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

Abstract

The method may include preparing a reaction mixture by combining an isocyanate component with an isocyanate-reactive component comprising 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, and an average acetal content of at least 0.05% by weight; and combining the reaction mixture with one or more reinforcing materials.

Description

[Technical Field]

[0001] The embodiments relate to polyurethanes and polyurethane / (methacrylate) hybrid compositions used in the manufacture of polyurethane composites and reinforcing materials with improved mechanical properties.

[0002] Introduction Polyurethane (PU) compound can be manufactured into reinforced composites by a variety of manufacturing processes, including pultrusion, injection molding, and filament winding. Pultrusion is a continuous manufacturing process for producing fiber-reinforced polymer composite profiles with a fixed cross-sectional area, often used in structural applications. Injection molding is a process in which PU resin is brought into contact with fibers and impregnated into the fibers by applying a vacuum, and is applied to the manufacture of articles such as wind turbine blades. Filament winding, on the other hand, is applied to the manufacture of articles such as pipes or closed end structures (pressure vessels or tanks), typically involving winding resin-pre-impregnated filaments onto a rotating mandrel.

[0003] As with most manufacturing techniques, productivity is increased by shortening demolding time while maintaining or improving product quality. To shorten demolding time, catalysts or polyols containing higher concentrations of reactive primary hydroxyl groups (e.g., ethylene oxide (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 an 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 project]

[0004] In one embodiment, an embodiment of the present disclosure includes a method for forming a composite material, comprising: preparing a reaction mixture by combining an isocyanate component with an isocyanate-reactive component comprising 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, and an average acetal content of at least 0.05 wt%, and combining the reaction mixture with one or more reinforcing materials. [Modes for carrying out the invention]

[0005] Embodiments relate to two-component polyurethane and polyurethane / (meth)acrylate hybrid compositions for use in the manufacture of composites, comprising a Lewis acid-catalyzed polyether polyol produced by polymerization in the presence of a perfluoroalkyl-substituted arylborane catalyst. The polymer-forming composition comprises an isocyanate component and an isocyanate-reactive component comprising at least a Lewis acid-catalyzed polyether polyol. The Lewis acid-catalyzed polyether polyols disclosed herein may have 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, and an average acetal content of at least 0.05% by weight. The method also includes the formation of composites, comprising combining the components in the presence of a reinforcing material using a preferred process such as injection molding, pultrusion, or filament winding.

[0006] 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.

[0007] The PU compositions and composites disclosed herein contain polyether polyols produced by Lewis acid catalytic 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 comparative PO-based polyols prepared by KOH catalytic action, and less phase separation during processing than comparative EO-based polyols. In some cases, PU formulations containing Lewis acid-catalyzed polyether polyols may 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).

[0008] 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 exist as a third component combined after the mixing of the isocyanate and the isocyanate-reactive component. The compositions disclosed herein are substantially water-free (i.e., the maximum water content in the formulation is 0.1% or less) and may generate negligible amounts of foam when the reactant components are combined.

[0009] 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.

[0010] 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.

[0011] 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, methylenediphenyl diisocyanate (MDI, including its isomers), polymer MDI, triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methyl-pentamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-trimethylhexamethylene Examples include 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 including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate or biuret structures, and combinations thereof may be used, in particular. 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®.

[0012] The isocyanate compounds may include isocyanate prepolymers resulting from the reaction of an isocyanate-reactive compound with a molar-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% corresponding to the weight percentage of NCO groups remaining after the completion of the reaction between the isocyanate and the isocyanate-reactive compound present in the prepolymer. 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.

[0013] 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.

[0014] 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.

[0015] The PU composition may contain an isocyanate-reactive component comprising at least one polyether polyol prepared using a Lewis acid catalyst and optionally one or more hydroxy-functionalized (meth)acrylates. As used herein, the use of "(meth)" in combination with various acrylate species indicates that the scope herein encompasses both acrylate and methacrylate variants of the reference compound.

[0016] 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 such as KOH 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 85% 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 supplied to the reactor in an amount of more than 0 to 0.005 or less (for example, more than 0.0001, 0.003 or less, 0.001 or less, etc.) molar equivalents per mole of the initiator supplied to the reactor. The Lewis acid catalyst may be active in a lower temperature range (for example, 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 (for example, consists of) a first fluoro / chloro or fluoroalkyl-substituted phenyl group, R 2 includes (for example, consists of) a second fluoro / chloro or fluoroalkyl-substituted phenyl group, R 3 includes (for example, consists of) a third fluoro / chloro or fluoroalkyl-substituted phenyl group or a first functional group or a functional polymer group, and optional R 4 is a second functional group or a functional polymer group (for example, consists of)]. As used herein, a fluoro / chloro or fluoroalkyl-substituted phenyl group means that there is a fluoro / chloro-substituted phenyl group or a fluoroalkyl-substituted phenyl group as described below. 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, 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 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 O oxygen, 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 also 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] The Lewis acid-catalyzed polyether polyol 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. The Lewis acid-catalyzed polyether polyol 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, 400 Da to 2,000 Da, or 400 Da to 1,500 Da.

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

[0026] The Lewis acid-catalyzed polyether polyol may be present in the isocyanate-reactive component at a weight percent (wt%) in the range of at least 10 wt% or at least 20 wt%, for example, 10 wt% to 95 wt%, 15 wt% to 95 wt%, or 15 wt% to 80 wt%.

[0027] The isocyanate-reactive component may include one or more hydroxy-functional (meth)acrylate monomers that react with the isocyanate component and / or polymerize in the presence of a free radical initiator to produce a PU acrylate hybrid composition. The hydroxy-functional (meth)acrylate monomer has the general structure:

[0028]

Chemical formula

[0029] Hydroxy-functional (meth)acrylates may be added to a polyurethane acrylate hybrid composition in weight percentages (weight%) ranging from 15% to 40% by weight, 20% to 38% by weight, 25% to 35% by weight, or 27% to 32% by weight.

[0030] The isocyanate-reactive component may include one or more anthraquinone curing indicators that provide a visual indicator of the progress of the PU acrylate hybrid composition during curing. In some cases, curing may be indicated by a transition from light green to brownish-red, indicating that the composition is substantially cured. Suitable anthraquinone curing indicators include anthraquinone dyes such as 1-(methylamino)-4-p-toluidinoanthraquinone (CAS: 128-85-8), 1,4-bis(ethylamino)-9,10-anthraquinone, 1,4-di(4'-methylphenylamino)anthraquinone, and 1,4-bis(o-sulfo-p-toluidino)anthraquinone.

[0031] Anthraquinone curing indicators may be added to the polyurethane acrylate hybrid composition in weight percent (W%) ranging from 0.001% to 0.15% by weight, 0.001% to 0.10% by weight, or 0.01% to 0.05% by weight.

[0032] The methods of this disclosure may include forming composite articles and materials by any preferred method. In some cases, composite components are prepared by combining isocyanates and isocyanate-reactive compounds to form a reactive mixture, which is then combined with a reinforcing material. 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.

[0033] Methods for forming composite materials may include vacuum-assisted resin transfer molding (VARTM, also known as injection), pultrusion, filament winding or braiding, reinforced reactive injection molding (RRIM), structural reactive injection molding (SRIM), resin transfer molding (RTM), in-situ curing pipe application, reactive extrusion, and other reactive processing techniques. Reactive processing techniques may include single-step composite material production, such as polymer material formation and reinforcement occurring in the same process or cycle.

[0034] In some cases, the pultrusion process may involve stretching a pre-selected reinforcing material, such as a fiberglass roving, mat, or cloth, through a resin bath in which the reinforcing material has been thoroughly impregnated with a reinforcing PU or PU / (meth)acrylate hybrid composition. The impregnated fibers may then be formed into a desired geometric shape and drawn into a heated steel die. Once inside the die, curing of the reinforcing composition is initiated by controlling the temperature inside the die. The laminate is continuously pulled by the pultrusion machine, thereby solidifying the laminate into the shape of the die. While compositions and methods have been discussed with respect to examples of polyurethane composites produced by injection or pultrusion, it is assumed that polyurethane composites may be produced by any preferred method without departing from the scope of this disclosure.

[0035] Cured articles prepared from curable resin compositions can be used to produce composites, articles, coatings, adhesives, inks, encapsulated materials, or castings. Composites can be used in applications such as wind turbines (e.g., spur caps, wind blades), boat hulls, truck bed covers, automotive trim and exterior panels, pipes, tanks, window liners, breakwaters, pressure vessels, and composite ladders.

[0036] 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.

[0037] 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]

[0038] 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.

[0039] [Table 1]

[0040] Example 1: Polyurethane composite material In this example, polyurethane compositions were prepared, and the properties of the present invention samples and comparative samples containing polypropylene oxide-based polyols were analyzed. The present invention samples (I1-I3) were blended using Lewis acid-catalyzed PO-based polyols in three different amounts ranging from 20 to 55 parts, and the results were compared with comparative formulations (C1-C3) blended using polyol 2 (which has the same OH value and functional value, but was prepared using a KOH catalyst). The formulations are shown in Table 2.

[0041] [Table 2]

[0042] Unless otherwise specified in the test method, samples were generally prepared by mixing each component of the isocyanate-reactive compounds using a DAC 600.1 FVZ-K speed mixer until uniform dispersion. The isocyanate compounds were then combined and mixed in specific ratios. The mixture was poured into a suitable mold, and the mold was transferred to a 100°C oven for 90 minutes. The plaque was then removed from the mold, and the shape of the test specimen was cut accordingly using a waterjet cutter.

[0043] The test method was carried out as follows. The results of the characteristic measurements for each sample are shown in Table 3.

[0044] Viscosity: Viscosity increase was measured using a Brookfield DV-II+Pro viscometer. For each sample, the isocyanate and isocyanate-reactive component were mixed at 2350 RPM for 15 seconds according to Table 5 to ensure the same sample temperature each time. 10–10.5 grams of the mixture (depending on the mixing ratio) were poured into a disposable chamber (HT-2DB-100) and then dropped into a Thermosel (Brookfield Engineering). The Thermosel temperature was maintained at an isothermal 26°C. The viscosity increase over time was then measured using a disposable spindle (SC4-27).

[0045] Glass transition temperature and storage modulus by dynamic mechanical analysis (DMA): Dynamic mechanical analysis (DMA) was performed using a TA Instruments Advanced Rheometric Expansion System (ARES-G2) with liquid nitrogen environment control, and a torsion rectangular fixture was used. A 3 mm thick rectangular sample (45 mm long and 12.8 mm wide) was punched out from a foam prepared in a metal mold. The temperature was increased from -70°C to 200°C at a rate of 3°C / min. The test frequency was 1 Hz, the axial force was 0.098 N, the strain was 0.05%, and the data acquisition interval was 30 seconds per point. The main outputs identified from the characterization were the storage modulus in shear mode (G') and Tanδ.

[0046] Tensile modulus, elongation at fracture, and ultimate tensile strength: Elongation at fracture (%), ultimate tensile strength (MPa), and tensile modulus (MPa) were all obtained using an MTS machine with ASTM D1708 standards. 3 mm thick hardened samples were tested after molding (and aging for at least 2 days under ASTM conditions). Micro-tensile samples were punched out in a dogbone shape.

[0047] IZOD Impact Test: A sample was molded to a length of 45 mm, a width of 12.7 mm, and a thickness of 3 mm. A notch with a length of 2.54 mm was made in the center of the sample. A CEAST Notchvis automatic notcher (POR-TL-090) was used for notching. Impact resistance was measured at 23°C and 50% relative humidity using a Model 92T equipped with a Model 892 Impact Display System, according to ASTM D256 (Method for Determining the Izod Pendulum Impact Resistance of Plastics).

[0048] [Table 3]

[0049] In Table 3, I1-I3 are characterized by a better reactivity profile (faster reaction), and the impact is proportional to the amount of Lewis acid catalyst polyol in the formulation. However, since the mixed viscosity is less than 1000 cPs after 10 minutes, the open time remains acceptable, and the samples of the present invention exhibit unexpected improvements in polymer properties, including higher glass transition temperature, elastic modulus, elongation, and tensile strength.

[0050] Example 2: Compatibility / miscibility of polyols in the formulation In this example, the compatibility / miscibility of various isocyanate-reactive component formulations was tested by combining the components as shown in Tables 4 and 5, according to the method described in Example 1. Following the combination, the formulations were sealed in glass vials and left on a horizontal surface at room temperature for one week. The samples were visually inspected for phase separation and discoloration.

[0051] In the samples, the formulations incorporated polyol 2 (C4-C6), polyol 4 (C7-C9), and Lewis acid-catalyzed polyols (I4-I6) at various concentrations. The ratio of polyol 1 to polyol 3 was kept nearly constant in all formulations.

[0052] [Table 4]

[0053] [Table 5]

[0054] For isocyanate-reactive components prepared using the primary polyol component of Polyol 2 (glycerin-initiated, total PO polyether polyol, having >95% secondary OH-terminated groups), all samples (20% by weight, 40% by weight, and 55% by weight) showed no phase separation or discoloration / color change, indicating their suitability for pultrusion applications.

[0055] Similarly, the isocyanate-reactive components prepared using the primary polyol component of Lewis acid-catalyzed polyols were stable, showing no visual phase separation or discoloration / color change at concentrations of 20% by weight, 40% by weight, and 55% by weight.

[0056] However, samples C7-C9, formulated with polyol 4 (glycerin-started polyol, all EO) at concentrations of 20%, 40%, and 55% by weight, showed phase separation a few days after preparation. The degree of phase separation was estimated to be approximately 15% or more by volume, depending on the amount of polyol used. The presence of phase separation is problematic for compound resins used in composite applications. The samples also showed gradual discoloration over time, turning slightly yellow, indicating undesirable side reactions. The phase separation is thought to be due to the poor compatibility between the total EO polyol and the other compound components. Therefore, while the use of total EO polyol is expected to provide an enhanced reactivity profile compared to PO-based polyols, phase separation limits its usefulness in composite formation applications.

[0057] Example 3: Compact composite formulation designed for injection applications In this example, hybrid polyurethane / acrylate formulations were prepared as compact composite materials, and various performance parameters were measured. Polymer samples were prepared substantially as described in Example 1. The formulations and results are shown in Table 6.

[0058] The test was conducted as follows:

[0059] Tensile and Impact Properties: 1. After the chemical temperature reaches 25°C, add 100g of isocyanate and 100g of compounded polyol to a 1000mL speed mixer cup. Mix the mixture with a speed mixer at 1500rpm for 1 minute. 2. Remove air bubbles from the PU resin by vacuum, then pour the resin into a steel mold. The dimensions of the mold cavity are 20cm x 20cm x 0.4cm. 3The resin gels and hardens in the mold after a curing cycle of 2 hours at 50°C + 6 hours at 70°C. 4. Remove from the mold to obtain a casting plate for testing. 5. Test specimens were machined from the hardened casting plate according to ISO 527 and ISO 179. 6. Conduct tests and record the relevant mechanical properties.

[0060] Tensile properties (strength, modulus of elasticity, elongation at fracture) test conditions: ISO 527-2, test speed: 2 mm / min.

[0061] Impact performance test conditions: ISO179, impact velocity: 2.9 m / s, impact energy: 4 J.

[0062] 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.

[0063] [Table 6]

[0064] The results show that I7, containing a Lewis acid-catalyzed polyol, exhibits a relatively longer open time than C10, followed by more rapid curing. Table 6 also shows that the Lewis acid-catalyzed polyol unexpectedly results in the formation of polymers with improved mechanical properties in both strength and elongation compared to polyol 2. For composite manufacturing technologies such as injection molding or pultrusion, a longer open time is desirable, and a slow increase in viscosity is preferable to allow for wetting and rheology of the fibers during processing. Furthermore, it is important that the formulation cures rapidly after the gelation reaction begins, possessing excellent final mechanical properties, good wetting performance, and without forming bubbles.

[0065] 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 reaction mixture is prepared by combining an isocyanate-reactive component containing at least one Lewis acid catalyst polyether polyol having a weight percentage (W%) of 90% or more 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, and an average acetal content of at least 0.05% by weight. A method comprising combining the reaction reaction with one or more reinforcing materials.

2. The method according to claim 1, wherein the isocyanate-reactive component comprises at least 10% 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 more than 0.850 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 [wherein, M is boron, aluminum, indium, bismuth, or erbium, and R １ , R ２ , R ３ and R ４ are each independent, R １ includes a first fluoro / chloro or fluoroalkyl-substituted phenyl group, R ２ includes a second fluoro / chloro or fluoroalkyl-substituted phenyl group, R ３ includes 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 method according to claim 1, wherein the isocyanate-reactive component further comprises a hydroxy(meth)acrylate monomer, a prepolymer, or a polymer.

8. The method according to claim 1, wherein the isocyanate component is present in the reaction mixture in a weight percentage (weight%) ranging from 35% to 65% by weight.

9. The method according to claim 1, wherein the method for forming the composite material includes pultrusion, injection, or filament winding.

10. A composite material prepared by the method described in claim 1.

Images