Composite material formed using Lewis acid polymerized polyol and method for preparing the same

Abstract

The method involves forming a composite material, comprising reacting an isocyanate component with an isocyanate-reactive component which comprises at least one Lewis acid catalyst polyether polyol having a weight percentage (W%) of 90% or more of polypropylene oxide, a primary hydroxyl concentration of at least 30% by weight, a functional value of at least 2, an OH value in the range of 100 mg KOH / g to 800 mg KOH / g, an average acetal content of at least 0.05% by weight, and a water content in the range of 0.1% to 2% by weight based on the weight of the isocyanate-reactive component, wherein at least one of the isocyanate component, the isocyanate-reactive component, or a third component is a reinforcing material.

Description

[Technical Field]

[0001] The embodiments relate to polyurethane compositions used in the manufacture of polyurethane composites and reinforcing materials with improved mechanical properties.

[0002] Introduction Polyurethane (PU) compounds can be manufactured into reinforced composites for structural components using several methods, including long fiber injection molding (LFI) and reinforced reaction injection molding (RRIM). In the LFI method, PU resin is sprayed or injected into an open mold simultaneously with chopped glass fibers. Once the mold is covered with the LFI-PU material, the mold is closed, and compression occurs at high temperatures, inducing the curing of the polyurethane. An advantage of the LFI-PU manufacturing process is that it allows the use of reinforcing fibers of discontinuous length, which can be concentrated in the target structural location. The final composite article can then exhibit good surface quality and low thermal expansion.

[0003] As with most manufacturing technologies, productivity improvements are achieved by reducing demolding time while maintaining or improving product quality. To reduce demolding time, catalysts or polyols containing higher concentrations of reactive primary hydroxyl groups (e.g., EO derivatives) can be used in higher quantities. However, the use of polyurethane catalysts can be very expensive, increase volatility, and shorten the curing time of the formulation during processing. Polyols containing high concentrations of primary hydroxyl groups can be obtained using EO as the alkoxylation agent, which results in higher hygroscopicity and can lead to water accumulation in the formulation when exposed to air. The increased polarity of EO-containing polyols can also lead to compatibility issues with non-polar formulation components, as well as problems related to the generation of haze and turbidity. [Overview of the Initiative]

[0004] In one embodiment, an embodiment of the present disclosure is a method for forming a composite material, comprising reacting an isocyanate component with an isocyanate-reactive component which comprises at least 90% by weight of polypropylene oxide, at least 30% by weight of primary hydroxyl concentration, at least 2 functional values, an OH value in the range of 100 mg KOH / g to 800 mg KOH / g, an average acetal content of at least 0.05% by weight, and a water content in the range of 0.1% by weight to 2% by weight based on the weight of the isocyanate-reactive component, wherein at least one of the isocyanate component, the isocyanate-reactive component, or a third component is a reinforcing material. [Brief explanation of the drawing]

[0005] [Figure 1] This is a graphical representation of compressive strength as a function of displacement for comparative polyols and Lewis acid polymerized polyols, measured according to ASTMD1621. [Modes for carrying out the invention]

[0006] Embodiments relate to a two-component polyurethane composition for use in the manufacture of composite materials, comprising a specific type of Lewis acid catalyst polyether polyol produced by polymerization in the presence of a perfluoroalkyl-substituted arylborane catalyst. The polyurethane composition comprises an isocyanate component and an isocyanate-reactive component comprising at least a Lewis acid catalyst polyether polyol. The Lewis acid catalyst polyether polyols disclosed herein may have a weight percentage (W%) of 90 Wt or more of polypropylene oxide, a primary hydroxyl concentration of at least 30 Wt, a functional value of at least 2, an OH value in the range of 100 mg KOH / g to 800 mg KOH / g, and an average acetal content of at least 0.05 Wt. The method also comprises the formation of a composite material, comprising combining the components in the presence of a reinforcing material using a preferred process such as LFI.

[0007] The use of Lewis acid polymerization catalysts (e.g., perfluoroalkyl-substituted arylborane catalysts) for the production of polyether polyols can improve polyol reactivity with isocyanate components, particularly for polypropylene oxide-based (or polyether polyols containing) polyether polyols, by increasing the percentage of primary hydroxyl groups. Increasing the concentration of primary hydroxyl groups is associated with faster curing times and improved appearance of the final product. Comparative formulations containing a concentration of polyethylene oxide to increase the percentage of primary OH-terminated functional groups result in some reduction of demolding time during production. However, the presence of polyethylene oxide also leads to reduced compatibility with non-polar polymer phases and layers such as PVC skin layers, the formation of open-cell structures susceptible to discoloration by oxidizing gases, and scorching associated with high reactivity. On the other hand, while polypropylene oxide-based polyether polyols exhibit good compatibility with non-polar phases, the preparation of polyether polyols from monomers with more than 2 carbon atoms (i.e., propylene oxide, butylene oxide) using standard KOH alkoxylation catalysts produces products with >95% secondary OH groups.

[0008] The PU compositions and composites disclosed herein contain polyether polyols produced by Lewis acid-catalyzed polymerization, which increase the percentage of primary hydroxyl groups and associated performance properties (e.g., reactivity, demolding time, etc.). The PU compositions and composites disclosed herein exhibit rapid demolding and cycle times, while unexpectedly showing improved mechanical strength compared to comparatively reactive polyols (e.g., EO-based polyols). In some cases, PU formulations containing Lewis acid-catalyzed polyether polyols can enable the formation of composites with good mechanical properties and good adhesion to PVC skin layers. The PU compositions disclosed herein can be rapidly cured with long working times according to ASTM D7487-18, as determined by FOAMAT® Foam Qualification System (Foamat Messtechnik GmbH, Karlsruhe, DE).

[0009] The PU compositions disclosed herein generally comprise a two-component curable composition, i.e., a product obtained by combining an isocyanate component ("side A") and an isocyanate-reactive component ("side B"). During the process, the isocyanate and the isocyanate-reactive component are mixed to initiate a curing reaction and form a PU composition or composite. During the formation of the PU composite, the isocyanate and the isocyanate-reactive component may be combined in the presence of a reinforcing material (e.g., carbon fiber, glass fiber). In some cases, the reinforcing material may be combined with at least one of the isocyanate or the isocyanate-reactive component before PU formation, or may be present as a third component combined after mixing of the isocyanate and the isocyanate-reactive component.

[0010] The isocyanate component may contain one or more isocyanate compounds, such as polymer isocyanates, aromatic isocyanates, or carbodiimide-modified isocyanates. The isocyanate compound may be a monomer, oligomer, prepolymer, etc. The isocyanate component may, for example, contain one or more isocyanate and / or polyisocyanate compounds. The isocyanate component may contain isocyanate compounds having an apparent functional value of 1.5 or more, or ≥2.0 or more.

[0011] The isocyanate component may include isocyanate compounds having a number-average molecular weight of 150 g / mol to 750 g / mol. In some cases, the isocyanate compounds may have a number-average molecular weight ranging from a lower value of 150 g / mol, 200 g / mol, 250 g / mol, or 300 g / mol to a higher value of 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, or 750 g / mol. The number-average molecular weight values ​​reported herein are determined by end-group analysis, gel permeation chromatography, and other methods known in the art. The isocyanate compounds may be monomers and / or polymers known in the art.

[0012] The isocyanate component may include one or more of the following: aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, etc. Examples of isocyanates include, but are not limited to, polymethylene polyphenyl isocyanate, toluene 2,4- / 2,6-diisocyanate (TDI), methylenediphenyl diisocyanate (MDI, including its isomers), polymers and prepolymers MDI, triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), tetramethylene diisocyanate, and hexamethylene diisocyanate. Examples include diisocyanate (HDI), 2-methyl-pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 4,4'-diisocyanato-3,3'-dimethyl-dicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1,3-diisooctylcyanato-4-methylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, and combinations thereof. In addition to the isocyanates described above, partially modified polyisocyanates, particularly those containing uretdione, isocyanurate, carbodiimide, uretonimine, allophanate, or biuret structures, and combinations thereof, may also be used.Examples of commercially available isocyanates include, but are not limited to, polyisocyanates available from Dow Chemical Company under trade names VORANATE®, VORATRON®, PAPI®, VORAFORCE®, and ISONATE®.

[0013] The isocyanate compounds may include isocyanate prepolymers resulting from the reaction of an isocyanate-reactive compound with a stoichiometrically excess isocyanate compound or polymer isocyanate compound under conditions that do not cause gelation or solidification, and the isocyanate prepolymers may have a higher average isocyanate equivalent weight of >140 g / eq. The formation of isocyanate prepolymers is known in the art and may involve reacting (1) at least one isocyanate compound with (2) at least one polyol compound. The isocyanate prepolymers may be described by NCO%, which is defined as the weight percentage of residual isocyanate groups remaining after the reaction of an isocyanate compound with a stoichiometrically deficient isocyanate-reactive compound. The isocyanate components disclosed herein may include one or more isocyanate compounds having an NCO content of more than 20% by weight, for example, 20% to 50% by weight, or in the range of 20% to 48% by weight.

[0014] The isocyanate component comprises at least one isocyanate group-containing material (e.g., polyisocyanate and / or isocyanate-terminated prepolymer). For example, the isocyanate component comprises at least one aromatic polyisocyanate, e.g., methylenediphenyl diisocyanate (MDI) and / or toluene diisocyanate (TDI). To form a polyurethane polymer, the isocyanate and the isocyanate-reactive component may be mixed immediately before use and applied to the substrate, and / or applied separately to the substrate and mixed on the substrate. The isocyanate component may contain at least 50% by weight (at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, etc.) of one or more polyisocyanates based on the total weight of the isocyanate component.

[0015] The PU compositions disclosed herein may contain an isocyanate component in weight percent (weight%) ranging from 15% to 80% by weight, 20% to 80% by weight, or 20% to 70% by weight.

[0016] The PU composition may contain an isocyanate-reactive component containing at least one polyether polyol prepared using a Lewis acid catalyst. Lewis acid-catalyzed polyether polyols can be prepared by polyaddition (alkoxylation) of an alkylene oxide to an initiator (i.e., a polyhydroxy-functional starter compound) in the presence of a catalyst known in the art that can determine the proportion of primary and secondary hydroxyls in the resulting polymer or oligomer. For example, alkoxylation using a Lewis acid catalyst results in an increase in the amount of primary hydroxyls, while using a basic catalyst produces secondary hydroxyls as the main product. Typical methods for producing polyether polyols using Lewis acid catalysts are described, for example, in International Publications 2019055725 and 2019055727.

[0017] The initiator comprises one or more compounds with a low molecular weight and a numerical hydroxyl functional value of at least 2. The initiator is any organic compound that is alkoxylated in the polymerization reaction. The initiator may contain as many as 10 hydroxyl groups. For example, the initiator may be a diol or a triol. A mixture of initiators may be used. The initiator has a hydroxyl equivalent less than the hydroxyl equivalent of the polyether product, and may have hydroxyl equivalents such as less than 500 g / mol equivalent, less than 300 g / mol equivalent, greater than 20 g / mol equivalent, 20-300 g / mol equivalent, 20-200 g / mol equivalent, or 30-150 g / mol equivalent. Exemplary initiator compounds, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexanedimethanol, bisphenol A, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sugars, and sugar alcohols, such as sorbitol and sucrose, and / or alkoxylates of any of these, have a weight-average molecular weight less than the weight-average molecular weight of the polymerization product.

[0018] Lewis acid-catalyzed polyether polyols may have a functional value of at least 2, for example, in the range of 2 to 6, or 2 to 4. Lewis acid-catalyzed polyether polyols may have an average primary hydroxyl content of at least 25% or 30%, for example, in the range of 25% to 85% or 30% to 80%. The Lewis acid-catalyzed polyols disclosed herein may have a low VOC content (e.g., propionaldehyde and acetal) and selectivity of up to 65% for primary hydroxyl-terminated polyol chains derived from PO. Lewis acid-catalyzed polyether polyols may have an average acetal content of at least 0.05% by weight, or at least 0.1% by weight.

[0019] The Lewis acid catalyst may be an arylborane catalyst having at least one fluoro / chloro or fluoroalkyl-substituted phenyl group, which may enable an improvement in the reaction yield. The polymerization catalyst may be fed to the reactor in an amount of more than 0 to 0.005 or less (e.g., more than 0.0001, 0.003 or less, 0.001 or less, etc.) molar equivalents per mole of initiator fed to the reactor. The Lewis acid catalyst may be active in a lower temperature range (e.g., 60 °C to 110 °C).

[0020] The Lewis acid polymerization catalyst has the general formula M(R 1 )1(R 2 )1(R 3 )1(R 4 ) 0又は1 [wherein, M is boron, aluminum, indium, bismuth, or erbium; R 1 includes (e.g., consists of) a first fluoro / chloro or fluoroalkyl-substituted phenyl group; R 2 includes (e.g., consists of) a second fluoro / chloro or fluoroalkyl-substituted phenyl group; R 3 includes (e.g., consists of) a third fluoro / chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group; optional R 4 is a second functional group or functional polymer group (e.g., consists of them)]. As used herein, a fluoro / chloro or fluoroalkyl-substituted phenyl group means that a fluoro / chloro-substituted phenyl group or a fluoroalkyl-substituted phenyl group as described below is present. A fluoroalkyl-substituted phenyl group means a phenyl group in which at least one hydrogen atom is substituted with a fluoroalkyl group. A fluoro-substituted phenyl group means a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom. A chloro-substituted phenyl group means a phenyl group in which at least one hydrogen atom is substituted with a chlorine atom. A fluoro / chloro-substituted phenyl group means a phenyl group in which at least one hydrogen atom is substituted with a fluorine or chlorine atom, and the phenyl group may include a combination of fluorine and chlorine atom substituents. R 1 、R2 and R 3 each may independently contain a fluoro / chloro or fluoroalkyl-substituted phenyl group, or each may independently consist essentially of a fluoro / chloro or fluoroalkyl-substituted phenyl group. M in the general formula may exist as a metal salt ion or as an integrally bonded part of the formula.

[0021] R 3 and optional R 4 Regarding R and optional R, the functional group or functional polymer group may be a Lewis base that forms a complex with a Lewis acid catalyst (e.g., a boron-based Lewis acid catalyst), and / or a molecule or part (e.g., a cyclic ether such as tetrahydrofuran) containing at least one electron pair available for forming a coordination bond with a Lewis acid. The Lewis base may be a polymeric Lewis base. The functional group or functional polymer group means a molecule containing at least one of water, alcohol, alkoxy (examples include linear or branched ethers and cyclic ethers), ketone, ester, organosiloxane, amine, phosphine, oxime, and substituted analogs thereof. Each of alcohol, linear or branched ether, cyclic ether, ketone, ester, alkoxy, organosiloxane, and oxime may contain 2 to 20 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, and / or 3 to 6 carbon atoms. For example, the functional group or functional polymer group may have the formula (OYH) n [where O is oxygen of O, H is hydrogen, Y is H or an alkyl group, and n is an integer (e.g., an integer from 1 to 100)]. However, other known functional polymer groups that can be combined with a Lewis acid catalyst such as a boron-based Lewis acid catalyst may be used. Exemplary cyclic ethers include tetrahydrofuran and tetrahydropyran.

[0022] In some cases, the Lewis acid polymerization catalyst may be the one shown in Structure I.

[0023] [Chemical formula]

[0024] Lewis acid-catalyzed polyether polyols may have an OH value in the range of 100 mg KOH / g to 900 mg KOH / g, 100 mg KOH / g to 800 mg KOH / g, or 100 mg KOH / g to 750 mg KOH / g. Lewis acid-catalyzed polyether polyols may have a number average molecular weight in the range of 400 Da or more, 450 Da or more, or 500 Da or more, for example, in the range of 400 Da to 2,000 Da, or 400 Da to 1,500 Da.

[0025] Lewis acid-catalyzed polyether polyols may have a polypropylene oxide content of 80% by weight or 90% by weight or more. In some cases, Lewis acid-catalyzed polyether polyols may contain polypropylene oxide homopolymers (including polypropylene oxide homopolymers polymerized in the presence of a polyhydroxy starter compound).

[0026] Lewis acid catalyst polyether polyols may be present in the isocyanate reactive component in weight percent (weight%) ranging from 40% to 95% by weight, 45% to 95% by weight, or 50% to 90% by weight.

[0027] The methods disclosed herein may include a long fiber injection molding process for preparing flammable modified fiber-reinforced polyurethane composites. Long fiber injection (LFI) is a well-known technique in the automotive market for rapidly curing bipartite polyurethanes. The flammable modified fiber-reinforced polyurethane composites of the present invention can be prepared by carrying out a long fiber injection molding process, supplying a curable polyurethane resin component, comprising a reactive polyurethane component, polyols and isocyanates, and isocyanate-reactive brominated compounds, together with metal hydrate particulate fillers and fibers, optionally together with phosphorus compounds, to a suitable mixing head, and discharging the wetted fibers onto a mold. The PU compositions disclosed herein can be rapidly cured with long working times in accordance with ASTM D7487-18, as determined by FOAMAT® Foam Qualification System (Foamat Messtechnik GmbH, Karlsruhe, DE). The PU composition may have a density of less than 0.850 g / mL, or in the range of 0.3 g / mL to 0.85 g / mL, or 0.3 g / mL to 0.85 g / mL, according to ASTM D3574-17 Test A.

[0028] Polyurethane foam compositions may contain one or more blowing agents, including chemical blowing agents such as water and aqueous fluids, hydrocarbons, acids, and volatile organic compounds, and physical blowing agents such as gases such as nitrogen, air, and carbon dioxide. The blowing agent may be added to the foam-forming composition during mixing in a weight percentage (W%) ranging from 0.1% to 15% by weight, or from 1% to 10% by weight. The blowing agent may be added to the isocyanate component and / or isocyanate-reactive component in an amount sufficient to provide the mixture in the corresponding W% amounts. In some cases, the blowing agent may be water, which may be added in a weight percentage of the composition ranging from 0.1% to 2% by weight, based on the weight of the foam-forming composition.

[0029] The isocyanate component and / or isocyanate-reactive component may have one or more functional additives that may be useful in the specific manufacturing process in which they are used, or that impart desired properties to the resulting foam. These include, for example, catalysts, chain extenders, odor modifiers, fillers, colorants, flame retardants, pigments, antistatic agents, reinforcing fibers, antioxidants, preservatives, and acid scavengers.

[0030] Polyurethane compositions and composite structural components, particularly for large vehicles such as buses. Polyurethane systems for LFI composite components include two-component polyurethane formulations that are mixed in LFI and injected together into a PVC-skinned deep-drawn metal mold to produce the final article. PU compositions may be used to prepare molded composite components by processes including mixing the PU composition with a reinforcing material, or they may be injected into the reinforcing material by, for example, LFI, reinforced reactive injection molding (RRIM), structural reactive injection molding (SRIM), resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM), and other reactive processing techniques. Reactive processing techniques may include single-step composite production, such as polymer material formation and reinforcement occurring in the same process or cycle. While compositions and methods have been discussed with respect to examples of polyurethane composites produced by LFI, it is assumed that polyurethane composites may be produced by any preferred method without departing from the scope of this disclosure.

[0031] Suitable reinforcing materials include any one or more of the following: glass fibers, E-glass fibers, carbon nanotubes, carbon fibers, polyester fibers, natural fibers, glass fibers, aramid fibers, nylon fibers, mineral fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, and metal fibers. The reinforcing material may include fibers with an aspect ratio (length / diameter) in the range of 600 to 1000. In some cases, the reinforcing material may include fibers (e.g., carbon or glass) having a filament diameter in the range of 15 μm to 25 μm.

[0032] Fiber-reinforced polymer composites, and methods and systems for producing fiber-reinforced polymer composites. Embodiments of the present invention also include building structures incorporating the fiber-reinforced composites of the present invention, such as doors, door skins, structural panels for walls and doors (e.g., garage door panels), door frame components, door and window components (e.g., window components, window frames, and coverings for door frames, plant-ons for doors), roofing panels, shutters, siding, and other building structures including the fiber-reinforced polymer composites.

[0033] While the formulation components and properties are disclosed individually, it is assumed that component elements (e.g., compounds in isocyanates or isocyanate-reactive components) may be included, excluded, or combined in any manner or in any partial combination, utilizing either the above-mentioned concentration range or the sub-ranges contained therein. Furthermore, the listed formulation properties can similarly be achieved by various combinations of the listed components within the listed ranges.

[0034] All parts and percentages are by weight unless otherwise specified. All molecular weight values ​​are based on number-average molecular weight unless otherwise specified. [Examples]

[0035] The following embodiments are provided to illustrate embodiments of the present invention, but are not intended to limit their scope. Table 1 provides the materials used in the following embodiments.

[0036] [Table 1]

[0037] Example 1: Properties of the polyurethane composition In this example, polyurethane reactivity was assayed by compounding samples containing polyurethane compositions by varying the constituent polyol components and combining them with specific ratios of isocyanates. 112 g of polyurethane was prepared as a sample. The components were equilibrated at 25°C and combined using a Heidolph mixer at 3000 rpm. After 10 seconds, the creaming time (CT) was measured when the PU began to expand. Next, the gelation time (GT) was measured by repeatedly dipping a rod into the foam, and the time at which filaments formed was identified as the gelation time. The tack-free time (TFT) is the time during which the resulting polymer surface is not tacky. After waiting 24 hours, the free-rise density (FRD) of the sample was measured. The foam was cut in half through the core to a size of 5 cm × 5 cm × 2.5 cm.

[0038] Sample I1 of the present invention comprises a Lewis acid catalyst polyol according to this disclosure, which is a PO-based polyol containing approximately 60-65% primary OH groups. Comparative polyol 1 in C1 is a PO-based polyol having similar properties to the Lewis acid catalyst polyol, but is prepared by standard KOH alkoxylation catalysis resulting in >95% secondary OH groups. Comparative polyol 2 in C2 is an EO-based polyol having similar OH value and functional value to the Lewis acid catalyst polyol with 100% primary OH content. The sample formulations and results are shown in Table 2.

[0039] [Table 2]

[0040] In Table 2, the isocyanate index corresponds to 100 (a / b), where a = equivalent weight of isocyanate groups in 72 parts of the isocyanate component, and b = equivalent weight of isocyanate-reactive groups in 40 parts of the blended polyol component.

[0041] Table 2 shows that the polyurethane reactivity of C2, which contains an EO-based polyol, is the fastest in terms of rise time and tack-free time, while C1 is the slowest. I1 has a similar reactivity to C2.

[0042] Example 2: Compression stress test of polyurethane composition In the following examples, polyurethane samples prepared substantially in the same manner as described in Example 1 were tested to quantify their compressive strength and modulus of elasticity. The compressive stress test was performed at 1 mm / min according to ASTM D1621. The yield point in the stress calculation was 10%. Foam samples were prepared, aged for 24 hours, and weighed 160 kg / m². 3 The dimensions were determined to be 50mm x 50mm x 25mm based on the density.

[0043] As shown in Figure 1, I1, formulated using a Lewis acid catalyst polyol, exhibits similar compressive strength and elastic modulus to C2 containing polyol 2 (EO-based polyol), while its performance is lower compared to C1 containing polyol 1 (PO-based, mainly secondary OH).

[0044] Example 3: Compatibility and storage stability of polyol formulations In this example, isocyanate-reactive (side B) formulations containing polyol samples were prepared and their storage stability was assayed. The samples were formulated as shown in Table 2, left to stand, and observed every 24 hours for signs of separation. Samples formulated with Lewis acid-catalyzed polyol or comparative polyol 1 did not show separation throughout the investigation period. On the other hand, comparative polyol 2 (EO-based polyol) was unsuitable, and the corresponding compounded polyol showed phase separation during storage, with a layer equivalent to approximately 15% of the entire polyol formulation forming on top.

[0045] Example 4: Properties of a polyurethane composition containing a filler The sample was formulated essentially as described in Example 1. The filler was dried at 80°C for 24 hours and then added to the formulated polyol component.

[0046] The reactivity profile of the reaction mixture was prepared as a 145 g sample and analyzed using the FOAMAT Foam Qualification system. A horizontal laboratory mold measuring 200 mm × 200 mm × 3 mm was used to prepare plaques at an applied density of 600 g / L for thermal and mechanical properties. Bending properties were measured using full-thickness specimens at a speed of 10 mm / min using the standard UNI EN ISO 178.

[0047] Thermal analysis to determine the glass transition temperature (Tg) was performed using a UNIVERSAL V TA Q800-DMA instrument. Test method used: double cantilever at 1 Hz, heating rate of 3°C / min; sample dimensions 60 × 12 × 4 mm; initial temperature 45°C; final temperature 240°C.

[0048] The sample was prepared using a flat mold with dimensions of 300 mm × 300 mm × 12 mm, with water heated to 90°C. The tested system was used for composite products manufactured by the LFI process, but the prepared sample did not contain glass fibers in order to evaluate only the behavior of the PU foam. Acmos 37-7009 was used as an external release agent. The reactants were equilibrated at 25°C before the reaction. The liquid weight was 650 g. The reaction temperature after combination was 50°C. The top of the mold was maintained at 45°C and the bottom of the mold at 35°C. The demolding time for the sample was 18 minutes. The estimated sample volume was 1.11 L. The average sample weight was 570 g, and the average density of the sample was 515 g / L ± 5 g / L.

[0049] The formulation and results are shown in Table 3.

[0050] [Table 3]

[0051] As shown in Table 3, the reactivity of I2 is much faster compared to C3, and it also shows a remarkable improvement in strength and module performance obtained with I2.

[0052] While the above describes exemplary embodiments, other and further embodiments can be devised without departing from their basic scope, the scope of which is determined by the following claims.

Claims

1. A method for forming a composite material, Isocyanate components, The present invention involves reacting an isocyanate-reactive component with at least one Lewis acid catalyst polyether polyol having a weight percentage (wt%) of 90 wt% or more of polypropylene oxide, a primary hydroxyl concentration of at least 30 wt%, a functional value of at least 2, an OH value in the range of 100 mg KOH / g to 800 mg KOH / g, an average acetal content of at least 0.05 wt%, and a water content in the range of 0.1 wt% to 2 wt% based on the weight of the isocyanate-reactive component. A method wherein at least one of the isocyanate component, the isocyanate-reactive component, or the third component contains a reinforcing material.

2. The method according to claim 1, wherein the isocyanate-reactive component comprises at least 50% by weight of the polyether polyol.

3. The method according to claim 1, wherein the polyether polyol is a polypropylene oxide polyol.

4. The method according to claim 1, wherein the composite material has a density of less than 0.85 g / mL.

5. The method according to claim 1, wherein the polyether polyol has a weight-average molecular weight of 200 Da to 1,000 Da and a functional value of 2 to 4.

6. The Lewis acid catalyst used to produce the polyether polyol has the general formula M(R １ ) １ (R ２ ) １ (R ３ ) １ (R ４ ) ０又は１ [where M is boron, aluminum, indium, bismuth, or erbium, and R １ , R ２ , R ３ and R ４ are each independent, R １ contains a first fluoro / chloro or fluoroalkyl-substituted phenyl group, R ２ contains a second fluoro / chloro or fluoroalkyl-substituted phenyl group, R ３ contains a third fluoro / chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group, and optional R ４ is a second functional group or functional polymer group], the method according to claim 1.

7. The composition according to claim 1, wherein the Lewis acid catalyst forms a coordination bond with tetrahydrofuran.

8. The method according to claim 1, wherein the isocyanate component is present in a weight percentage (weight%) in the range of 56% to 86% by weight.

9. The method according to claim 1, wherein the composite material is prepared by long fiber injection molding (LFI).

10. An article prepared by the method described in claim 1.

Images