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

Abstract

Provided are a composite material including a polyurethane composition, a fiber reinforcement material, and a polyurethane resin obtained from the polyurethane composition, as well as a method for preparing the polyurethane resin, The polyurethane composition includes A) an isocyanate component, B) an isocyanate-reactive component including B1) a first polyol, B2) an isocyanate-reactive (meth)acrylate monomer, and B3) an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer, and C) a free radical initiator.

Description

[Technical field]

[0001] The present disclosure relates to a polyurethane composition, a composite material comprising a fiber reinforced material and a polyurethane resin obtained from the polyurethane composition, and a method for preparing the polyurethane resin. The reacted polyurethane resin has a low content of unreacted NCO and exhibits improved polymer properties, making the reacted polyurethane resin suitable for a wide range of composite manufacturing processes and end uses. [Background technology]

[0002] Composite materials are a type of heterogeneous material, containing fiber reinforcement materials to achieve high strength and a polymer matrix to fix and protect the fibers. 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 matrix. To ensure good impregnation quality and processability, the liquid resin should have low viscosity and long open time while at the same time providing a curing time that allows for adequate production cycle times. Apart from that, the physical-mechanical properties, thermal stability, and degree of conversion of functional groups in the cured resin are also important.

[0003] Polyurethane resins exhibit excellent physical and mechanical properties such as low heat generation, good surface quality, and high toughness and fatigue resistance. However, the inherently fast reactivity resulting in short open times makes traditional 2k polyurethane (PU) solutions unsuitable for some composite manufacturing processes that require long open times, such as vacuum infusion. Recently, hybrid PU systems containing ethylenically unsaturated monomers have been developed that exhibit significantly extended open times. US Patent Application Publication No. 10344130(B2) discloses a composition containing isocyanate, polyol, and HPMA, in which the NCO+OH reaction and free radical polymerization occur simultaneously after blending all components in one pot, exhibiting a maximum open time of 115 minutes and optimal performance when the polyol is in the range of 21-60%. However, after polymerization of such hybrid cure systems, a significant amount of unreacted NCO often remains in the cured article, which indicates incomplete polymerization and can adversely affect polymer properties such as heat distortion temperature (HDT) and impair long-term material performance.

[0004] For the above reasons, there remains an unanswered need in the polyurethane manufacturing industry to develop hybrid polyurethane compositions that have low unreacted NCO content and improved polymer properties when cured. After sustained research, the present inventors have surprisingly developed a hybrid polyurethane composition that achieves the desirable characteristics mentioned above when cured. Summary of the Invention

[0005] The present disclosure provides, inter alia, 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 resin.

[0006] In a first aspect of the present disclosure, the present disclosure provides a method for producing a pharmaceutical composition comprising: A) an isocyanate component; B) an isocyanate-reactive component, B1) a first polyol; and B2) isocyanate-reactive (meth)acrylate monomers; and B3) an isocyanate-reactive component comprising an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer; C) a free radical initiator.

[0007] 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, defoamers, pigments, fillers, inhibitors, and moisture scavengers.

[0008] In a second aspect of the disclosure, the disclosure provides a composite material comprising a fiber reinforced material and a polyurethane resin obtained from the polyurethane composition described herein.

[0009] In a third aspect of the present disclosure, the present disclosure provides a method for producing a pharmaceutical composition comprising: 1) providing an isocyanate component A); 2) an isocyanate-reactive component B), B1) a first polyol; and B2) isocyanate-reactive (meth)acrylate monomers; and B3) providing an isocyanate-reactive component B) comprising an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer; 3) providing a free radical initiator C); 4) then reacting the isocyanate component A) with an isocyanate-reactive component B) in the presence of a free radical initiator C) to form the polyurethane resin.

[0010] 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 PREFERRED EMBODIMENTS

[0011] 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, and all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

[0012] definition Numerical ranges disclosed herein include all values ​​between the lower limit and the upper limit (inclusive). When a range includes an explicit value (e.g., a range of 1, or 2, or 3-5, or 6, or 7), any subrange between any two of the explicit values ​​is included (e.g., the range 1-7 above includes the subranges 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0013] Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight and all testing methods are current as of the filing date of this disclosure.

[0014] The term "composition" refers to a mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any preceding description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed. The term "or" refers to the listed members individually and in any combination, unless stated otherwise. The use of the singular includes the use of the plural, and vice versa.

[0016] An "isocyanate" is a chemical that contains at least one isocyanate group in its structure. An isocyanate group is represented by the formula: -N=C=O. An isocyanate that contains 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, etc. Isocyanates can be aromatic or aliphatic.

[0017] A "polyol" is an organic compound that contains 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, that are formed during the synthesis of the polyol as part of a side reaction that forms unsaturated species, i.e., species with double bonds.

[0018] A "polyether" is a compound that contains two or more ether linking groups in the same linear chain of atoms.

[0019] A "polyester" is a compound that contains two or more ester linking groups in the same linear chain of atoms.

[0020] A "polymer" is a polymeric compound prepared by polymerizing monomers, whether they are the same type or different types of monomers. 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 in and / or within the polymer. It also encompasses all forms of copolymers, e.g., random, block, etc. It should be noted that while polymers are often referred to as being "made from" one or more particular monomers, "based on" a particular monomer or monomer type, "containing" a particular monomer content, etc., in this context, the term "monomer" is understood to refer to the polymerized remains of the specified monomer, and not to the unpolymerized species. Generally, polymers herein are based on "units" that are the polymerized form of the corresponding monomers.

[0021] "Hydroxyl number" refers to the content of hydroxyl groups in a polyol. Methods for measuring the hydroxyl number are well known to those skilled in the art and are disclosed, for example, by Houben Weyl, Methoden der Organischen Chemie, vol. XIV / 2 Makromolekulare Stoffe, p. 17, Georg Thieme Verlag; Stuttgart 1963.

[0022] "Average equivalent weight" is the average of the equivalent weights associated with the various components in the mixture. When a mixture is formed by different polyols, the average equivalent weight can be calculated as follows: The average OH number of the mixture is measured as OHav using one of the various experimental techniques known in the art, such as titration or infrared spectroscopy: Then, Calculate the average equivalent weight as EWav=56100 / OHav.

[0023] "Average functionality" is the average of the functionalities associated with the various components in the mixture. When the mixture is formed by different polyols, the average functionality can be calculated as follows: Average functionality = x1f1 + x2f2 where x1 and x2 are the molar ratios of polyol 1 and polyol 2 having functionalities f1 and f2, respectively.

[0024] Isocyanate component A) The isocyanate component A) can include A1) a first polyisocyanate compound.

[0025] 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 comprises at least one aromatic ring (e.g., an aryl group or a heteroaryl group), and all the isocyanate groups in the polyisocyanate compound are directly bonded to the aromatic ring without any linking group between them. The carbodiimide-modified derivatives of the aromatic polyisocyanates mentioned above can also be used in the polyisocyanate compound A1, and the term carbodiimide-modified derivatives can include carbodiimide-modified aromatic polyisocyanates that comprise 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 combinations thereof.

[0026] Generally, the amount of the first polyisocyanate compound A1 can vary based on the actual requirements of the polyurethane product. For example, in an illustrative embodiment, the content of the first polyisocyanate compound A1 can be 15wt%-70wt%, 15wt%-60wt%, or 18wt%-50wt%, or 23wt%-40wt%, or 25wt%-37wt%, based on the total weight of the polyurethane composition.

[0027] In another preferred embodiment, the content of the first polyisocyanate compound A1 may be 30% by weight to 100% by weight, or 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 75% by weight, based on the total weight of the isocyanate component A).

[0028] Isocyanate component A) may further comprise a prepolymer formed by reaction of a polyisocyanate compound, which may be described similarly to component A1 described above, with a polyol, the prepolymer having an NCO content of 10-25% based on the weight of the prepolymer. Preferably, the amount of prepolymer may be 10-70% by weight, or 10-65% by weight, or 15-60% by weight, or 20-55% by weight, or 25-40% by weight, based on the total weight of isocyanate component A).

[0029] More preferably, the isocyanate component A) comprises, in addition to the first polyisocyanate compound A1), at least one of A2) or A3): A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a second polyol, the second 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 third polyol, the third polyol having an average equivalent weight of 250-3000 g / eq and an average functionality of 2-3, the second prepolymer having an NCO content of 10-20%, based on the weight of the second prepolymer; The total amount of the first prepolymer A2) and the second prepolymer A3) is 10 to 70% by weight, or 10 to 65% by weight, or 15 to 60% by weight, or 20 to 55% by weight, or 25 to 40% by weight, based on the total weight of the isocyanate component A).

[0030] First Prepolymer A2 The first prepolymer A2 is formed by reaction of a second polyol with a second polyisocyanate compound. The second polyisocyanate compound can be an isocyanate monomer or an isocyanate polymer, where the latter in each case refers 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.

[0031] The second 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 (which may broadly include tetrahydrofuran) 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, but not limited to, 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, for example, glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, and any combination thereof.

[0032] The content of the second 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.

[0033] 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] Second Prepolymer A3 The second prepolymer A3 is formed by the reaction of a third 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.

[0035] The third polyol component used in prepolymer A3 is a polyether polyol that can be prepared by reacting an olefin oxide (which may broadly include tetrahydrofuran) 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, but not limited to, ethylene oxide and / or propylene oxide. Starter molecules include compounds having at least one, preferably 2 to 8, more preferably 2 to 4 hydroxyl groups per molecule; they may contain one or more primary amine groups in the molecule.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 and 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 consisting of TDA and PMDA, and most preferably from TDA.

[0036] In one preferred embodiment of the present application, the third 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.

[0037] The content of the third 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.

[0038] 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.

[0039] Prepolymer A2 may be referred to as the first prepolymer, and prepolymer A3 may be referred to as the second prepolymer.

[0040] The first prepolymer A2 and the second prepolymer A3 can be used individually or in combination in any ratio.

[0041] 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 25% by weight to 40% by weight, based on the total weight of the isocyanate component A.

[0042] B1) First polyol The second polyol is that used in the synthesis of prepolymer A2. The third polyol is that used in the synthesis of prepolymer A3. The first polyol B1 is part of the isocyanate-reactive component B) of the polyurethane composition of the present invention. The first polyol B1 has an average equivalent weight of 80-600 g / eq, preferably 80-510 g / eq, and an average functionality of 2-5, preferably 2-3. 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] Polyether polyols can be prepared by known methods, for example, by reacting an olefin oxide (which may broadly include tetrahydrofuran) 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, but not limited to, 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 with formaldehyde and dialkanolamine, and also 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 consisting of TDA and PMDA, most preferably from TDA.

[0044] The polyester polyol is prepared by the reaction of a dibasic carboxylic acid or a dibasic carboxylic anhydride with a polyol. The dibasic carboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid having 2 to 12 carbons, and is preferably, 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 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, ε-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 or 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 mixtures thereof. The dihydrocarbyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.

[0046] Generally, the amount of the first polyol can vary based on the actual requirements of the polyurethane product. For example, in one illustrative embodiment, the content of the first polyol can be 10% by weight to 40% by weight, or 12% by weight to 35% by weight, or 14% by weight to 30% by weight, or 15% by weight to 25% by weight, or 16% by weight 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 isocyanate-reactive (meth)acrylate monomer can vary based on the actual requirements of the polyurethane product. For example, in one illustrative embodiment, the content of isocyanate-reactive (meth)acrylate monomer can be 15% to 40% by weight, or 20% to 38% by weight, or 25% to 35% by weight, or 27% to 32% by weight, based on the total weight of the polyurethane composition.

[0050] B3) Acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomers An acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer is a (meth)acrylate monomer having one or more acetoacetoxy- or one or more acetoacetamide-functional groups. An acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer can be represented by the formula:

[0051] [ka] In the formula, X is O or N, and R 1 is a divalent hydrocarbon radical, preferably C 1 ~C 6 Alkyl or C 2 ~C 4 alkyl and Y is a (meth)acrylate group.

[0052] Acetoacetoxy- or acetoacetamido-functional (meth)acrylate monomers useful in the present invention may include acetoacetoxyethyl methacrylate (AAEM), acetoacetoxyethyl acrylate, acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, acetoacetamidoethyl methacrylate, acetoacetamidoethyl acrylate, acetoacetamidopropyl (meth)acrylate, acetoacetamidobutyl (meth)acrylate, or combinations thereof.

[0053] Generally, the amount of acetoacetoxy or acetoacetamide functional (meth)acrylate monomer can vary based on the actual requirements of polyurethane product.For example, as an illustrative embodiment, the content of acetoacetoxy or acetoacetamide functional (meth)acrylate monomer can be 0.5wt%-15wt%, or 1wt%-14wt%, or 1.5wt%-13wt%, or 2.0wt%-12wt%, or 3.0wt%-11wt%, or 4.0wt%-10.5wt%, or 7.0wt%-10wt%, based on the total weight of polyurethane composition.

[0054] 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) and the peroxide may be selected from the group consisting of tert-butyl peroxybenzoate, 4,4-di(tert-butylperoxy)butyl 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.

[0055] Generally, the content of the free radical initiator used herein is greater than zero, 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%, based on the total weight of the polyurethane composition.

[0056] 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, defoamers, pigments, fillers, inhibitors, and moisture scavengers.

[0057] The polyurethane composition of the present application may include one or more catalysts capable of promoting the reaction between isocyanate groups and hydroxyl groups. Without being limited by theory, the catalysts include, for example, 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; dichloromethane, ... Acidic metal salts of strong acids such as iron 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 organotin compounds such as dioctyltin diacetate; bismuth salts of organic carboxylic acids, e.g. bismuth octanoate; organometallic derivatives of trivalent and pentavalent As, Sb and Bi, as well as 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 tetra zirconium based catalysts such as acetylacetonate, zirconium hexafluoroacetylacetonate, zirconium trifluoroacetylacetonate, tetrakis(ethyltrifluoroacetyl-acetonate)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), or the reaction between the second polyisocyanate and the second polyol, or the reaction between the third polyisocyanate and the third polyol, is a bismuth salt of an organic carboxylic acid or a tin salt of an organic carboxylic acid, such as bismuth(III) octoate or bismuth(III) neodecanoate, or stannous octoate.

[0058] Generally, the catalyst content used herein is greater than zero 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.

[0059] The polyurethane composition of the present application may optionally include a radical polymerization accelerator. The accelerator can be selected from all types of metal or amine accelerators. In general, the content of the accelerator used herein is greater than zero and at most 2.0% by weight, preferably at most 1.5% by weight, more preferably at most 1.0% by weight, more preferably at most 0.5% by weight, or at most 0.1% by weight, or at most 0.05% by weight, based on the total weight of the polyurethane composition.

[0060] The polyurethane composition of the present application may optionally contain an inhibitor. The inhibitor may be a commonly used inhibitor, such as hydroquinone monomethyl ether (MeHQ). In general, the content of the inhibitor used herein is greater than zero and is at most 2.0% by weight, preferably at most 1.5% by weight, more preferably at most 1.0% by weight, more preferably at most 0.5% by weight, or at most 0.1% by weight, or at most 0.05% by weight, based on the total weight of the polyurethane composition.

[0061] The polyurethane composition of the present application may optionally include 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 zero and is at most 2.0% by weight, preferably at most 1.5% by weight, more preferably at most 1.0% by weight, more preferably at most 0.8% by weight, or at most 0.5% by weight, based on the total weight of the polyurethane composition.

[0062] 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. In general, the content of the water scavenger used herein is greater than zero 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.

[0063] According to a preferred embodiment of the present disclosure, the polyurethane composition is substantially free of water or moisture intentionally added thereto. For example, "free of water" 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.%, more preferably less than 100 ppm water by weight based on the total weight of the mixture of raw materials.

[0064] The polyurethane composition of the present invention may further comprise conventional additives such as, for example, light stabilizers, ultraviolet (UV) absorbing compounds, leveling agents, wetting agents, dispersants, neutralizing agents, or rheology modifiers, or mixtures thereof. These additives may be present in an amount of zero to 20% by weight, 0.1 to 10% by weight, based on the weight of the polyurethane composition.

[0065] The curing of the polyurethane composition of the present disclosure, which is actually a PU-acrylate hybrid formulation, is based on heat-induced radical polymerization and polyol + isocyanate addition polymerization. The polyurethane resin obtained in the present disclosure is a polyurethane-polyacrylate hybrid resin system. The acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer B3 can improve the conversion degree of NCO groups in the polyurethane composition of the present disclosure, resulting in improved resin properties after curing. The polyurethane resin of the present invention can be prepared using techniques known in the art. The process for preparing the polyurethane resin typically includes: 1) providing an isocyanate component A); 2) an isocyanate-reactive component B), B1) a first polyol; and B2) isocyanate-reactive (meth)acrylate monomers; B3) providing an isocyanate-reactive component B) comprising an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer; 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 a polyurethane resin.

[0066] When optionally other additives D) known in the art, such as catalysts for the reaction between isocyanate groups and hydroxyl groups, radical polymerization accelerators, defoamers, pigments, fillers, inhibitors, and moisture scavengers, are used, the process for preparing the polyurethane resin typically comprises the steps of: 1) providing an isocyanate component A); 2) an isocyanate-reactive component B), B1) a first polyol; and B2) isocyanate-reactive (meth)acrylate monomers; B3) providing an isocyanate-reactive component B) comprising an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer; 3) providing a free radical initiator C); 4) optionally providing other additives D); 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.

[0067] The polyurethane composition of the present invention can be prepared by a one-shot process. The polyurethane composition of the present invention can be prepared without using any reactive diluent such as styrene, methyl methacrylate, etc.

[0068] The polyurethane composition can be cured at a temperature ranging from 4°C to 150°C, preferably from ambient temperature (25°C) to 80°C.

[0069] 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, including glass fiber or carbon fiber, as known in the art.

[0070] 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 herein 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 include 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 like, and those skilled in the art will recognize that such may vary within the scope of the claims appended hereto. EXAMPLES

[0071] The materials used in the examples are shown in Table 1 below.

[0072] [Table 1]

[0073] Formulations and Test Results Synthesis of prepolymers 1 and 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 (about 70° C.) with stirring under nitrogen padding. 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 for the removal of the exotherm generated by the reaction of the isocyanate groups with the hydroxyl groups. After the addition of the polyol components was complete, the prepolymer was consumed by keeping it with stirring at about 70° C. while monitoring the NCO content according to ASTM D5155. When the NCO reached the target NCO value, the prepolymer formation was considered complete. Further considerations apply as known by those skilled in the art of making prepolymers.

[0074] Prepolymer 1: It has an NCO content = 23% and a viscosity = 575 mPa.s at 25°C. It was formed by reaction of 4,4'-monomer MDI (87% by weight) with tripropylene glycol (13% by weight).

[0075] Prepolymer 2: It has an NCO content = 15%. It was formed by the reaction of an isomeric mixture of ISOCYNATE 2 (18.1 wt%) and ISOCYNATE 1 (31.8 wt%) with Polyol 2 (polypropylene glycol with EW = 1002 g / eq, OH number = 56 mg KOH / g) (12.6 wt%) and Polyol 3 (propoxylated glycerin with 15% EO cap and EW = 2040 g / eq, OH number = 28 mg KOH / g) (37.5 wt%).

[0076] Sample preparation All ingredients were blended in the specified proportions in the order listed in the table, 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, 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 70°C overnight to fully cure. Cast mold plates were obtained by demolding the next morning for cutting and testing.

[0077] Examples 1 to 3 of the present invention Inventive Examples 1-3 were prepared according to the formulations shown in Table 2.

[0078] Comparative Example 1 Comparative Example 1 did not use AAEM as compared to the inventive examples.

[0079] The Isocyanate Index is the ratio of NCO groups (from isocyanate and prepolymer components) to NCO reactive groups (from polyols and HPMA and other isocyanate reactive components) multiplied by 100. An index of 100 therefore corresponds to the situation where the number of NCO groups is the same as the number of NCO reactive groups. The comparative example and the inventive example were run with the same Isocyanate Index of 102.7, which corresponds to a slight stoichiometric excess of NCO groups.

[0080] [Table 2]

[0081] Inventive Examples 1-3 were formulations containing increasing levels of AAEM from 3.2% to 9.9% by weight in the hybrid polyurethane formulation. Comparative Example 1 was a formulation without AAEM. Cured samples were characterized by FTIR to measure residual unreacted NCO. Residual NCO was determined by the FTIR peak at 2274 cm -1 and 1520cm -1 and C=C, which are attributed to free NCO and C=C as internal standards, respectively. As shown in Table 2, Comparative Example 1 showed a significant amount of residual NCO, but by introducing AAEM, the residual NCO was dramatically reduced.

[0082] Test Method: Fourier transform infrared spectroscopy- attenuated total reflectance (FTIR-ATR) FTIR-ATR results were collected on a PerkinElmer Model equipped with an ATR accessory for the cured samples and the corresponding isocyanate mixtures. Twelve scans were collected for each sample. The NCO residue was calculated based on the following formula:

[0083]

number

[0084] Heat distortion temperature (HDT) HDT was measured according to the protocol provided by TA instruments "Using the DMA Q800 for ASTM International D 648 Deflection Temperature Under Load".

Claims

1. 1. A polyurethane composition comprising: A) an isocyanate component; B) an isocyanate-reactive component, B1) a first polyol; and B2) an isocyanate-reactive (meth)acrylate monomer; and B3) an isocyanate-reactive component comprising an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer; C) a free radical initiator.

2. 2. The composition of claim 1, wherein the isocyanate component A) comprises A1) a first polyisocyanate compound.

3. 3. The composition of claim 2, wherein said isocyanate component A) further comprises a prepolymer formed by reaction of a polyisocyanate compound with a polyol, said prepolymer having an NCO content of 10 to 25%, based on the weight of said prepolymer.

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

5. The isocyanate component A) comprises, in addition to the first polyisocyanate compound A1), at least one of A2) or A3): A2) a first prepolymer formed by the reaction of a second polyisocyanate compound with a second polyol, said second polyol having an average equivalent weight of 30 to 200 g / eq and an average functionality of 2 to 3, said first prepolymer having an NCO content of 21 to 25%, based on the weight of said first prepolymer; A3) a second prepolymer formed by the reaction of a third polyisocyanate compound with a third polyol, said third polyol having an average equivalent weight of 250 to 3000 g / eq and an average functionality of 2 to 3, said second prepolymer having an NCO content of 10 to 20%, based on the weight of said second prepolymer; The composition of claim 2, wherein the total amount of said first prepolymer A2) and said second prepolymer A3) is 10 to 70% by weight, based on the total weight of said isocyanate component A).

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

7. 2. 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.

8. The acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer B3) is represented by 【Chemistry 1】 In the formula, X is O or N, and R １ The composition of claim 1 , wherein is a divalent hydrocarbon radical and Y is a (meth)acrylate group.

9. 9. The composition of claim 8, wherein the acetoacetoxy-functional (meth)acrylate monomer B3) is selected from the group consisting of acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, or combinations thereof.

10. The composition of claim 8, wherein the content of the acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer is from 0.5% to 15% by weight, based on the total weight of the polyurethane composition.

11. 2. The composition of claim 1, wherein the content of the isocyanate-reactive (meth)acrylate monomer B2) is from 15% to 40% by weight, based on the total weight of the polyurethane composition.

12. The composition of claim 1, wherein the first polyol has an average functionality of 2 to 5 and an average equivalent weight of 80 to 600 g / eq.

13. 10. The composition of claim 1, wherein the polyurethane composition further comprises other additives selected from the group consisting of catalysts for the reaction between isocyanate groups and hydroxyl groups, radical polymerization accelerators, defoamers, pigments, fillers, inhibitors, and moisture scavengers.

14. 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 13.

15. A method for preparing a polyurethane resin using the polyurethane composition according to any one of claims 1 to 13, comprising the steps of: 1) providing an isocyanate component A); 2) an isocyanate-reactive component B), B1) a first polyol; and B2) an isocyanate-reactive (meth)acrylate monomer; and B3) providing an isocyanate-reactive component B) comprising an acetoacetoxy- or acetoacetamide-functional (meth)acrylate monomer; 3) providing a free radical initiator C); 4) then reacting said isocyanate component A) with said isocyanate-reactive component B) in the presence of said free radical initiator C) to form said polyurethane resin.

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