Polyurethane composition, composite material prepared using the same, and method for preparing the same

Abstract

A polyurethane composition, a composite material prepared therewith, and a method for preparing a polyurethane resin using the polyurethane composition are provided, the polyurethane composition comprising A) A1) and at least one of A2) and A3): A1) a first polyisocyanate compound; A2) a first prepolymer formed by reaction of a second polyisocyanate compound with a first polyol, the first prepolymer having an NCO content of 21-25%; A3) a second prepolymer formed by reaction of a third polyisocyanate compound with a second polyol, the second prepolymer having an NCO content of 10-20%, an isocyanate component, the total amount of the first prepolymer and the second prepolymer being 10-70% by weight, based on the total weight of the isocyanate component; B) an isocyanate-reactive component comprising a third polyol and an isocyanate-reactive (meth)acrylate monomer; and C) a free radical initiator.

Description

[Technical Field]

[0001] The present disclosure relates to polyurethane compositions, composite materials comprising fiber reinforced materials and polyurethane resins obtained from the polyurethane compositions, and methods for preparing the polyurethane compositions. The polyurethane resins have tunable viscosity, long open time, and good physical and mechanical properties, making them suitable for a wide range of composite manufacturing processes and end uses. [Background technology]

[0002] Composite materials are a type of heterogeneous material that contains fiber reinforcement materials to achieve high strength and a polymer matrix to fixate the fibers and protect them from damage. The performance and service life of composite materials not only depend on the reinforcement materials, but also largely on the quality of impregnation and the properties of the polymer resins used. Composite materials typically require that the liquid polymer resin has low viscosity and a long open time to ensure good impregnation quality, while also providing a curing time that allows for adequate manufacturing cycle times. Apart from that, the physical and mechanical properties of the cured resin, such as tensile strength / flexural strength and modulus, are also important for achieving a longer lifespan of the final product.

[0003] Typical Customer Critical Quality (CTQ) measures depend on the manufacturing process and end use of the final composite material.

[0004] For the vacuum infusion process for wind blade applications, a long open time (up to several hours) with tunability and low initial resin viscosity (<150 mPa.s for good infusion quality) is desirable. According to Germanischer Lloyd standards (Rules for Classification and Construction II Materials and Welding, 2: Non-metallic Materials), cured polymers for wind blade infusion must also meet various additional requirements, such as a flexural strength of >100 MPa (ISO 178), a strain rate of >2.5% (ISO 178), and a heat distortion temperature (HDT) of >70°C (ISO 75-2, Mode A).

[0005] Epoxy resins are currently the dominant resin technology in the wind blade injection market due to their ease of processing (long open time with high adjustability ranging from 1 to 10 hours) and good polymer physical property performance. However, due to their high cost and slow cure profile, there is a need in the market for better performing alternative solutions.

[0006] Conventional polyurethane resins typically consist of two components: an isocyanate and a blended polyol. They represent a cost-effective alternative to epoxy resins, providing polymer properties characterized by high toughness, hardness, and good abrasion and fatigue resistance. However, while the inherently fast reactivity of conventional two-component polyurethane solutions advantageously results in fast cure profiles, they also result in open time values ​​that are too short for certain applications. For this reason, two-component polyurethane solutions are undesirable for composite applications requiring long open times, such as vacuum infusion.

[0007] For the above reasons, there is still a need in the polyurethane manufacturing industry to develop a polyurethane composition having low viscosity, long open time, fast curing profile, and good physical and mechanical properties after curing. After continuous research, the present inventors have surprisingly developed a polyurethane composition that provides low initial viscosity, long open time, high adjustability of reaction profile, and satisfactory physical, mechanical, and thermal properties after curing. Summary of the Invention

[0008] The present disclosure provides, among other things, a unique polyurethane composition for composite applications, a composite material comprising a fiber reinforced material and a polyurethane resin derived from the polyurethane composition, and a method for preparing the polyurethane composition.

[0009] In a first aspect of the present disclosure, the present disclosure provides a method for producing a cellular membrane comprising: A) A1) and at least one of A2) or A3): A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25% based on the weight of the first prepolymer; A3) a second prepolymer formed by reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20% based on the weight of the second prepolymer; An isocyanate component comprising: an isocyanate component in which the total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight based on the total weight of the isocyanate component A); B) an isocyanate-reactive component, B1) a third polyol, and B2) Isocyanate-reactive (meth)acrylate monomers an isocyanate-reactive component comprising: C) a free radical initiator; The present invention provides a polyurethane composition comprising:

[0010] The polyurethane composition may further comprise other additives, which may be selected from the group consisting of catalysts for the reaction between isocyanate groups and hydroxyl groups, radical polymerization accelerators, antifoaming agents, pigments, fillers and moisture scavengers.

[0011] In one preferred embodiment, the first prepolymer A2) and the second prepolymer A3) are used individually or in any combination in any ratio, and the total weight of the first prepolymer A2) and the second prepolymer A3) is less than 45% by weight, based on the total weight of the isocyanate component A).

[0012] In another preferred embodiment, the total weight of the first prepolymer A2) and the second prepolymer A3) is 45% by weight to 70% by weight, based on the total weight of the isocyanate component A), and the weight ratio of the first prepolymer A2) to the second prepolymer A3) is 5:1 to 1:5.

[0013] In a second aspect of the present disclosure, the present disclosure provides a composite material comprising a fiber reinforced material and a polyurethane resin obtained from the polyurethane composition described herein.

[0014] In a third aspect of the present disclosure, the present disclosure provides a method for producing a medicament for a medicament comprising: 1) A1) and at least one of A2) and A3): A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25 wt.%; A3) A second prepolymer formed by the reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20 wt.%. providing an A) isocyanate component comprising: The total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight based on the total weight of the A) isocyanate component; and 2) providing an isocyanate-reactive component B); B1) a third polyol, including polyether, polyester, and polycarbonate polyols, having an average equivalent weight of 80 to 600 g / eq and an average functionality of 2 to 5; B2) Isocyanate-reactive (meth)acrylate monomers providing an isocyanate-reactive component B) comprising: 3) providing a free radical initiator C); 4) then reacting the isocyanate component A) with the isocyanate-reactive component B) in the presence of a free radical initiator C) to form the polyurethane composition described herein; The present invention provides a method for preparing a polyurethane resin, comprising:

[0015] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. DETAILED DESCRIPTION OF THE INVENTION

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Additionally, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

[0017] definition Numerical ranges disclosed herein include all values ​​between and including the lower and upper limits. Ranges containing explicit values ​​(e.g., ranges of 1, or 2, or 3-5, or 6, or 7) include any subranges between any two explicit values ​​(e.g., the range 1-7 above includes the subranges 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0018] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0019] The term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0020] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not that component is specifically disclosed herein. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless specifically stated to the contrary. In contrast, the term "consisting essentially of" excludes any other component, step, or procedure from the scope of any succeeding statement, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not expressly delineated or listed. The term "or" refers to the listed members individually as well as in any combination, unless otherwise stated. The use of the singular includes the use of the plural, and vice versa.

[0021] An "isocyanate" is a chemical substance containing at least one isocyanate group in its structure. An isocyanate group is represented by the formula: -N=C=O. An isocyanate containing more than one or at least two isocyanate groups is a "polyisocyanate." An isocyanate with two isocyanate groups is a diisocyanate, an isocyanate with three isocyanate groups is a triisocyanate, and so on. Isocyanates can be aromatic or aliphatic.

[0022] A "polyol" is an organic compound containing multiple hydroxyl (-OH) groups. In other words, a polyol contains at least two hydroxyl groups. Non-limiting examples of suitable polyols include diols (containing two hydroxyl groups), triols (containing three hydroxyl groups), and multi-hydroxyl-containing polyols. Polyether polyols may also contain small amounts of monofunctional species (monols), i.e., species with only one hydroxyl group, formed during polyol synthesis as part of a side reaction to form unsaturated species, i.e., species with double bonds.

[0023] A "polyether" is a compound containing two or more ether linking groups in the same linear chain of atoms.

[0024] A "polyester" is a compound containing two or more ester linking groups in the same linear chain of atoms.

[0025] A "polymer" is a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term "polymer" encompasses the term "homopolymer" (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure), and the term "interpolymer" (used interchangeably with the term "copolymer") includes bipolymers (used to refer to a polymer prepared from two different types of monomers), terpolymers (used to refer to a polymer prepared from three different types of monomers), and polymers prepared from four or more different types of monomers. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. It also encompasses copolymers of all forms, e.g., random, block, etc. While polymers are often referred to as "made from" one or more specific monomers, "based on" a particular monomer or monomer type, or "containing" a particular monomer content, it should be noted that in this context, the term "monomer" is understood to refer to the polymerized remains of a particular monomer, not the unpolymerized species. Generally, polymers herein are based on "units" that are the polymerized form of the corresponding monomers.

[0026] "Hydroxyl number" refers to the content of hydroxyl groups in a polyol.Methods for measuring hydroxyl number are well known to those skilled in the art, and are disclosed, for example, by Houben Weyl, Method der Organischen Chemie, vol. XIV / 2 Makromolekulare Stoffe, p. 17, Georg Thieme Verlag; Stuttgart 1963. "Average equivalent weight" is the average of the equivalent weights associated with the various components in a mixture.When a mixture is formed by different polyols, the average equivalent weight can be calculated as follows: Using one of the various experimental techniques well known in the art, such as titration or infrared spectroscopy, the average OH number of the mixture is measured as OHav: Then, the average equivalent weight is calculated as EWav=56100 / OHav.

[0027] "Average functionality" is the average of the functionalities associated with the various components in a mixture. When a mixture is formed by different polyols, the average functionality can be calculated as follows: given the average OH number of the mixture (OHav), given the functionality of the first component (f1), given the functionality of the second component (f2), given the OH number of the first component (OH1), given the OH number of the second component (OH2), given the weight fraction of the first component (a), given the weight fraction of the second component (b=1-a), the average functionality of the mixture is: Functionality av.=(OHavxf1xf2) / [(OH1xf2xa)+(OH2xf1xb)]

[0028] First Polyisocyanate Compound A1 According to various embodiments of the present disclosure, the first polyisocyanate compound A1 used in component A is an aromatic compound having at least two isocyanate groups. According to a preferred embodiment of the present disclosure, the polyisocyanate compound contains at least one aromatic ring (e.g., an aryl group or a heteroaryl group), and all isocyanate groups in the polyisocyanate compound are directly bonded to the aromatic ring without any connecting group therebetween. Carbodiimide-modified derivatives of the above-mentioned aromatic polyisocyanates can also be used in polyisocyanate compound A1, and in this case, the term carbodiimide-modified derivatives can include carbodiimide-modified aromatic polyisocyanates containing at least two isocyanate groups. In another preferred embodiment, suitable aromatic polyisocyanate compounds include m-phenylene diisocyanate, 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI), various isomers of diphenylmethane diisocyanate (MDI), various oligomers of MDI present in polymeric MDI (polyphenylmethane polyisocyanate), carbodiimide-modified MDI products, or mixtures thereof. In another preferred embodiment, suitable aromatic polyisocyanate compounds include various isomers of diphenylmethane diisocyanate (MDI) and carbodiimide-modified MDI products. In another preferred embodiment, suitable aromatic polyisocyanate compounds include various isomers of diphenylmethane diisocyanate (MDI) in monomeric form, polymeric form, or a combination thereof.

[0029] Generally, the amount of the first polyisocyanate compound A1 can vary based on the actual requirements of the polyurethane product. For example, in one exemplary embodiment, the content of the first polyisocyanate compound A1 can be 15% to 70%, 15% to 60%, 18% to 50%, 23% to 40%, or 25% to 37% by weight, based on the total weight of the polyurethane composition.

[0030] In another preferred embodiment, the content of the first polyisocyanate compound A1 may be 30% by weight to 95% by weight, or 30% by weight to 90% by weight, or 35% by weight to 90% by weight, or 40% by weight to 85% by weight, or 45% by weight to 80% by weight, or 50% by weight to 70% by weight, based on the total weight of the isocyanate component A.

[0031] First Prepolymer A2 The first prepolymer A2 is formed by reacting the first polyol with a second polyisocyanate compound. The second polyisocyanate compound can be a monomeric isocyanate or a polymeric isocyanate, where the latter refers in both cases to an isocyanate molecule having two NCO groups, such as MDI or TDI. The second polyisocyanate compound used to form the prepolymer A2 is an aromatic compound having at least two isocyanate groups; this can be described similarly to component A1 described above.

[0032] The first polyol component used in prepolymer A2 has an average equivalent weight of 30-200 g / eq and an average functionality of 2-3. In a preferred embodiment of the present application, the polyol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)-cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, trimethylolpropane, glycerol, pentaerythritol, and sugar compounds such as, for example, glucose, sorbitol, mannitol, and sucrose, polyhydric phenols, resols, and any combination thereof. In another preferred embodiment, the polyol is a polyether polyol that can be prepared by reacting an olefin oxide with a starter in the presence of a catalyst. The catalyst is preferably, but not limited to, an alkali hydroxide, an alkali alkoxide, antimony pentachloride, boron trifluoride-diethyl etherate, or a combination thereof. Suitable polymerization catalysts may include potassium hydroxide, cesium hydroxide, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate, or a tetraphosphazenium compound. The olefin oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or a combination thereof; preferably, ethylene oxide and / or propylene oxide.The starter molecule is one of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)-cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, trimethylolpropane, glycerol, pentaerythritol, and sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, and any combination thereof.

[0033] The content of the first polyol in the prepolymer A2 can be adjusted by a person skilled in the art, as long as the resulting prepolymer A2 has an NCO content of 21% to 25% by weight, preferably 22% to 24% by weight, based on the total weight of the first prepolymer.

[0034] Prepolymer A2 has an NCO content of 21% to 25% by weight, preferably 22% to 24% by weight, based on the total weight of the first prepolymer.

[0035] Second Prepolymer A3 The second prepolymer A3 is formed by the reaction of the second polyol with a third polyisocyanate compound. The third polyisocyanate compound used to form the prepolymer A3 is an aromatic compound having at least two isocyanate groups; this can be described similarly to component A1 described above.

[0036] The second polyol component used in prepolymer A3 is a polyether polyol that can be prepared by reacting an olefin oxide with a starter in the presence of a catalyst. The catalyst is preferably, but not limited to, an alkali hydroxide, an alkali alkoxide, antimony pentachloride, boron trifluoride-diethyl etherate, or a combination thereof. Suitable polymerization catalysts may include potassium hydroxide, cesium hydroxide, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate, or a tetraphosphazenium compound. The olefin oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or a combination thereof; preferably, ethylene oxide and / or propylene oxide. The starter molecules include compounds having at least one, preferably 2 to 8, more preferably 2 to 4 hydroxyl groups per molecule; they may also contain one or more primary amine groups in the molecule. Suitable starter molecules include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol, The polyol may be selected from the group comprising ethanol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol with formaldehyde and Mannich condensation products of phenol with formaldehyde and dialkanolamines, and also melamine.The starter molecule having one or more primary amine groups in the molecule may be selected, for example, from the group consisting of aniline, ethylenediamine, TDA (toluenediamine), MDA (methylenedianiline) and PMDA (polymeric MDA), more preferably from the group comprising TDA and PMDA, most preferably from TDA.

[0037] In one preferred embodiment of the present application, the second polyol component used in prepolymer A3 comprises at least one polyether polyol and has an average functionality of 2 to 3 and an equivalent weight of 250 to 3,000 g / eq, more preferably 500 to 2,500 g / eq, even more preferably 1,000 to 2,000 g / eq.

[0038] The content of the second polyol component used in prepolymer A3 is 20% by weight to 70% by weight, preferably 35% by weight to 70% by weight, and more preferably 40% by weight to 60% by weight, based on the total weight of prepolymer A3.

[0039] Prepolymer A3 has an NCO content of 10% to 20% by weight, or 12% to 19% by weight, or 13% to 18% by weight, or 14% to 16% by weight.

[0040] Prepolymer A2 may be referred to as the first prepolymer, and prepolymer A3 may be referred to as the second prepolymer. The total weight of the first prepolymer and the second prepolymer is 10% by weight to 70% by weight, or 10% by weight to 65% by weight, or 15% by weight to 60% by weight, or 20% by weight to 55% by weight, or 30% by weight to 50% by weight, based on the total weight of isocyanate component A.

[0041] The first prepolymer A2 and the second prepolymer A3 can be used individually or in any combination, provided that the total weight of the first prepolymer A2 and the second prepolymer A3 is less than 45% by weight, preferably less than 40%, preferably 10 to 40% by weight, more preferably 10 to 39% by weight, even more preferably 12 to 38% by weight, or 25 to 37% by weight, based on the total weight of the isocyanate component A; provided that the total weight of the first prepolymer A2 and the second prepolymer A3 is 45% to 70% by weight, based on the total weight of the isocyanate component A, the weight ratio of the first prepolymer A2 to the second prepolymer A3 is 5:1 to 1:5, preferably 4:1 to 1:4, or 4:1 to 1:2, or 4:1 to 1.4:1.

[0042] B1) Third Polyol The first polyol is used in the synthesis of prepolymer A2. The second polyol is used in the synthesis of prepolymer A3. The third polyol B1 is part of the isocyanate-reactive component B) of the polyurethane composition of the present invention. The third polyol B1 has an average equivalent weight of 80 to 600 g / eq and an average functionality of 2 to 5. It includes polyols commonly used in the art to prepare polyurethanes, including, but not limited to, polyether polyols, polycarbonate polyols, polyester polyols, or combinations thereof.

[0043] The polyether polyol can be prepared by a known method, for example, by reacting an olefin oxide with a starter in the presence of a catalyst. The catalyst is preferably, but not limited to, an alkali hydroxide, an alkali alkoxide, antimony pentachloride, boron trifluoride-diethyl etherate, or a combination thereof. The olefin oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or a combination thereof; preferably, ethylene oxide and / or propylene oxide. Suitable starter molecules are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)-cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol. The starter molecule having one or more primary amine groups in the molecule may be selected from the group consisting of ethanol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol with formaldehyde and Mannich condensation products of phenol, formaldehyde and dialkanolamine, and melamine. The starter molecule having one or more primary amine groups in the molecule may be selected from the group consisting of aniline, ethylenediamine, TDA (toluenediamine), MDA (methylenedianiline) and PMDA (polymeric MDA), more preferably from the group including TDA and PMDA, and most preferably from TDA.

[0044] The polyester polyol is prepared by reacting a dibasic carboxylic acid or dibasic carboxylic acid anhydride with a polyol. The dibasic carboxylic acid is preferably an aliphatic carboxylic acid having 2 to 12 carbon atoms, including, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, or a combination thereof. The dibasic carboxylic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a combination thereof. The polyol reacted with the dibasic carboxylic acid or anhydride is preferably, but not limited to, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-methylpropanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, glycerin, trimethylolpropane, or a combination thereof. The polyester polyol also includes a polyester polyol prepared from a lactone. The polyester polyol prepared from a lactone is preferably, but not limited to, 8-caprolactone.

[0045] Polycarbonate polyols can be prepared by adding carbon dioxide and an alkylene oxide compound to a starter containing active hydrogen in the presence of a double metal cyanide catalyst. Polycarbonate diols prepared by reacting a diol with a dihydrocarbyl carbonate, diaryl carbonate, or phosgene are also suitable for the purposes of the present invention. The diol is preferably, but not limited to, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxymethylene diol, or a mixture thereof. The dihydrocarbyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.

[0046] Generally, the amount of the third polyol can vary based on the actual requirements of the polyurethane product. For example, in one exemplary embodiment, the content of the third polyol can be 5% to 40% by weight, 6% to 35% by weight, 7% to 30% by weight, 8% to 25% by weight, or 10% to 20% by weight, based on the total weight of the polyurethane composition.

[0047] B2) Isocyanate-reactive (meth)acrylate monomers The isocyanate-reactive (meth)acrylate monomer B2 has at least one C=C bond and at least one isocyanate-reactive group such as OH. The isocyanate-reactive (meth)acrylate monomer B2 can be selected from hydroxy C1-10 alkyl (meth)acrylate monomers, more preferably hydroxy C1-6 alkyl (meth)acrylate monomers, even more preferably hydroxypropyl (meth)acrylate monomers, hydroxyethyl (meth)acrylate or hydroxybutyl (meth)acrylate monomers.

[0048] The term (meth)acrylate is intended to include both the corresponding acrylate and methacrylate structures: thus, the term hydroxypropyl (meth)acrylate can correspond to hydroxypropyl methacrylate and / or hydroxypropyl acrylate.

[0049] Generally, the amount of the isocyanate-reactive (meth)acrylate monomer can vary based on the actual requirements of the polyurethane product. For example, in one exemplary embodiment, the content of the isocyanate-reactive (meth)acrylate monomer can be 25% to 40% by weight, 26% to 38% by weight, 27% to 37% by weight, or 28% to 35% by weight, based on the total weight of the polyurethane composition.

[0050] C) Free Radical Initiators The free radical initiator can be an azo compound or a peroxide. Preferably, the azo compound may be 2,2-azobisisobutyronitrile (AIBN); the peroxide may be selected from the group consisting of tert-butyl peroxybenzoate, butyl 4,4-di(tert-butylperoxy)valerate, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxyl)hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxyl)hexyne-3, di-tert-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, isopropylcumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, tert-butyl hydroperoxide, and any combination thereof.

[0051] Generally, the content of free radical initiator used herein is greater than 0, at least 0.1 wt.%, or at least 0.2 wt.%, or at least 0.3 wt.%, and at most 6.0 wt.%, preferably at most 5.0 wt.%, more preferably at most 4.0 wt.%, more preferably at most 3.0 wt.%, or at most 2.0 wt.%, or at most 1.0 wt.%, relative to the total weight of the polyurethane composition.

[0052] D) Other additives The polyurethane composition optionally further comprises other additives, which may be selected from the group consisting of catalysts for the reaction between isocyanate groups and hydroxyl groups, radical polymerization accelerators, antifoaming agents, pigments, fillers and moisture scavengers.

[0053] The polyurethane composition of the present application may contain one or more catalysts capable of promoting the reaction between isocyanate groups and hydroxyl groups. Without being limited by theory, examples of the catalyst include glycine salts, tertiary amines, tertiary phosphines such as trialkylphosphines and dialkylbenzylphosphines, morpholine derivatives, piperazine derivatives, chelates of various metals such as those obtainable from metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni with acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, and the like, ferric chloride, and and stannic chloride; salts of organic acids with various metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and Cu; tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctanoate. organotin compounds such as bismuth diacetate; bismuth salts of organic carboxylic acids, for example, bismuth octoate; organometallic derivatives of trivalent and pentavalent As, Sb, and Bi, and metal carbonyls of iron and cobalt; titanium(IV)-based catalysts such as tetraisopropyl titanate, tetra(n-butyl) titanate, tetraoctyl titanate, titanium acetate, titanium diisopropoxybis(acetylacetonate), and titanium diisopropoxybis(ethylacetoacetate); zirconium tetraacetyl acetonate, zirconium-based catalysts such as zirconium hexafluoroacetylacetonate, zirconium trifluoroacetylacetonate, tetrakis(ethyltrifluoroacetylacetonate)zirconium, tetrakis(2,2,6,6-tetramethyl-heptanedionate), zirconium dibutoxybis(ethylacetoacetate), and zirconium diisopropoxybis(2,2,6,6-tetramethyl-heptanedionate); or mixtures thereof.According to the most preferred embodiment of the present disclosure, the catalyst for the reaction between the isocyanate component A) and the isocyanate-reactive component B), and the reaction between the first polyisocyanate and the first polyol, or the reaction between the second polyisocyanate and the second polyol, is a bismuth salt of an organic carboxylic acid, such as bismuth(III) octoate or bismuth(III) neodecanoate.

[0054] Generally, the content of catalyst used herein is greater than 0 and at most 2.0 wt.%, preferably at most 1.5 wt.%, more preferably at most 1.0 wt.%, more preferably at most 0.5 wt.%, or at most 0.1 wt.%, or at most 0.05 wt.%, relative to the total weight of the polyurethane composition.

[0055] The polyurethane composition of the present application may optionally contain a radical polymerization accelerator. The accelerator can be selected from any type of metal or amine accelerator. Generally, the content of the accelerator used herein is greater than 0 and at most 2.0 wt.%, preferably at most 1.5 wt.%, more preferably at most 1.0 wt.%, more preferably at most 0.5 wt.%, or at most 0.1 wt.%, or at most 0.05 wt.%, based on the total weight of the polyurethane composition.

[0056] The polyurethane composition of the present application may optionally contain an inhibitor. The inhibitor can be a commonly used inhibitor. Generally, the content of the inhibitor used herein is greater than 0 and at most 2.0 wt %, preferably at most 1.5 wt %, more preferably at most 1.0 wt %, more preferably at most 0.5 wt %, or at most 0.1 wt %, or at most 0.05 wt %, relative to the total weight of the polyurethane composition.

[0057] The polyurethane composition of the present application may optionally contain an antifoaming agent. The antifoaming agent may be a silicone or organic antifoaming agent. Generally, the content of the antifoaming agent used herein is greater than 0 and at most 2.0 wt %, preferably at most 1.5 wt %, more preferably at most 1.0 wt %, more preferably at most 0.8 wt %, or at most 0.5 wt %, based on the total weight of the polyurethane composition.

[0058] The polyurethane composition of the present application may optionally contain a water scavenger. The water scavenger can be a commonly used zeolite or liquid water scavenger. Generally, the content of the water scavenger used herein is greater than 0 and at most 10% by weight, preferably at most 8% by weight, more preferably at most 7% by weight, more preferably at most 6% by weight, or at most 5% by weight, or at most 1% by weight, based on the total weight of the polyurethane composition.

[0059] According to a preferred embodiment of the present disclosure, the polyurethane composition is substantially free of intentionally added water or moisture therein. For example, "water-free" or "water-free" means that the mixture of all raw materials used to prepare the polyurethane composition contains less than 3 wt. %, preferably less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, more preferably less than 0.2 wt. %, more preferably less than 0.1 wt. %, and more preferably less than 100 ppm by weight of water or moisture, based on the total weight of the mixture of raw materials.

[0060] The polyurethane composition of the present invention may further comprise conventional additives, such as, for example, a light stabilizer, an ultraviolet (UV) absorbing compound, a leveling agent, a wetting agent, a dispersing agent, a neutralizing agent, or a rheology modifier, or mixtures thereof. These additives may be present in an amount of 0 to 20%, 0.1 to 10%, by weight, based on the weight of the polyurethane composition.

[0061] The polyurethane compositions of the present invention can be prepared using techniques known in the art. The method for preparing the polyurethane compositions includes: 1) A1) and at least one of A2) and A3) A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25%; A3) A second prepolymer formed by the reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20%. providing an isocyanate component, component A), comprising: The total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight based on the total weight of the A) isocyanate component; and

[0062] 2) providing an isocyanate-reactive component B); B1) a third polyol, and B2) Isocyanate-reactive (meth)acrylate monomers providing an isocyanate-reactive component B) comprising: 3) providing a free radical initiator C); 4) providing optional other additives D) known in the art, such as catalysts for the reaction between isocyanate groups and hydroxyl groups, radical polymerization accelerators, antifoaming agents, pigments, fillers and moisture scavengers; 5) then reacting the isocyanate component A) with the isocyanate-reactive component B) in the presence of a free radical initiator C) and optionally other additives D) to form the polyurethane composition described herein; Usually includes.

[0063] The polyurethane compositions of the present invention may be prepared by a one-shot process. The polyurethane compositions of the present invention can be prepared without the use of any reactive diluents such as styrene, methyl methacrylate, etc.

[0064] The polyurethane composition can be cured at temperatures ranging from 4°C to 150°C, preferably from ambient temperature (25°C) to 80°C.

[0065] The polyurethane composition can be used in the preparation of a composite material. Thus, the composite material of the present application includes a fiber reinforced material and the polyurethane composition described herein. The fiber reinforced material can be any fiber known in the art.

[0066] The above description is intended to be general and is not intended to include all possible embodiments of the present invention. Similarly, the following examples are provided for illustrative purposes only and are not intended to define or limit the present invention in any way. Those skilled in the art will fully recognize that other embodiments within the scope of the claims will be apparent from consideration of the specification and / or practice of the invention disclosed herein. Such other embodiments may involve selection of specific ingredients and their configurations and proportions; mixing and reaction conditions; containers, development equipment and protocols; performance and selectivity; product and by-product identification; subsequent processing and use; and the skilled artisan will recognize that such may vary within the scope of the claims appended hereto. [Example]

[0067] The materials used in the examples are shown in Table 1 below.

[0068] [Table 1] Note: HPMA was further dried by adding molecular sieve beads; other materials were used as received without any further purification. The radical initiator was kept in the refrigerator for storage and removed from the refrigerator approximately 30 minutes before its use. Prior to casting, all major components were degassed under vacuum for 1 hour.

[0069] Formulations and Test Results Synthesis of prepolymers A2, A3-1 and A3-2: These prepolymers were formed by the reaction of an isocyanate component with a polyol component. The isocyanate component was added to a reactor and brought to reaction temperature (approximately 70°C) with stirring under a nitrogen pad. The polyol components, if they consist of two or more components, were premixed and then gradually added to the reactor at a rate slow enough to allow the exotherm resulting from the reaction of the isocyanate groups with the hydroxyl groups to dissipate. After the addition of the polyol components was complete, the prepolymer was consumed by beeping while stirring at approximately 70°C while monitoring the NCO content according to ASTM D5155. Prepolymer formation was considered complete when the NCO reached the target NCO value. Additional considerations apply, as known by those skilled in the art of making prepolymers.

[0070] Prepolymer A2: It has an NCO content of 23%. It was formed by reaction of 4,4'-monomer MDI (87% by weight) with tripropylene glycol (13% by weight).

[0071] Prepolymer A3-1: This has an NCO content of 15%. It was formed by reacting an MDI polymer having an isomer mixture of 30% 2,4'-MDI and 70% 4,4'-MDI (18.1 wt%) and an NCO content of 32 wt% (31.8 wt%) with polypropylene glycol having an EW of 1002 g / eq (12.6) and a PO-based triol having a 15% EO cap and an EW of 2040 g / eq (37.5).

[0072] Prepolymer A3-2: This has an NCO content of 18.4%. It was formed by reacting 4,4'-MDI monomer (65.5 wt%) with dipropylene glycol (4.1 wt%), an EO-capped PO-based triol having approximately 15% EO capping and an EW of 2040 g / eq (10.3 wt%), and an EO-capped PO-based diol having approximately 20% EO capping and an EW of 2025 g / eq (20.1 wt%).

[0073] Sample preparation All components were blended in the specified proportions in the order listed in the table, and then thoroughly mixed using a SpeedMixer (DAC 600.1 FVZ, Hauschild) with a dynamic program (800 rpm for 10 seconds, 1200 rpm for 10 seconds, 1600 rpm for 10 seconds, and 2000 rpm for 2 minutes). The resulting liquid resin was further degassed under vacuum for 6 minutes, cast into a vertical steel mold, and left in an oven at 40°C for 1 hour, followed by overnight at 70°C for complete curing. Cast plates were obtained by demolding the next morning for cutting and testing.

[0074] Examples 1 to 3 of the present invention Examples 1 to 3 of the present invention were prepared according to the formulations shown in Table 2.

[0075] Examples 4 to 10 of the present invention Inventive Examples 4-10 were prepared in the same manner as above, and differ from Examples 1-3 in that they used A) prepolymers having different ratios of isocyanate component to total weight or different final prepolymer weight percentages.

[0076] Comparative Example 1 Comparative Example 1 used a lower amount of HPMA compared to the other inventive examples.

[0077] Comparative Examples 2 and 3 Comparative Examples 2-3 are prepared according to prior art formulations using PMDI without the specified prepolymer or combination thereof.

[0078] Comparative Examples 4-5 Comparative Examples 4-5 were formulations containing the individual prepolymers at the same levels of weight percent prepolymer as inventive Examples 7 and 9.

[0079] [Table 2]

[0080] Inventive Examples 1-3 and Comparative Example 1 demonstrate the performance of resins with different levels of HPMA. As the amount of HPMA increased, the open time increased and the initial viscosity of the uncured resin decreased accordingly. When the HPMA level exceeded 30%, resins with open times greater than 2 hours were obtained, along with good physical, mechanical, and thermal properties. When the HPMA level was increased to 37% (Inventive Example 1), the material strength showed a decrease compared to the other inventive examples in Table 2. When the HPMA level was 10% (Comparative Example 1), the thermal stability did not meet industry standards. The results demonstrated that the preferred HPMA monomer range for the present invention is 25-40 wt%.

[0081] Instead, Comparative Examples 2-3, which contained only isocyanate polymer without prepolymer, showed significantly lower physical and mechanical performance compared to the similar levels of HPMA % (30-37%) used in the inventive examples, demonstrating the positive effect of the prepolymer on physical and mechanical properties, which increases the upper limit of HPMA that can be used in this process, and therefore leads to resins with correspondingly longer open times.

[0082] [Table 3]

[0083] When the total prepolymer content was at a relatively low level (<45% as shown in Inventive Examples 4, 5, and 6), all three formulations containing individual prepolymers showed improved performance compared to Comparative Example 3, which did not contain any prepolymers. However, when the prepolymer content exceeded a certain level, the formulations containing a single prepolymer had difficulty meeting the performance criteria. As shown in Comparative Example 4, when only Prepolymer A2 (45% based on the total weight of the isocyanate component) was used, the material became brittle, resulting in insufficient strength and strain at break, while when only Prepolymer A3 (56% based on the total weight of the isocyanate component) was used, stiffness was compromised, resulting in insufficient strength (Comparative Example 5).

[0084] Surprisingly, when both prepolymers were combined in the selected ratio (Inventive Examples 7-10), all formulations exhibited satisfactory strength and maintained other desirable properties well. Prepolymers with NCO contents <10% or >25% are outside the scope. At NCO contents <10%, the prepolymers are very viscous (typically >4000 MPa.s at 25°C) and often contain large amounts of long-chain polyols, resulting in liquid resins with undesirably high initial viscosity, short open time, and poor rigidity. At NCO contents >25%, the final cured resins have poor mechanical strength and are brittle.

[0085] Inventive Examples 8 and 10 showed the effect of prepolymer % (based on the total weight of the isocyanate component): the higher the prepolymer %, the less brittle the material, but also the higher the initial viscosity and the shorter the open time.

[0086] The open time and viscosity were measured with a rheometer AntonPaar MCR102, and the tests were carried out at 25°C in rotational mode with 25 mm parallel plates and a shear rate of 10 s. The open time is defined as the time required for the mixture to reach 500 MPa.s after initial mixing.

[0087] The bending tests were carried out in accordance with standard method ISO 178. A three-point bending template was applied: load cell: 1 kN, speed: 10 mm / min; for each sample, five specimens with dimensions of 80 x 10 x 4 mm were measured.

[0088] Heat distortion temperature (HDT) was measured according to standard method ISO 75-2 - Mode A. Tests were performed using a DMA instrument with a three-point bending geometry. A static force was applied to the sample while it was heated from 35°C to 150°C at a ramp rate of 2°C / min. The displacement was measured in μm and the temperature was recorded.

[0089] The glass transition temperature (Tg) was measured using a DMA apparatus with a three-point bending geometry. The sample was heated from 40°C to 200°C at a rate of 3°C / min. The present application provides, for example, the following inventions. [1] A polyurethane composition comprising: A) A1) and at least one of A2) or A3): A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25% based on the weight of the first prepolymer; A3) a second prepolymer formed by the reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20% based on the weight of the second prepolymer; An isocyanate component comprising: an isocyanate component in which the total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight based on the total weight of the isocyanate component A); B) an isocyanate-reactive component, B1) a third polyol, and B2) Isocyanate-reactive (meth)acrylate monomers the isocyanate-reactive component comprising C) a free radical initiator; 1. A polyurethane composition comprising: [2] The composition according to [1] above, wherein the first prepolymer A2) and the second prepolymer A3) are used individually or in any combination in any ratio, and the total weight of the first prepolymer A2) and the second prepolymer A3) is less than 45% by weight based on the total weight of the isocyanate component A). [3] The composition according to the above [1], wherein the total weight of the first prepolymer A2) and the second prepolymer A3) is 45% by weight to 70% by weight relative to the total weight of the isocyanate component A), and the weight ratio of the first prepolymer A2) to the second prepolymer A3) is 5:1 to 1:5. [4] The composition according to the above [1], wherein the content of the polyisocyanate compound A1) is 30% by weight to 90% by weight based on the total weight of the isocyanate component A). [5] The composition according to the above [1], wherein the first prepolymer A2) has an NCO content of 22% by weight to 24% by weight, based on the weight of the first prepolymer A2). [6] The composition according to the above [1], wherein the second prepolymer A3) has an NCO content of 12% by weight to 19% by weight, based on the total weight of the second prepolymer A3). [7] The composition according to the above [1], wherein the total weight of the first prepolymer A2) and the second prepolymer A3) is 45% by weight to 70% by weight relative to the total weight of the isocyanate component A), and the weight ratio of the first prepolymer to the second prepolymer is 4:1 to 1:4. [8] The composition according to the above [1], wherein the isocyanate-reactive (meth)acrylate monomer B2) is selected from hydroxy C1-10 alkyl (meth)acrylate monomers. [9] The composition according to [1] above, wherein the isocyanate-reactive (meth)acrylate monomer B2) is selected from hydroxypropyl (meth)acrylate monomers and hydroxybutyl (meth)acrylate monomers.

[10] The composition according to the above [1], wherein the content of the isocyanate-reactive (meth)acrylate monomer B2) is 25% by weight to 40% by weight based on the total weight of the polyurethane composition.

[11] The composition according to [1] above, wherein the third polyol has an average functionality of 2 to 5 and an average equivalent weight of 80 to 600 g / eq.

[12] The composition according to [1] above, wherein the polyurethane composition further comprises other additives selected from the group consisting of a catalyst for the reaction between an isocyanate group and a hydroxyl group, a radical polymerization accelerator, an antifoaming agent, a pigment, a filler, and a moisture scavenger.

[13] A composite material comprising a fiber-reinforced material and a polyurethane resin obtained from the polyurethane composition according to any one of the above [1] to

[12] .

[14] A method for preparing a polyurethane resin using the polyurethane composition according to any one of [1] to

[12] above, 1) A1) and at least one of A2) and A3); A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25% based on the weight of the first prepolymer; A3) a second prepolymer formed by the reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20% based on the weight of the second prepolymer; providing an isocyanate component, component A), comprising: The total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight based on the total weight of the isocyanate component; and 2) providing an isocyanate-reactive component B); B1) a third polyol, and B2) Isocyanate-reactive (meth)acrylate monomers providing an isocyanate-reactive component B) comprising: 3) providing a free radical initiator C); 4) then reacting the isocyanate component A) with the isocyanate-reactive component B) in the presence of the free radical initiator C) to form the polyurethane resin; A method comprising:

Claims

1. 1. A polyurethane composition comprising: A) A1) and at least one of A2) or A3): A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25% based on the weight of the first prepolymer; A3) a second prepolymer formed by the reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20% based on the weight of said second prepolymer; An isocyanate component comprising: an isocyanate component in which the total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight, based on the total weight of the isocyanate component A); B) an isocyanate-reactive component, B1) a third polyol having an average functionality of 2 to 5 and an average equivalent weight of 80 to 600 g / eq, and B2) Isocyanate-reactive (meth)acrylate monomers the isocyanate-reactive component comprising C) a free radical initiator; 1. A polyurethane composition comprising:

2. 2. The composition of claim 1, wherein the first prepolymer A2) and the second prepolymer A3) are used individually or in any combination in any ratio, and the total weight of the first prepolymer A2) and the second prepolymer A3) is less than 45% by weight, based on the total weight of the isocyanate component A).

3. 2. The composition of claim 1, wherein the total weight of the first prepolymer A2) and the second prepolymer A3) is 45% to 70% by weight, based on the total weight of the isocyanate component A), and the weight ratio of the first prepolymer A2) to the second prepolymer A3) is 5:1 to 1:

5.

4. 2. The composition according to claim 1, wherein the content of the polyisocyanate compound A1) is from 30% to 90% by weight, based on the total weight of the isocyanate component A).

5. 2. The composition of claim 1, wherein the first prepolymer A2) has an NCO content of 22% to 24% by weight, based on the weight of the first prepolymer A2).

6. 2. The composition of claim 1, wherein the second prepolymer A3) has an NCO content of 12% to 19% by weight, based on the total weight of the second prepolymer A3).

7. 2. The composition of claim 1, wherein the total weight of the first prepolymer A2) and the second prepolymer A3) is 45% to 70% by weight, based on the total weight of the isocyanate component A), and the weight ratio of the first prepolymer to the second prepolymer is 4:1 to 1:

4.

8. The composition of claim 1, wherein the isocyanate-reactive (meth)acrylate monomer B2) is selected from hydroxy C1-10 alkyl (meth)acrylate monomers.

9. The composition of claim 1 , wherein the isocyanate-reactive (meth)acrylate monomer B2) is selected from hydroxypropyl (meth)acrylate monomers and hydroxybutyl (meth)acrylate monomers.

10. 2. The composition of claim 1, wherein the content of the isocyanate-reactive (meth)acrylate monomer B2) is from 25% to 40% by weight, based on the total weight of the polyurethane composition.

11. 10. The composition of claim 1, wherein the polyurethane composition further comprises other additives selected from the group consisting of a catalyst for the reaction between isocyanate groups and hydroxyl groups, a radical polymerization accelerator, an antifoaming agent, a pigment, a filler, and a moisture scavenger.

12. A composite material comprising a fiber reinforced material and a polyurethane resin obtained from the polyurethane composition according to any one of claims 1 to 11.

13. A method for preparing a polyurethane resin using the polyurethane composition according to any one of claims 1 to 11, comprising the steps of: 1) A1) and at least one of A2) and A3); A1) a first polyisocyanate compound; A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a first polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, the first prepolymer having an NCO content of 21 to 25% based on the weight of the first prepolymer; A3) a second prepolymer formed by the reaction of a third polyisocyanate compound with a second polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, the second prepolymer having an NCO content of 10 to 20% based on the weight of said second prepolymer; providing an isocyanate component, component A), comprising: the total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight based on the total weight of the isocyanate component; and 2) providing an isocyanate-reactive component B), B1) a third polyol having an average functionality of 2 to 5 and an average equivalent weight of 80 to 600 g / eq, and B2) Isocyanate-reactive (meth)acrylate monomers providing an isocyanate-reactive component B) comprising: 3) providing a free radical initiator C); 4) then reacting the isocyanate component A) with the isocyanate-reactive component B) in the presence of the free radical initiator C) to form the polyurethane resin; A method comprising:

Images