Resin composition and composite material, urea-containing polyurethane acrylate resin and preparation method thereof

Abstract

A resin composition including urea-containing polyurethane acrylic resin is provided. The urea-containing polyurethane acrylic resin is prepared by amidating isocyanate groups in a polyurethane acrylate polymer with an amine compound to form a urea group.

Description

Technical Field

[0001] This disclosure relates to a resin composition and composite material and a method for preparing the resin, and particularly to a resin composition and composite material comprising a urea-containing polyurethane acrylate resin and a method for preparing the urea-containing polyurethane acrylate resin. Prior Technology

[0002] Polyurethane acrylate (PUA) resins are widely used in electronic devices, building materials, coatings, and paints. However, how to modify them to make them more widely used and / or have better quality is a research topic. Summary of the Invention

[0003] This disclosure provides a resin composition and composite material, as well as a method for preparing urea-containing polyurethane acrylate resin, which can be widely used and has better quality.

[0004] The resin composition disclosed herein includes urea-containing polyurethane acrylate resin. This urea-containing polyurethane acrylate resin is prepared by amide-modifying the isocyanate groups in the polyurethane acrylate polymer with amine compounds to form urea groups.

[0005] The resin composition disclosed herein includes a urea-containing polyurethane acrylate resin as shown in Formula 1 below.

[0006] The composite material disclosed herein includes the aforementioned resin composition and fiber material. The total amount of the resin composition is 67 to 240 parts by weight per 100 parts by weight.

[0007] The method for preparing urea-containing polyurethane acrylate resin disclosed herein includes: providing a polyurethane acrylate polymer, adding an amine compound, and heating to cause the polyurethane acrylate polymer to undergo a modification reaction.

[0008] Based on the above, since the polyurethane acrylate resin used in the resin composition and composite material disclosed herein is a modified urea-containing polyurethane acrylate resin, it can be widely used and has better quality. Simple Explanation of the Diagram

[0009] none. Implementation

[0010] In this article, unless otherwise specified, when using the antecedent "approximately" to express a numerical value, it can be directly represented as that specific numerical value. Furthermore, when using the antecedent "approximately" to express that numerical value, it can include the range of measurement errors that can be included in general measurement methods, or the range of error propagation after derivation and calculation using it.

[0011] In this document, when expressing numerical values ​​or ranges, possible embodiments include a specific value, another specific value, and a range between the two specific values. For example, when expressing a range of 1 to 10, and also expressing specific values ​​of 3 and 7, one embodiment may include a specific value of 1, a specific value of 3, a specific value of 7, a specific value of 10, a range of 1 to 3, a range of 1 to 7, a range of 3 to 7, a range of 3 to 10, and a range of 7 to 10. For example, when expressing specific values ​​of 2, 5, and 8, one embodiment may include a specific value of 2, a specific value of 5, a specific value of 8, a range of 2 to 5, a range of 2 to 8, and a range of 5 to 8.

[0012] [<1.] [Urea-containing polyurethane acrylic] [Ester Resin] [>] Urea-based polyurethane acrylate resins can be obtained by reacting isocyanate compounds, polyol compounds, hydroxyl-containing (meth)acrylate compounds, and amine compounds.

[0013] [<1.1 ] [Isocyanate compounds] [>] The isocyanate compound is a difunctional (i.e., at least difunctional) isocyanate compound; for example, an isocyanate compound containing an isocyanate group (NCO). Commercially available difunctional isocyanate compounds may include, but are not limited to: Tosoh Corporation, models: MR200, NM; Wanhua Chemical, models: PM200, MDI-50; BASF SE, model: M20S; Covestro AG, model: 44V20; Huntsman Corporation, model: 5005.

[0014] This disclosure does not limit isocyanate compounds to a single compound form. Taking difunctional isocyanate compounds in polymer form as an example, they can be polymers of a single monomer, such as toluene diisocyanate (TDI) or isophorone diisocyanate (IPDI); or, mixtures of polymers of multiple monomers; or, copolymers, such as diphenylmethane diisocyanate (MDI-50).

[0015] [<1.2 ] [Polyol compounds] [>] The polyol compound is a bifunctional polyol compound; for example, a bifunctional polyether polyol compound, including but not limited to polyoxyethylene ether, polyoxyethylene alkyl ether, polyoxypropylene ether, polyoxypropylene alkyl ether, or polytetrahydrofuran. In the above embodiments, although polymers are used as examples of polyol compounds, this disclosure is not limited to this, and the polyol compound may also be a non-polymer form.

[0016] This disclosure does not limit the polyol compound to a single compound form. Taking a difunctionalized polyol compound in polymer form as an example, it can be a polymer of a single monomer; or a mixture of polymers of multiple monomers; or a copolymer.

[0017] In one embodiment, if the bifunctionalized polyol compound is in polymer form, its number average molecular weight is preferably below about 2000 g / mol.

[0018] [<1.3 ] [Contains hydroxyl groups] [(] [methyl] [)] [Acrylic compounds] [>] In this disclosure, hydroxyl-containing (meth)acrylate is an abbreviation for "hydroxyl-containing acrylate" or "hydroxyl-containing methacrylate". Hydroxyl-containing (meth)acrylates can be used in combination. Specifically, hydroxyl-containing (meth)acrylate compounds may include, but are not limited to, at least one or more of the following: hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0019] [<1.4 ] [Amine compounds] [>] Amine compounds may include amine polymers, monoamine compounds, diamine compounds, or mixtures thereof. Amine polymers may be, for example, polyetheramines with a number-average molecular weight of about 400 g / mol or less. Monoamine compounds may include primary aliphatic amines, secondary aliphatic amines, primary alicyclic amines, secondary alicyclic amines, or mixtures thereof. An example of aliphatic secondary amines is dibutylamine. Diamine compounds may include primary aliphatic amines, primary alicyclic amines, secondary alicyclic amines, or mixtures thereof. An example of aliphatic primary amines is polyetheramine (D230). Alicyclic primary amines include isophorone diamine (IPDA) and 4,4'-diaminodicyclohexylmethane (PACM). Alicyclic secondary amines include piperazine.

[0020] [<1.5] [Diluted Monomer] [>] Diluting monomers possess functional groups suitable for the reaction; or they can form corresponding free radical groups. In this way, they can form polymer chains with the corresponding reactants through sequential addition, thereby adjusting viscosity / flowability. Therefore, diluting monomers can also be called viscosity-adjusting monomers. The selection can be based on the types of isocyanate compounds, polyol compounds, hydroxyl-containing (meth)acrylate compounds, or amine compounds mentioned above. More appropriately, diluting monomers can be selected from compounds that are structurally similar to or have the same functional groups as the aforementioned isocyanate compounds, polyol compounds, hydroxyl-containing (meth)acrylate compounds, or amine compounds to promote sequential addition polymerization reactions. For example, diluting monomers can be selected from one or more mixtures of methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, propyl (meth)acrylate, hydroxypropyl (meth)acrylate, tetrahydrofuran (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, styrene, methylstyrene, and vinyltoluene.

[0021] In one embodiment, the total amount of the urea-containing polyurethane acrylate resin ultimately produced by the subsequent reaction is 100 parts by weight, and the total amount of the diluted monomer is 30 to 45 parts by weight.

[0022] [<1.6 ] [Inhibitor] [>] The addition of inhibitors can improve the stability of resin compositions. In one embodiment, the inhibitor may include phenolic compounds; for example, 2,5-dihydroxytoluene or 2,6-di-tert-butylhydroxytoluene.

[0023] In one embodiment, the total amount of inhibitor is 0.01 to 0.03 parts by weight, based on 100 parts by weight of the total amount of the urea-containing polyurethane acrylate resin composition finally generated by the subsequent reaction.

[0024] [<1.7 ] [Ratio relationship between reactants] [>] From the perspective of reagent preparation, describing the amount of each component used in a composition as a weight or weight ratio is more straightforward. However, from the perspective of the reactivity between components, considering the number and / or type of functional groups in the compound (especially compounds with specific reaction purposes, such as bifunctionalized compounds), and the actual composition ratio in commercially available reagents, it may be more accurate to describe it as a molar ratio or molar equivalent ratio (or equivalent ratio) of the compound or its functional groups. The relationship between the molar ratio or equivalent ratio of functional groups and the weight or weight ratio of each component in the composition can be derived and calculated using appropriate detection methods, such as titration, infrared spectroscopy (IR spectrum), or nuclear magnetic resonance spectroscopy (NMR spectrum), but this disclosure is not limited to these methods.

[0025] In one embodiment, the equivalent ratio of the isocyanate group of the isocyanate compound to the hydroxyl group of the polyol compound is 15:1 to 1:1; more preferably, it is 9:1 to 3:1.

[0026] In one embodiment, the equivalent ratio of the hydroxyl group of the polyol compound to the amino group of the amine compound is 9:1 to 7:3.

[0027] In one embodiment, the equivalence ratio of the hydroxyl groups of the hydroxyl (meth)acrylate compound to the isocyanate groups of the isocyanate compound is from 1:1.1 to 1:1.5.

[0028] [<2.] [Urea-containing polyurethane acrylic] [Synthesis methods of ester resins] [>]

[0029] [<2.1 ] [Prepolymerization] [>] First, the isocyanate compound is mixed with the diluted monomer and heated for use as the first reaction reagent in the subsequent reaction. A suitable heating temperature can be between 40 °C and 70 °C; for example, 45 °C to 60 °C.

[0030] Then, the polyol compound is added to the first reaction reagent at an appropriate temperature to carry out a prepolymerization reaction, thereby obtaining the corresponding polyurethane prepolymer.

[0031] In one embodiment, the aforementioned prepolymerization reaction may be further enhanced with a catalyst. The catalyst may include organometallic (e.g., tin, zinc, bismuth, or titanium) catalysts or organic-base catalysts. Organometallic catalysts include, for example, dibutyltin dilaurate (DBTDL). Organic-base catalysts include, for example, 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0032] In one embodiment, the amount of catalyst added is from 50 milligrams (mg) to 200 milligrams, based on a total amount of 1 kg of urea-containing polyurethane acrylate resin ultimately produced by the subsequent reaction.

[0033] In one embodiment, the aforementioned prepolymerization reaction may be further modified by adding an inhibitor to reduce or slow down unwanted polymerization. Inhibitors may include, for example, butylated hydroxytoluene (BHT) or 2,5-dihydroxytoluene.

[0034] In one embodiment, after the addition of the polyol compound, the mixture can be further kept at the aforementioned appropriate temperature to allow for a sufficient reaction for a period of time, for example, 1 to 4 hours. In one embodiment, appropriate detection methods (such as viscosity measurement, spectral analysis, sampling titration, thermal analysis, etc.) can be used to determine whether a sufficient proportion or amount of polyurethane prepolymer has been generated.

[0035] [<2.2 ] [Polymerization reaction] [>] Then, after obtaining a sufficient proportion or amount of polyurethane prepolymer, a hydroxyl (meth)acrylate compound is added to the polyurethane prepolymer held at the aforementioned appropriate temperature to carry out a polymerization reaction to obtain a polyurethane acrylate polymer.

[0036] In one embodiment, the total mole number of isocyanate groups in the polyurethane prepolymer is greater than the total mole number of hydroxyl groups in the hydroxyl (meth)acrylate compound, based on the total amount of the polyurethane prepolymer and the hydroxyl (meth)acrylate compound added. That is, the obtained polyurethane acrylate polymer still contains isocyanate groups.

[0037] In one embodiment, after the addition of the hydroxyl (meth)acrylate compound, the mixture can be allowed to react sufficiently for a period of time at an appropriate temperature, for example, 1 to 4 hours. In one embodiment, it can be determined whether a sufficient proportion or amount of polyurethane acrylate polymer has been generated by appropriate measurement methods as described above.

[0038] [<2.3 ] [Modification reaction] [>] Next, amine compounds are added to the polyurethane acrylate polymer held at the aforementioned appropriate temperature to carry out a modification reaction. The modification reaction is essentially the process of amide-amination of the residual isocyanate groups in the polyurethane acrylate polymer to urea groups by the amine compounds.

[0039] In one embodiment, based on the total amount of the aforementioned polyurethane prepolymer, the total amount of the aforementioned hydroxyl (meth)acrylate compound added, and the total amount of the amine compound added, the sum of the moles of hydroxyl groups in the hydroxyl (meth)acrylate compound and the moles of amine groups in the amine compound is greater than the total moles of isocyanate groups in the polyurethane prepolymer. That is, after the aforementioned modification reaction, the remaining isocyanate groups in the polyurethane acrylate polymer can be substantially amided. This is defined as the percentage ratio of the total weight of isocyanate groups to the total weight of the polyurethane acrylate polymer (i.e., the weight percentage of isocyanate groups (hereinafter referred to as the NCO value)) being less than 0.5%. The NCO value can be determined according to standard methods (e.g., ISO 14896:2009 Plastics - Polyurethane raw materials - Determination of isocyanate content).

[0040] In one embodiment, the amine compound may be added continuously / evenly (e.g., by dropwise addition) in the range of 5 to 40 minutes (preferably, 10 to 30 minutes).

[0041] Appropriate reaction temperature and a suitable rate of amine addition can amide isocyanate groups. However, if the local instantaneous concentration of the added amine is too high, it may promote unintended reactions (e.g., excessive or unintended crosslinking), potentially altering subsequent reactivity or physical properties (e.g., viscosity, glass transition temperature (Tg), tensile strength, or impact strength). Therefore, amines must be added continuously or evenly.

[0042] In one embodiment, after the addition of the amine compound, the reaction can be allowed to proceed for a sufficient period of time at an appropriate temperature, for example, 1 to 2 hours. In one embodiment, the NCO value can be measured using the standard method described above to determine whether the remaining isocyanate groups have been substantially amylated to urea groups.

[0043] [<3.] [Urea-containing polyurethane acrylic] [Ester Resin] [>] The urea-containing polyurethane acrylate resin synthesized by the above method may include, for example, the polymer shown in [Formula 1].

[0044] [Formula 1]

[0045] In [Formula 1], R1 is hydrogen or methyl; R2 is an organic group containing an alkyl group, such as a linked alkyl group containing one to three carbons (i.e., -CH2-, -C2H4-, ...). R3 is an organic group containing an aromatic group, such as phenyl. , , or n1 is an integer greater than or equal to 1, for example, 1 to 3; R4 is an organic group, such as alkyl, alkenyl, or alkyl ether. The aforementioned alkyl groups include, for example, alkyl groups linked with one to three carbons. The aforementioned alkenyl groups include, for example, allyl. The aforementioned alkyl ether groups include, for example, ether groups consisting of two independently linked alkyl groups having one to four carbons, including but not limited to dimethyl ether (i.e., -CH2-O-CH2-), methyl ethyl ether (i.e., -CH2-O-C2H4-), diethyl ether (-C2H4-O-C2H4-), dipropyl ether (-C3H6-O-C3H6-), or dibutyl ether (-C4H8-O-C4H8-), etc.

[0046] In [Equation 1], R5 is the linking group shown in [Equation 2] below.

[0047] [Equation 2]

[0048] In [Formula 2], T21 is an organic group, such as alkyl, alkenyl, or alkyl ether. Its definition is the same as that of R4 in the previous paragraph.

[0049] In [Equation 2], T2 is an organic group containing an aromatic group, such as phenyl, , , or n2 is an integer greater than or equal to 1, for example, 1 to 3.

[0050] In [Equation 2], T22 is hydrogen or methyl.

[0051] In [Formula 1], R6 is an organic group, such as a nitrogen-containing organic group; R7 is hydrogen or a cyclic organic compound co-constituted with R6.

[0052] In [Equation 1], m and n are integers greater than or equal to 1. Based on physical characteristics, m is preferably less than 100 and n is preferably less than 100.

[0053] In one embodiment, the urea-containing polyurethane acrylate resin disclosed herein may be as shown in the following [Formula 1-1], [Formula 1-2], [Formula 1-3], [Formula 1-4], and [Formula 1-5].

[0054] [Equation 1-1]

[0055] [Equation 1-2]

[0056] [Equation 1-3]

[0057] [Equations 1-4]

[0058] [Equations 1-5]

[0059] In Equations 1-1, 1-2, 1-3, 1-4, and 1-5, the definitions of R1, R2, R3, R4, R5, m, and n are the same as in Equation 1.

[0060] In [Equation 1-1], [Equation 1-2], [Equation 1-3], [Equation 1-4], and [Equation 1-5], R81, R82, R83, and R84 are independent organic groups, such as hydrogen, etc. The definitions of R1', R2', R3', R4', R5', m', and n' are the same as the definitions of R1, R2, R3, R4, R5, m, and n, respectively.

[0061] In one embodiment, the formation of urea groups in the urea-containing polyurethane acrylate resin can be further detected by nuclear magnetic resonance spectroscopy. In one embodiment, when the aforementioned urea-containing polyurethane acrylate resin is detected by solution nuclear magnetic resonance spectroscopy, two signal peaks with a separation distance greater than 0.5 ppm can be observed in the proton NMR spectrum within the shift range of 8-10 ppm, which can be inferred to be generated by the active hydrogen of amide and urea groups, respectively. Since the urea-containing polyurethane acrylate resin molecule contains polar groups, the active hydrogen of amide and urea groups is affected by intramolecular and / or intermolecular hydrogen bonding forces, causing the detected signal peaks to be located at a lower field shift position.

[0062] [<4.] [Resin Composition] [>]

[0063] The resin composition includes at least the aforementioned urea-containing polyurethane acrylate resin. That is, the resin composition includes at least a resin obtained by reacting isocyanate compounds, polyol compounds, hydroxyl-containing (meth)acrylate compounds, and amine compounds.

[0064] In one embodiment, the resin composition may further include one or more additives. The additives may be added appropriately during and / or after the synthesis of the urea-containing polyurethane acrylate resin. That is, the additives may be part of the resin composition.

[0065] Additives may include diluents, flame retardants, inhibitors, release agents, hardeners, viscosity modifiers, wetting and dispersing agents, or low-shrinkage agents, but this disclosure is not limited thereto.

[0066] [<5.] [Application of Resin Composition] [>] In one embodiment, when casting plates made of resin compositions are compared in terms of mechanical performance, the urea-containing polyurethane acrylate resin disclosed herein is at least equivalent to unmodified polyurethane acrylate resin (i.e., polyurethane acrylate resin without urea groups) in basic performance; and even superior in specific applications (e.g., applications in composite materials).

[0067] In one embodiment, the aforementioned resin composition comprising urea-based polyurethane acrylate resin can be blended with other materials to form a composite material. For example, the resin composition of the aforementioned embodiment (including the resin composition comprising urea-based polyurethane acrylate resin) can be blended with a fiber material to form a fiber-reinforced polymer (FRP). The aforementioned fiber material may include glass fiber, carbon fiber, polymer fiber (e.g., synthetic fiber), or other fibers. Fiber-reinforced polymers can possess high strength and lightweight characteristics, and are widely used in aerospace, automotive, construction, and other fields.

[0068] In one embodiment, the total amount of the resin composition is 100 parts by weight, and the total amount of the fiber material is 67 to 240 parts by weight.

[0069] In one embodiment, the fibers included in the composite material are carbon fibers, and the composite material can be a carbon fiber reinforced polymer (CFRP). The urea-containing polyurethane acrylate resin disclosed herein is formed by modifying the polyurethane acrylate resin structure to form urea groups. In the carbon fiber reinforced polymer, the modified urea groups can generate polar forces (such as hydrogen bonds) or bonds with the carbon fiber surface, resulting in a composite material with superior inter-layer shear strength (ILSS), which can be comparable to or even superior to commercially available epoxy resins. Therefore, the urea-containing polyurethane acrylate resin and / or its resin composition disclosed herein can have wider applications and better quality.

[0070] In one embodiment, the aforementioned resin composition of urea-containing polyurethane acrylate resin can be dissolved in a suitable solvent or liquid curing agent (e.g., methyl ethyl ketone peroxide) and then impregnated with fiber materials for use.

[0071] [<6.] [Examples and Comparisons] [>]

[0072] [<6.1 ] [Preparation of Resin Composition] [>]

[0073] [<] [Example] [1>] [Resin Composition] [1] 280.0 g of poly(methylene phenyl isocyanate) (brand: Wanhua; model: PM200; isocyanate group content: 2.083 equivalents), 0.106 g of 2,6-dibutyl-p-cresol (inhibitor), and 0.148 g of dibutyltin dilaurate (catalyst) were dispersed in 363 g of methyl methacrylate (dilutable monomer), and mixed evenly in a reaction vessel and heated to 45 °C ~ 60 °C for later use. Next, 125.0 g of polypropylene glycol (brand: Donglian Chemical; average molecular weight: 400; hydroxyl group content: 0.625 equivalents) was added dropwise to the above reaction vessel over a period of 40 min ~ 60 min, with the temperature controlled below 60 °C during the addition. After the addition was complete, the temperature was maintained for 2 to 4 hours. Next, 180.75 g of 2-hydroxyethyl methacrylate (HEMA, hydroxyl content 1.389 equivalents) was added dropwise over 40-60 minutes, with the temperature maintained below 60 °C during this period. After the addition was complete, the temperature was held for 1-2 hours. Finally, 7.99 g of polyether diamine (D230, average molecular weight: 230 g / mol; amino group content 0.069 equivalents) was added dropwise to the above reaction vessel over 10-30 minutes, with the temperature maintained below 60 °C during this period. After the addition was complete, the temperature was held for 1-2 hours. After confirming that the NCO value was below 0.5%, 90.75 g of methyl methacrylate was added for dilution. The resulting product was resin composition 1, with a viscosity of approximately 151 centi-poise (cps).

[0074] [<] [Example] [2>] [Resin Composition] [2] The difference between Example 2 and Example 1 is that 7.99 g of polyether diamine is replaced with 7.30 g of 4,4'-diaminodicyclohexylmethane (the content of the amino group is 0.069 equivalents). The finished product after the reaction is resin composition 2, with a viscosity of about 213 cps.

[0075] [<] [Example] [3>] [Resin Composition] [3] The difference between Example 3 and Example 1 is that 7.99 g of polyether diamine is replaced with 5.92 g of isophorone diamine (the content of amino groups is 0.069 equivalents). The finished product after the reaction is resin composition 3, with a viscosity of about 128 cps.

[0076] [<] [Example] [4>] [Resin Composition] [4] The difference between Example 4 and Example 1 is that 7.99 g of polyether diamine is replaced with 3.00 g of piperazine (with an amino group content of 0.069 equivalents). The resulting product after the reaction is resin composition 4, with a viscosity of approximately 133 cps.

[0077] [<] [Example] [5>] [Resin Composition] [5] The difference between Example 5 and Example 1 is that 7.99 g of polyether diamine is replaced with 15.97 g of polyether diamine (the content of amino groups is 0.139 equivalents). The finished product after the reaction is resin composition 5, with a viscosity of approximately 190 cps.

[0078] [<] [Example] [6>] [Resin Composition] [6] The difference between Example 6 and Example 1 is that 7.99 g of polyether diamine is replaced with 23.96 g of polyether diamine (the content of amino groups is 0.208 equivalents). The finished product after the reaction is resin composition 6, with a viscosity of approximately 239 cps.

[0079] [<] [Comparative Example] [1>] [Resin Composition] [7] The difference between Comparative Example 1 and Example 1 is that 125.0 g of polypropylene glycol was replaced with 138.9 g of polypropylene glycol (the content of hydroxyl groups was 0.694 equivalents) and no amine compounds were added. The finished product after the reaction was resin composition 7, with a viscosity of approximately 121 cps.

[0080] [<6.2] [Preparation of composite materials] [>]

[0081] [<] [Example] [7>] [Composite Materials] [1] By weight, 100 parts of the aforementioned resin composition 1 were mixed with 0.2 parts of 6% cobalt salt accelerator and 1 part of methyl ethyl ketone peroxide (MEKP). After thorough mixing, the mixture was impregnated with commercially available carbon fiber woven fabric (brand: SHENG PENG APPLIED MATERIALS CO., LTD.; model: carbon fiber woven-3K). The fabric was then molded using vacuum assisted resin transfer molding (VARTM), cured at room temperature for 24 hours, and then cured at 105 °C for 2 hours to achieve complete curing, thus obtaining the finished product of <Example 7>.

[0082] [<] [Example] [8>] [Composite Materials] [2] The difference between Example 8 and Example 7 is that resin composition 2 is used instead of resin composition 1.

[0083] [<] [Example] [9>] [Composite Materials] [3] The difference between Example 9 and Example 7 is that resin composition 3 is used instead of resin composition 1.

[0084] [<] [Example] [10>] [Composite Materials] [4] The difference between Example 10 and Example 7 is that resin composition 4 is used instead of resin composition 1.

[0085] [<] [Example] [11>] [Composite Materials] [5] The difference between Example 11 and Example 7 is that resin composition 5 is used instead of resin composition 1.

[0086] [<] [Example] [12>] [Composite Materials] [6] The difference between Example 12 and Example 7 is that resin composition 1 is replaced by resin composition 6.

[0087] [<] [Comparative Example] [2>] [Composite Materials] [7] The difference between Comparative Example 2 and Example 7 is that resin composition 7 is used instead of resin composition 1.

[0088] [<] [Comparative Example] [3>] [Composite Materials] [8] By weight, 31 parts of commercially available aliphatic polyetheramine curing agent (brand: Huntsman Corporation) were added to 100 parts of bisphenol A mixed with bisphenol F type epoxy resin (brand: Nan Ya Plastics). After thorough mixing, the mixture was impregnated with commercially available carbon fiber woven fabric. After molding using the above-mentioned process, the product was cured at 40 °C for 8 hours and then cured at 70 °C for 8 hours to achieve complete curing, thus obtaining the finished product of <Comparative Example 3>.

[0089] [<] [Comparative Example] [4>] [Composite Materials] [9] By weight, 100 parts of commercially available bisphenol A type vinyl resin (brand: SWANCOR) were mixed with 0.2 parts of 6% cobalt salt accelerator, 0.05 parts of N,N-dimethylaniline (DMA) accelerator, and 1 part of methyl ethyl ketone peroxide. The mixture was then impregnated with commercially available carbon fiber woven fabric. After molding using the above-mentioned process, the product was cured at room temperature for 24 hours and then cured at 105 °C for 2 hours to achieve complete curing, thus obtaining the finished product of <Comparative Example 4>.

[0090] [<6.3 ] [Evaluation Items] [>]

[0091] [<] [Mean interlaminar shear strength (unit:)] [MPa] [Measurement] [>] In accordance with ISO 14130, the composite materials from Examples 7 to 12 and Comparative Examples 2 to 4 were each cut into five samples with dimensions of 20 mm x 10 mm x 2 mm. The interlaminar shear strength of each sample was then measured using a universal material testing machine (Instron; model: 5892), and the average interlaminar shear strength was calculated. The test results are shown in Tables 1 to 3.

[0092] [<] [Mechanical Property Testing of Cast Plates] [>] Mechanical properties were tested on resin compositions 1 to 7 (the curing system was the same as the conditions for preparing the composite material: 0.2 parts 6% cobalt salt accelerator; 1 part methyl ethyl ketone peroxide; cured at room temperature for 24 hours, then cured at 105 °C for 2 hours). The tensile test standard was ASTM D638, the flexural test standard was ASTM D790, and the heat distortion temperature test standard was ASTM D648. The specific test results are shown in Table 4.

[0093] Table 1: Comparison of interlaminar shear strength between urea-containing polyurethane acrylate resin composites modified with different amine compounds and unmodified polyurethane acrylate resin composites. Example 7 Example 8 Example 9 Example 10 Comparative Example 2 Fiber content (wt%) 58 56 56 57 56 Interlaminar shear strength (MPa) 41.43 41.18 40.62 44.15 39.03

[0094] As shown in Table 1, the urea-containing polyurethane acrylate resin composite material has superior interlaminar shear strength compared with the unmodified polyurethane acrylate resin composite material.

[0095] Table 2: Comparison of interlaminar shear strength of urea-containing polyurethane acrylate resin composites and epoxy resin composites modified with different amine compounds Example 7 Example 8 Example 9 Example 10 Comparative Example 3 Fiber content (%) 58 56 56 57 58 Interlaminar shear strength (MPa) 41.43 41.18 40.62 44.15 45.25

[0096] As shown in Table 2, epoxy resin has a relatively high structural polarity and good interlaminar adhesion to carbon fiber. Therefore, epoxy resin composites are generally known to have better interlaminar shear strength. Urea-containing polyurethane acrylate resin composites can achieve interlaminar shear strength close to that of epoxy resin composites.

[0097] Table 3: Comparison of interlaminar shear strength of urea-containing polyurethane acrylate resin composites modified with different proportions of polyether diamine, epoxy resin composites, and vinyl ester resin composites. Example 7 Example 11 Example 12 Comparative Example 3 Comparative Example 4 Types of resins Polyurethane acrylate Epoxy vinyl Fiber content (%) 58 58 58 55 58 Interlaminar shear strength (MPa) 41.43 45.91 48.64 45.25 29.05

[0098] As shown in Table 3, increasing the reaction equivalent number of polyether diamine, that is, increasing the urea equivalent number of polyurethane acrylate resin, can effectively increase the adhesion between carbon fiber and resin, and can further have better interlaminar shear strength than epoxy resin composites.

[0099] Table 4: Mechanical Performance Testing Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Tensile strength (MPa) 88.03 77.45 72.23 75.73 83.35 78.66 81.67 Tensile modulus (MPa) 3662 3491 3520 3488 3543 3619 3404 Elongation at break (%) 5.31 3.83 3.29 3.33 4.60 3.30 4.25 Bending strength (MPa) 157.71 144.39 147.46 145.92 155.60 154.57 150.23 Flexural modulus (MPa) 3791 3481 3590 3543 3677 3630 3551 Heat distortion temperature (°C) 103.6 104.1 108.0 105.6 106.1 106.5 104.9

[0100] As shown in Table 4, the modified urea-containing polyurethane acrylate resin has comparable mechanical properties to the unmodified polyurethane acrylate resin.

[0101] [<7.] [Industrial applicability] [>]

[0102] The modified urea-containing polyurethane acrylate resin composite material disclosed in the foregoing embodiments can be directly or indirectly applied in fields such as aerospace, automotive, and construction. The modified urea-containing polyurethane acrylate resin can also be used to replace unmodified polyurethane acrylate resin, and can have better quality or applicability.

[0103] none.

Claims

1. A method for preparing a urea-containing polyurethane acrylate resin, comprising: Provide polyurethane acrylate polymers; Add amine compounds; The polyurethane acrylate polymer is modified by heating to form a urea-containing polyurethane acrylate resin; wherein the urea-containing polyurethane acrylate resin is as shown in [Formula 1] below, in [Formula 1]: R1 is hydrogen or methyl; R2 is a linked alkyl group with one to three carbons; R3 is an organic group containing an aromatic group; R4 is an alkyl, alkenyl or alkyl ether group; R5 is a linking group as shown in [Formula 2] below: [Formula 2]; in [Formula 2]: T2 is an organic group containing an aromatic group; T21, T22, and R6 are independent organic groups; R7 is an independent hydrogen or a cyclic organic compound co-constituted with R6; and m and n are integers of 1 or more.

2. The method for preparing the urea-containing polyurethane acrylate resin as described in claim 1, wherein the weight percentage of isocyanate groups in the urea-containing polyurethane acrylate resin is less than 0.5%.

3. The method for preparing the urea-containing polyurethane acrylate resin as described in claim 1 further comprises reacting a hydroxyl-containing (meth)acrylate compound with a polyurethane prepolymer to form the polyurethane acrylate polymer; and reacting an isocyanate compound with a polyol compound to form the polyurethane prepolymer; wherein, The isocyanate group in the isocyanate compound has an equivalent ratio of 15:1 to 1:1 to the hydroxyl group in the polyol compound.

4. The method for preparing the urea-containing polyurethane acrylate resin as described in claim 3, wherein the equivalent ratio of the hydroxyl groups in the polyol compound to the amine groups in the amine compound is 9:1 to 7:

3.

5. The method for preparing the urea-containing polyurethane acrylate resin as claimed in claim 1, wherein the amine compound includes di-n-butylamine, polyether diamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, or a mixture thereof.

6. A resin composition comprising a urea-containing polyurethane acrylate resin as shown in [Formula 1]: [Formula 1], wherein: R1 is hydrogen or methyl; R2 is a linked alkyl group with one to three carbon atoms; R3 is an organic group containing an aromatic group; R4 is an alkyl, alkenyl, or alkyl ether group; R5 is a linking group as shown in [Formula 2]: [Formula 2]; wherein: T2 is an organic group containing an aromatic group; T21, T22, and R6 are independent organic groups; R7 is an independent hydrogen or a cyclic organic compound co-constituted with R6; and m and n are integers of 1 or more.

7. The resin composition as described in claim 6, further comprising: The diluent monomer, wherein the total amount of the diluent monomer is 30 to 45 parts by weight, based on 100 parts by weight of the total amount of the urea-containing polyurethane acrylate resin.

8. The resin composition as described in claim 6, further comprising: The inhibitor, wherein the total amount of the inhibitor is from 0.01 to 0.03 parts by weight, based on 100 parts by weight of the total amount of the urea-containing polyurethane acrylate resin.

9. A composite material, comprising: The resin composition as described in claim 6; And fiber materials, wherein, based on 100 parts by weight of the total resin composition, the total amount of the fiber materials is 67 to 240 parts by weight.