fibrous mat, or any combination thereof.

11. 9. The process of claim 8, wherein the core material comprises honeycomb paperboard, plastic honeycomb, aluminum honeycomb, balsa wood, rigid foam, compressed or uncompressed cotton fiber, compressed or uncompressed natural fiber, or compressed or uncompressed plastic fiber.

12. The process of claim 8 , wherein the reactive mixture coated sandwich structure is compressed together with one or more of an exterior layer or a decorative layer.

13. 13. The process of claim 12, wherein the outer layer comprises metal foil, metal sheet, polymethyl methacrylate in painted, paintable, or pigmented form, acrylate-modified styrene-acrylonitrile terpolymer, polycarbonate, polyamide, polybutylene terephthalate, and / or polyphenylene oxide thermoplastic composites, glass reinforced composite sheets, in-mold coatings, and combinations thereof.

14. 9. A polyurethane / polyisocyanurate molded article produced according to the process of claim 8.

15. 15. The polyurethane / polyisocyanurate molded article of claim 14, wherein the molded article is an automotive structural part.

16. 16. The polyurethane / polyisocyanurate molded article of claim 15, wherein the automotive structural part is a luggage compartment floor, a lower soundproof shield, a sound-absorbing belly pan, an aero shield, a splash shield, a vehicle bottom panel, a chassis shield, a door module, a rear package, a leaf spring, a roof, or a hood.

17. 1. A process for the production of polyurethane / polyisocyanurate moulded articles comprising the steps of: a) placing a substrate in a mold; b) applying the reaction mixture of claim 1 to the surface of the substrate; c) applying a first fibrous material having a first surface and a second surface to the first surface of the core material; d) applying a second fibrous material having a first surface and a second surface to a second surface of the core material to form a sandwich structure having a first surface and a second surface, the first fibrous material and the second fibrous material can be the same or different; e) placing the sandwich structure in the mold such that the first surface of the sandwich structure is adjacent to the reaction mixture; f) applying the reaction mixture of claim 1 to the second surface of the sandwich structure by spray application to form a reaction mixture-coated sandwich structure; g) shaping the reaction mixture coated sandwich structure in the mold at a temperature of about 100° C. to about 200° C. while curing the reaction mixture to form the polyurethane / polyisocyanurate molded article; f) removing the polyurethane / polyisocyanurate molded article from the mold; e) optionally post-treating the polyurethane / polyisocyanurate molded article; The process comprising:

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