Compound as well as preparation method and application thereof
By using compounds of isocyanate groups and functional groups, the problem of microcracks in materials during use has been solved, achieving long-term self-healing and improving the load-bearing capacity and durability of the materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2026-03-27
AI Technical Summary
Existing materials are prone to microcracks or other defects during long-term use, which reduces their load-bearing capacity and durability. Moreover, traditional self-healing materials are mostly external aids and cannot achieve long-term self-healing.
Compounds combining isocyanate groups and functional groups are used. The isocyanate groups react with the active groups in the substrate to be cured to increase the crosslinking density, and the functional groups realize molecular relinking, thereby achieving self-healing of the material.
The compound can achieve multiple self-repairs under the action of the material itself, effectively filling microcrack defects and improving the material's load-bearing capacity and durability.
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Figure CN121735972A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of self-repairing materials, in particular to a compound and a preparation method and application thereof. BACKGROUND
[0002] During long-term use, materials may have micro-cracks or other forms of defects due to the influence of external environment or material defects, which will reduce the carrying capacity, durability and overall performance of the material, and eventually lead to the failure of the material.
[0003] Self-repairing of materials can to some extent alleviate the influence of these defects. Most self-repairing is limited to a few repairs by external components, that is, only a certain repair can be carried out under the action of external components.
[0004] There are few long-term self-repairing solutions that match the material and are spontaneous, so the problem of continuous defects of the material cannot be well solved. SUMMARY
[0005] The embodiments of the present application provide a compound, a preparation method and application thereof, which belong to intrinsic self-repairing materials and are conducive to realizing the self-repairing function of the material.
[0006] In order to achieve the above-mentioned purpose, in a first aspect, the embodiments of the present application provide a compound, which comprises an isocyanate group and a functional group.
[0007] The functional group has a structure as shown in Formula I or Formula II:
[0008]
[0009] The embodiments of the present application provide a compound, which comprises an isocyanate group and a functional group. The isocyanate group can react with active groups in the curing substrate, which can improve the cross-linking density of the curing network. The functional group plays a role in molecular re-linking, which is conducive to realizing the self-repairing of the material and effectively filling the micro-crack defects of the damaged material.
[0010] Optionally, in some embodiments of the present application, the compound has a structure as shown in Formula III:
[0011]
[0012] wherein R1 or R4 is independently selected from C1-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C1-C75 substituted or unsubstituted cyclohexyl; or C1-C100 substituted or unsubstituted aromatic ring group;
[0013] R2is independently selected from C0-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C0-C75 substituted or unsubstituted cyclohexyl; or C0-C100 substituted or unsubstituted aromatic ring group;
[0014] R3is independently selected from -O-, -S-, -COO-, -NH- or -CONH-.
[0015] The embodiment of the present application provides a compound as shown in formula II, which has two isocyanate groups and two functional groups, more groups for chemical reaction, which is helpful to further improve the cross-linking density with the to-be-cured substrate, and meanwhile, the self-repair of the material can be better realized.
[0016] Optionally, in some embodiments of the present application, the compound has a structure as shown in formula IV:
[0017]
[0018] R1or R4is each independently selected from C1-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C1-C75 substituted or unsubstituted cyclohexyl; or C1-C100 substituted or unsubstituted aromatic ring group;
[0019] R2is independently selected from C0-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C0-C75 substituted or unsubstituted cyclohexyl; or C0-C100 substituted or unsubstituted aromatic ring group;
[0020] R3is independently selected from -O-, -S-, -COO-, -NH- or -CONH-.
[0021] The embodiment of the present application provides a compound as shown in formula III, which has more isocyanate groups, and more groups for curing and cross-linking with the to-be-cured substrate, and therefore, the cross-linking density with the to-be-cured substrate can be further improved.
[0022] Optionally, in some embodiments of the present application, the R1, R2 or R4 is independently selected from at least one of the following chemical structures:
[0023]
[0024] Optionally, in some embodiments of the present application, the raw materials of the compound at least include furan derivatives, bismaleimide derivatives and isocyanate derivatives.
[0025] Optionally, in some embodiments of the present application, the furan derivatives include any one of furan alcohol, furan acid, furfuryl mercaptan, furan amine and furan amide.
[0026] Optionally, in some embodiments of the present application, the bismaleimide derivative includes any one of an alkyl-containing bismaleimide, a cyclohexyl-containing bismaleimide, an aromatic ring-containing bismaleimide, and a heterocyclic ring-containing bismaleimide.
[0027] Optionally, in some embodiments of the present application, the isocyanate derivative includes any one of an alkyl-containing isocyanate, a cyclohexyl-containing isocyanate, and an aromatic ring-containing isocyanate.
[0028] Optionally, in some embodiments of the present application, the functional group is a self-repairing group.
[0029] In a second aspect, the embodiments of the present application provide a preparation method of a compound, including the following steps:
[0030] synthesizing an intermediate containing a functional group;
[0031] reacting the furan derivative and the bismaleimide derivative to obtain an intermediate containing a functional group;
[0032] synthesizing a compound;
[0033] reacting the intermediate containing a functional group and the isocyanate derivative to obtain the compound.
[0034] Optionally, in some embodiments of the present application, in the step of synthesizing the intermediate containing a functional group, the first solvent includes any one of an alcohol, an ether, a hydrocarbon, and a halogenated hydrocarbon.
[0035] under the protection of an inert gas, dissolving the furan derivative and the bismaleimide derivative in a first solvent to react, and obtaining an intermediate containing a functional group.
[0036] Optionally, in some embodiments of the present application, in the step of synthesizing the compound, the second solvent includes any one of an alcohol, an ether, a hydrocarbon, and a halogenated hydrocarbon.
[0037] dissolving the isocyanate derivative in a second solvent to obtain a first solution;
[0038] adding the intermediate containing a functional group to the first solution to react, and after the reaction is completed, removing the solvent to obtain the compound.
[0039] In a third aspect, the embodiments of the present application provide an application of the compound as described above in a self-repairing curing material.
[0040] The embodiments of the present application provide a compound, which can realize long-acting self-repairing based on its own components.
[0041] In some embodiments of the present application, the present application also has the following advantages:
[0042] The compound includes isocyanate groups and functional groups. The isocyanate groups can react with the active groups in the substrate to be cured, thereby increasing the crosslinking density of the cured network. At the same time, the functional groups play a role in molecular relinking, which is conducive to the self-repair of the material and effectively fills the microcrack defects of the damaged material. Attached Figure Description
[0043] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0044] Figure 1 This is a chemical reaction structural diagram of step S1 in some embodiments of this application;
[0045] Figure 2 This is a chemical reaction structural diagram of step S2 in some embodiments of this application;
[0046] Figure 3 This is a molecular structure diagram of the compound in Example 1 of this application;
[0047] Figure 4 This is a molecular structure diagram of the compound in Example 2 of this application;
[0048] Figure 5 This is a molecular structure diagram of the compound in Example 3 of this application;
[0049] Figure 6 This is a molecular structure diagram of the compound in Example 4 of this application;
[0050] Figure 7 This is a molecular structure diagram of the compound in Example 5 of this application;
[0051] Figure 8 This is a molecular structure diagram of the compound in Example 6 of this application;
[0052] Figure 9 This describes the surface scratches on the self-healing sample 1 before repair.
[0053] Figure 10 This is the surface repair condition of the self-healing sample 1 after repair in this application. Detailed Implementation
[0054] With reference to the drawings of the embodiments of the present application, the technical solutions in the embodiments of the present application will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the protection scope of the present application.
[0055] Currently, the self-repairing types mainly include the following two types: 1) extrinsic self-repairing, also called external aid self-repairing, which realizes self-repairing function by adding external components in the material, such as adding microcapsules containing self-repairing functional components, liquid core fiber type or porous microparticles; 2) intrinsic self-repairing, also called internal self-repairing, which usually does not need external intervention, but relies on the chemical structure and properties of the material itself to realize self-repairing. Common intrinsic self-repairing materials include, but are not limited to, thermoreversible D-A bond, dynamic ester bond, disulfide bond, multiple hydrogen bond, etc.
[0056] The difference between extrinsic self-repairing and intrinsic self-repairing lies in that: the extrinsic self-repairing is usually one-time self-repairing; while the intrinsic self-repairing can realize multiple self-repairing of the material, but the development of intrinsic materials is more difficult, and currently there are fewer choices of intrinsic materials.
[0057] Therefore, the present application provides a compound, a preparation method and application thereof, which belongs to a new intrinsic self-repairing material, can realize self-repairing of the material, and has a wide application prospect.
[0058] In a first aspect, the present application provides a compound, which comprises an isocyanate group and a functional group.
[0059] In some embodiments of the present application, the isocyanate group can be an -N=C=O group.
[0060] In some embodiments of the present application, the functional group can be a self-repairing group.
[0061] In some embodiments of the present application, the functional group has a structure as shown in Formula I or Formula II:
[0062]
[0063] It should be noted that the isocyanate group can react with active groups in the curing substrate, which can improve the crosslinking density of the curing network; the functional structure is obtained by reacting furan derivatives and bismaleimide derivatives, which plays a role of molecular re-linking, is conducive to realizing self-repairing of the material, and effectively fills the microcrack defects of the damaged material.
[0064] In some embodiments of the present application, the active group can be -OH, -SH, -COOH or -NH2.
[0065] In some embodiments of the present application, the number of isocyanate groups and functional groups can be one or more. The more isocyanate groups, the easier the compound is to form a curing network with the substrate to be cured, and the higher the crosslinking density with the substrate to be cured. The more functional groups, the easier the compound is to re-link with molecules, and the more conducive to achieving self-repair of the material.
[0066] In some embodiments of the present application, the compound has a structure as shown in Formula III:
[0067]
[0068] wherein R1or R4is each independently selected from C1-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C1-C75 substituted or unsubstituted cyclohexyl; or C1-C100 substituted or unsubstituted aromatic ring group;
[0069] R2is independently selected from C0-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C0-C75 substituted or unsubstituted cyclohexyl; or C0-C100 substituted or unsubstituted aromatic ring group;
[0070] R3is independently selected from -O-, -S-, -COO-, -NH- or -CONH-.
[0071] In some embodiments of the present application, the compound has a structure as shown in Formula IV:
[0072]
[0073] wherein R1or R4is each independently selected from C1-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C1-C75 substituted or unsubstituted cyclohexyl; or C1-C100 substituted or unsubstituted aromatic ring group;
[0074] R2is independently selected from C0-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl; or C0-C75 substituted or unsubstituted cyclohexyl; or C0-C100 substituted or unsubstituted aromatic ring group;
[0075] R3is independently selected from -O-, -S-, -COO-, -NH- or -CONH-.
[0076] In some embodiments of the present application, when R1or R4is each independently selected from C1-C50 substituted or unsubstituted straight chain or branched alkyl or alkenyl, the substituent groups include B, O, N, Si and halogen atoms.
[0077] In some embodiments of the present application, when R1or R4is each independently selected from a C1-C75 substituted or unsubstituted cyclohexyl group, the substituents include B, O, N, Si, and halogen atoms or substituted or unsubstituted straight-chained or branched alkyl or alkenyl groups, wherein the substituents of the alkyl or alkenyl groups include B, O, N, Si, and halogen atoms.
[0078] In some embodiments of the present application, when R1or R4is each independently selected from a C1-C100 substituted or unsubstituted aromatic cyclic group, the substituents include B, O, N, Si, and halogen atoms, substituted or unsubstituted straight-chained or branched alkyl or alkenyl groups, or substituted or unsubstituted cyclohexyl groups, wherein the substituents of the alkyl or alkenyl groups include B, O, N, Si, and halogen atoms, the substituents of the cyclohexyl groups include B, O, N, Si, and halogen atoms, and the substituents of the straight-chained or branched alkyl or alkenyl groups.
[0079] In some embodiments of the present application, R2may be independently selected from a C0-C50 substituted or unsubstituted straight-chained or branched alkyl or alkenyl group, wherein the substituents include B, O, N, Si, and halogen atoms.
[0080] In some embodiments of the present application, R2may be independently selected from a C0-C75 substituted or unsubstituted cyclohexyl group, wherein the substituents include B, O, N, Si, and halogen atoms or substituted or unsubstituted straight-chained or branched alkyl or alkenyl groups, wherein the substituents of the alkyl or alkenyl groups include B, O, N, Si, and halogen atoms.
[0081] In some embodiments of the present application, R2may be independently selected from a C0-C100 substituted or unsubstituted aromatic cyclic group, wherein the substituents include B, O, N, Si, and halogen atoms, substituted or unsubstituted straight-chained or branched alkyl or alkenyl groups, or substituted or unsubstituted cyclohexyl groups, wherein the substituents of the alkyl or alkenyl groups include B, O, N, Si, and halogen atoms, the substituents of the cyclohexyl groups include B, O, N, Si, and halogen atoms, and the substituents of the straight-chained or branched alkyl or alkenyl groups.
[0082] In some embodiments of the present application, the halogen atom can be selected from all halogen atoms such as F, Cl, Br, I, and the like.
[0083] In some embodiments of the present application, R1, R2, or R4may be independently selected from at least one of the following chemical structures:
[0084]
[0085] In some embodiments of the present application, the substrate to be cured includes, but is not limited to, any one of an epoxy resin, an unsaturated polyester, a polyurethane, and the like.
[0086] In some embodiments of the present application, the isocyanate group can react with -OH, -SH, -COOH or -NH2 groups in the substrate to be cured, facilitating cross-linking and curing with the substrate to be cured.
[0087] In some embodiments of the present application, when the substrate to be cured is an epoxy resin and R3 is selected as a -NH- group, the active hydrogen in the -NH- group can react with the epoxy group, playing a role of molecular linking and auxiliary curing.
[0088] In some embodiments of the present application, the specific structures of R1, R2 and R4 of the present application can be arbitrarily selected according to the performance requirements of the product. For example, when an alkyl group is selected, the flexibility of the substrate to be cured can be improved; when an alkyl group containing a silicon-oxygen bond is selected, the high and low temperature resistance of the substrate to be cured can be improved; when a halogen-containing substituent group is selected, the flame retardance of the substrate to be cured can be improved; when a cyclohexyl group is selected, the weather resistance of the substrate to be cured can be improved; when an aromatic ring is selected, the heat resistance and mechanical properties of the substrate to be cured can be improved. Based on the above selection, a series of auxiliary curing agents with different performances can be developed, which have self-repairing function.
[0089] In some embodiments of the present application, the raw materials of the compound at least include furan derivatives, bismaleimide derivatives and isocyanate derivatives.
[0090] In some embodiments of the present application, the furan derivatives include any one of furan alcohols, furan acids, furfuryl mercaptans, furan amines and furan amides.
[0091] In some embodiments of the present application, the furan alcohols include, but are not limited to, at least one of furfuryl alcohol, 3-furfuryl alcohol, 2-(furan-2-yl)ethanol, 1-(furan-2-yl)-2-propanol, 3-furanethanol, 2-furanpropanol and 1-(2-furyl)-1-butanol.
[0092] In some embodiments of the present application, the furan acids include, but are not limited to, at least one of furanecarboxylic acid, 3-furanecarboxylic acid, 2-furanacetic acid, furan-3-acetic acid, 3-furanpropanoic acid, 3-(furan-2-yl)-2-methylpropanoic acid, 3-(furan-2-yl)-2,2-dimethylpropanoic acid, 3-(2-furyl)-3-phenylpropanoic acid, 3-napthyl-2-((tetrahydrofuryl-2)-methyl)propanoic acid, 4-furan-2-yl-4-oxobutanoic acid, 3-furan-2-yl-4-phenyl-butyric acid and 4-(3-furan-2-yl-[1,2,4]oxadiazol-5-yl)-butyric acid.
[0093] In some embodiments of the application, the furanamines include, but are not limited to, at least one of furfurylamine, furan-3-amine, 2-furanethanamine, 1-furan-3-ethanamine, 2-(3-furyl)ethanamine, 1-(2-furyl)-2-propanamine, 3-(2-furyl)-1-methylpropanamine.
[0094] In some embodiments of the application, the furanamides include, but are not limited to, at least one of 3-furanethioamide, furan-2-thioamide, N-(2-furylmethyl)benzamide, N-phenyl-2-furanecarboxamide.
[0095] In some embodiments of the application, the bismaleimide derivatives include any one of alkyl-containing bismaleimides, cyclohexyl-containing bismaleimides, aromatic ring-containing bismaleimides, and heterocyclic ring-containing bismaleimides.
[0096] In some embodiments of the application, the bismaleimide derivatives include, but are not limited to, at least one of bismaleimide, oxydiphthalyl bismaleimide, bismaleimido methyl ether, bismaleimide-hexaethylene glycol, 1,4-bismaleimidobutane, dithio-bismaleimidethane, N,N'-m-phenylene bismaleimide, N,N'-(o-phenylene) bismaleimide, N,N-(1,4-phenylene) bismaleimide, N,N-(4-methyl-1,3-phenylene) bismaleimide, 1,11-bismaleimid-3,6,9-trioxoundecane, 1,5-bis(maleimid fumaric imide)-2-methyl-pentane, 1,2-bis(maleimido)ethane, 1,5-bis(maleimid fumaric imide)pentane, 1,9-bis(maleimid fumaric imide)nonane, 1,8-bis(maleimido)-3,6-dioxaoctane, 1,23-bis(maleimido)heptanediol, 1,8-bis(maleimid fumaric imide)octane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N-(4-maleimidobutyryl)succinimide, 3-maleimidopropionic acid N-hydroxysuccinimide ester, 6-(maleimidophenoxy)hexanoic acid succinimide ester.
[0097] In some embodiments of the application, the isocyanate derivatives include any one of alkyl-containing isocyanates, cyclohexyl-containing isocyanates, and aromatic ring-containing isocyanates.
[0098] In some embodiments of the present application, the isocyanate derivative includes, but is not limited to, at least one of naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, o-tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, trimethylhexane diisocyanate, toluene diisocyanate, m-xylylene diisocyanate, diphenylmethane diisocyanate, o-xylylene diisocyanate, polyhexamethylene diisocyanate, toluene 2,6-diisocyanate, 2,4-toluene diisocyanate, poly(isophorone diisocyanate), 1,4-cyclohexyl diisocyanate, toluene-2,5-diisocyanate, cyclohexane-1,4-diisocyanate, 4,4-diisocyanate dicyclohexyl methane, dodecylbenzene-2,4-diisocyanate, 1,4-cyclohexane dimethyl diisocyanate, 4-chloromethyl-1,3-phenylene diisocyanate, 4-chloro-6-methyl-m-phenylene diisocyanate, 2,2'-methylene diphenyl diisocyanate, 3,3-dichlorobiphenyl 4,4-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, alpha, alpha, alpha', alpha'-tetramethyl-1,3-benzene dimethyl diisocyanate, trimethylhexamethylene diisocyanate, toluene-2,6-diisothiocyanate, 1,6-hexane diisocyanate, 1,3-propane diisothiocyanate, isocyclohexyl imide, 4,4-methylene bis(2,6-diethylphenyl isocyanate), 4,4'-diisocyanato-3,3'-dimethyl diphenyl methane, 1,6-diisocyanato-2,4,4-trimethyl cyclohexane, 1,5-diisocyanato-2-methyl pentane.
[0099] In a second aspect, the embodiments of the present application provide a preparation method of a compound, including the following steps:
[0100] S1, synthesizing an intermediate containing a functional group:
[0101] reacting the furan derivative and the bismaleimide derivative to obtain the intermediate containing the functional group, and the chemical reaction structural formula is shown in Figure 1 .
[0102] S2, synthesizing the compound:
[0103] reacting the intermediate containing the functional group and the isocyanate derivative to obtain the compound, and the chemical reaction structural formula is shown in Figure 2 .
[0104] In some embodiments of the present application, the step S1 can be that the furan derivative and the bismaleimide derivative are dissolved in a first solvent to react under protection of an inert gas, and the intermediate containing the functional group is obtained after the reaction is completed.
[0105] In some embodiments of the present application, the inert gas in step S1 can be selected from any one of N2, helium, neon, argon, krypton, xenon, and radon.
[0106] In some embodiments of the present application, the furan derivative and the bismaleimide derivative are selected from the same range as the furan derivative and the bismaleimide derivative in the aforementioned compound, which will not be repeated here.
[0107] In some embodiments of the present application, the molar ratio of the bismaleimide derivative to the furan derivative is 0.5 to 2.
[0108] In some embodiments of the present application, the molar ratio of the bismaleimide derivative to the furan derivative is 0.6 to 2.
[0109] In some embodiments of the present application, the molar ratio of the bismaleimide derivative to the furan derivative is 0.75 to 2.
[0110] In some embodiments of the present application, the molar ratio of the bismaleimide derivative to the furan derivative is 1 to 2.
[0111] In some embodiments of the present application, the first solvent includes, but is not limited to, N,N-dimethylformamide, N-butylpyrrolidone, or butanone. The present application is open to the selection of the first solvent as long as any organic solvent that can dissolve the selected furan derivative and bismaleimide derivative, does not affect the reaction, and does not produce side reactions.
[0112] In some embodiments of the present application, the reaction temperature of step S1 is room temperature to 150°C. It should be noted that the present application does not particularly limit the reaction temperature of step S1, because R1, R2, and R3 involve a variety of reaction groups, and the reaction temperature of different reaction groups is different. Therefore, the present application is open to the reaction temperature as long as a suitable temperature can ensure that the furan derivative and the bismaleimide derivative react to form an intermediate containing a functional group.
[0113] In some embodiments of the present application, step S2 can be dissolving the isocyanate derivative in a second solvent to obtain a first solution; adding the intermediate containing a functional group to the first solution to react, removing the solvent after the reaction is complete, and obtaining the compound.
[0114] In some embodiments of the present application, the selection range of the isocyanate derivative is the same as the selection range of the isocyanate derivative in the aforementioned compound raw material, which will not be repeated here.
[0115] It should be noted that the selection of the second solvent can be the same as or different from the selection of the first solvent. When the selection of the first solvent is different from that of the second solvent, the residual first solvent in the intermediate containing the functional group needs to be removed before the reaction in step S2. The technical means for removing the solvent is a conventional technical means in the art, and will not be described here.
[0116] In some embodiments of the present application, the molar ratio of the intermediate containing the functional group to the isocyanate derivative ranges from 1 to 1.1.
[0117] In some embodiments of the present application, the molar ratio of the intermediate containing the functional group to the isocyanate derivative ranges from 1 to 1.05.
[0118] In some embodiments of the present application, the molar ratio of the intermediate containing the functional group to the isocyanate derivative ranges from 1 to 1.01.
[0119] In some embodiments of the present application, the reaction temperature in step S2 is -20°C to 100°C. It should be noted that the present application does not particularly limit the reaction temperature of step S2. Because the reaction groups involved in R1, R2, R3 and R4 are of various types, the reaction temperatures of different reaction groups are different. Therefore, the present application is open to the reaction temperature as long as it can ensure that the intermediate containing the functional group reacts with the isocyanate derivative to generate the compound of the present application.
[0120] In a third aspect, the embodiments of the present application provide a use of the compound as described above in a self-repairing curing material.
[0121] The compound as described above can be used in a self-repairing curing material to actively cure or assist curing, and has good self-repairing function.
[0122] The present application will be described in detail below through specific embodiments. The following embodiments are only part of the embodiments of the present application and are not a limitation of the present application. The raw materials used in the following embodiments are commercially available products unless otherwise specified.
[0123] Example 1
[0124] A self-repairing curing material includes the following steps:
[0125] S100, dry each raw material separately;
[0126] S200, under inert gas protection, furoyl alcohol and 4, 4'-bismaleimide benzene are dissolved in N, N-dimethylformamide, the dilution volume ratio is 20:1, the reaction is carried out under stirring at 60 DEG C, the reaction solution is monitored by Fourier transform infrared spectroscopy, when the infrared characteristic peaks of maleimide group and furan ring in furoyl alcohol basically disappear, the intermediate containing functional groups is obtained;
[0127] S300, isophorone diisocyanate is mixed with N, N-dimethylformamide, the dilution volume ratio is 20:1, the intermediate containing functional groups is gradually added dropwise into the mixed solution, the reaction is carried out under stirring at 50 DEG C, the content of residual isocyanate group in the reaction solution is determined by acetone-di-n-butylamine method, when the residual content is close to 50% of the input amount of isophorone diisocyanate, the reaction is completed, the solvent is removed, and the compound, i.e. the self-repairing curing material, is obtained;
[0128] In this embodiment, the molar ratio of furoyl alcohol, 4, 4'-bismaleimide benzene and isophorone diisocyanate is 2:1:2.01; the structural formula of the compound of this embodiment is referred to Figure 3 .
[0129] Example 2
[0130] A self-repairing curing material, comprising the following steps:
[0131] S100, each raw material is subjected to drying treatment;
[0132] S200, under inert gas protection, furoyl alcohol and 4, 4'-bismaleimide benzene are dissolved in N, N-dimethylformamide, the dilution volume ratio is 20:1, the reaction is carried out under stirring at 60 DEG C, the reaction solution is monitored by Fourier transform infrared spectroscopy, when the infrared characteristic peaks of maleimide group and furan ring in furoyl alcohol basically disappear, the intermediate containing functional groups is obtained;
[0133] S300, isophorone diisocyanate is mixed with N, N-dimethylformamide, the dilution volume ratio is 20:1, the intermediate containing functional groups is gradually added dropwise into the mixed solution, the reaction is carried out under stirring at 50 DEG C, the content of residual isocyanate group in the reaction solution is determined by acetone-di-n-butylamine method, when the residual content is close to 50% of the input amount of isophorone diisocyanate, the reaction is completed, the solvent is removed, and the compound, i.e. the self-repairing curing material, is obtained;
[0134] In this embodiment, the molar ratio of furoyl alcohol, 4, 4'-bismaleimide benzene and isophorone diisocyanate is 2:1:2.01; the structural formula of the compound of this embodiment is referred to Figure 4 .
[0135] Example 3
[0136] A self-repairing curing material, comprising the following steps:
[0137] S100, dry each raw material respectively;
[0138] S200, under the protection of inert gas, furoic acid and 4, 4'-bismaleimide diphenyl methane are dissolved in N, N-dimethylformamide, the dilution volume ratio is 20:1, the reaction is carried out under stirring at 70 DEG C, the reaction solution is monitored by Fourier transform infrared spectroscopy, when the infrared characteristic peaks of maleimide group and furan ring in furoin basically disappear, an intermediate containing functional groups is obtained;
[0139] S300, isophorone diisocyanate is mixed with N, N-dimethylformamide, the dilution volume ratio is 20:1, the intermediate containing functional groups is gradually added to the mixed solution, the reaction is carried out under stirring at 50 DEG C, the content of residual isocyanate group in the reaction solution is determined by acetone-di-n-butylamine method, when the residual content is close to 50% of the input amount of isophorone diisocyanate, the reaction is completed, the solvent is removed, and the compound, i.e. the self-repairing curing material, is obtained;
[0140] In this embodiment, the molar ratio of furoic acid, 4, 4'-bismaleimide diphenyl methane and isophorone diisocyanate is 2:1:2.01, and the structural formula of the compound of this embodiment is referred to Figure 5 .
[0141] Example 4
[0142] A self-repairing curing material, comprising the following steps:
[0143] S100, dry each raw material respectively;
[0144] S200, under the protection of inert gas, furoic acid and 4, 4'-bismaleimide diphenyl methane are dissolved in N, N-dimethylformamide, the dilution volume ratio is 20:1, the reaction is carried out under stirring at 70 DEG C, the reaction solution is monitored by Fourier transform infrared spectroscopy, when the infrared characteristic peaks of maleimide group and furan ring in furoin basically disappear, an intermediate containing functional groups is obtained;
[0145] S300, isophorone diisocyanate is mixed with N, N-dimethylformamide, the dilution volume ratio is 20:1, the intermediate containing functional groups is gradually added to the mixed solution, the reaction is carried out under stirring at 50 DEG C, the content of residual isocyanate group in the reaction solution is determined by acetone-di-n-butylamine method, when the residual content is close to 50% of the input amount of isophorone diisocyanate, the reaction is completed, the solvent is removed, and the compound, i.e. the self-repairing curing material, is obtained;
[0146] In this embodiment, the molar ratio of furfuryl alcohol, N,N'-1,3-phenylene bismaleimide and isophorone diisocyanate is 2:1:2.01, and the structural formula of the compound of this embodiment is as shown in Figure 6 .
[0147] Example 5
[0148] A self-repairing curing material, comprising the following steps:
[0149] S100, each raw material is subjected to drying treatment respectively;
[0150] S200, under the protection of inert gas, furfuryl alcohol and N,N'-1,3-phenylene bismaleimide are dissolved in N,N-dimethylformamide, the dilution volume ratio is 20:1, the reaction is carried out under stirring at 60°C, the reaction solution is monitored by Fourier transform infrared spectroscopy, and when the infrared characteristic peaks of the maleimide group and the furan ring in furfuryl alcohol basically disappear, an intermediate containing a functional group is obtained;
[0151] S300, isophorone diisocyanate is mixed with N,N-dimethylformamide, the dilution volume ratio is 20:1, the intermediate containing a functional group is gradually added to the mixed solution, the reaction is carried out under stirring at 50°C, the content of the residual isocyanate group in the reaction solution is determined by the acetone-di-n-butylamine method, and when the residual content is close to 50% of the input amount of isophorone diisocyanate, the reaction is completed, the solvent is removed, and a compound, i.e., a self-repairing curing material, is obtained;
[0152] In this embodiment, the molar ratio of furfuryl alcohol, N,N'-1,3-phenylene bismaleimide and isophorone diisocyanate is 2:1:2.01, and the structural formula of the compound of this embodiment is as shown in Figure 7 .
[0153] Example 6
[0154] A self-repairing curing material, comprising the following steps:
[0155] S100, each raw material is subjected to drying treatment respectively;
[0156] S200, under the protection of inert gas, 2,5-furandimethanol and 4,4'-bismaleimide benzene are dissolved in N,N-dimethylformamide, the dilution volume ratio is 20:1, the reaction is carried out under stirring at 60°C, the reaction solution is monitored by Fourier transform infrared spectroscopy, and when the infrared characteristic peaks of the maleimide group and the furan ring in furfuryl alcohol basically disappear, an intermediate containing a functional group is obtained;
[0157] S300, isoflurone diisocyanate is mixed with N, N-dimethylformamide, the dilution volume ratio is 20:1, the intermediate containing functional groups is gradually added into the mixed solution, the reaction is carried out under stirring at 50℃, the content of residual isocyanate groups in the reaction solution is determined by using the acetone-di-n-butylamine method, the reaction is completed when the residual content is close to 50% of the input amount of isoflurone diisocyanate, the solvent is removed, and the compound, i.e. the self-repairing curing material, is obtained;
[0158] In this embodiment, the molar ratio of 2,5-furan dimethyl alcohol, 4,4'-bismaleimide diphenyl methane and isoflurone diisocyanate is 2:1:4.01; the structural formula of the compound of this embodiment is referred to Figure 8 .
[0159] Preparation of the self-repairing sample:
[0160] Self-repairing sample 1:
[0161] 100 parts of epoxy resin E51 and 10.6 parts of diethylene triamine are stirred and uniformly dispersed, and then kept at 40℃ for 0.5h; 5 parts of the self-repairing curing material prepared in Example 1 is added into each of them, stirred and uniformly dispersed, vacuumed to remove bubbles, cured at 60℃ for 1h, and then cured at 90℃ for 2h to obtain the self-repairing sample 1.
[0162] Self-repairing sample 2:
[0163] 100 parts of epoxy resin E51 and 10.6 parts of diethylene triamine are stirred and uniformly dispersed, and then kept at 40℃ for 0.5h; 5 parts of the self-repairing curing material prepared in Example 2 is added into each of them, stirred and uniformly dispersed, vacuumed to remove bubbles, cured at 60℃ for 1h, and then cured at 90℃ for 2h to obtain the self-repairing sample 2.
[0164] Self-repairing sample 3:
[0165] 100 parts of epoxy resin E51 and 10.6 parts of diethylene triamine are stirred and uniformly dispersed, and then kept at 40℃ for 0.5h; 5 parts of the self-repairing curing material prepared in Example 3 is added into each of them, stirred and uniformly dispersed, vacuumed to remove bubbles, cured at 60℃ for 1h, and then cured at 90℃ for 2h to obtain the self-repairing sample 3.
[0166] Self-repairing sample 4:
[0167] 100 parts of epoxy resin E51 and 10.6 parts of diethylene triamine are stirred and uniformly dispersed, and then kept at 40℃ for 0.5h; 5 parts of the self-repairing curing material prepared in Example 4 is added into each of them, stirred and uniformly dispersed, vacuumed to remove bubbles, cured at 60℃ for 1h, and then cured at 90℃ for 2h to obtain the self-repairing sample 4.
[0168] Self-repairing sample 5:
[0169] 100 parts of epoxy resin E51, 10.6 parts of diethylene triamine were stirred and uniformly dispersed, and then kept at 40℃ for 0.5h. Then 5 parts of the self-repairing curing material prepared in Example 5 was added respectively, and stirred and uniformly dispersed. Vacuum was applied to remove bubbles. First, curing was carried out at 60℃ for 1h, and then curing was carried out at 90℃ for 2h to obtain self-repairing sample 5.
[0170] Self-repairing sample 6:
[0171] 100 parts of epoxy resin E51, 10.6 parts of diethylene triamine were stirred and uniformly dispersed, and then kept at 40℃ for 0.5h. Then 5 parts of the self-repairing curing material prepared in Example 6 was added respectively, and stirred and uniformly dispersed. Vacuum was applied to remove bubbles. First, curing was carried out at 60℃ for 1h, and then curing was carried out at 90℃ for 2h to obtain self-repairing sample 1.
[0172] Comparative sample 1, 100 parts of epoxy resin E51, 10.6 parts of diethylene triamine were stirred and uniformly dispersed, and then kept at 40℃ for 0.5h. Vacuum was applied to remove bubbles. First, curing was carried out at 60℃ for 1h, and then curing was carried out at 90℃ for 2h to obtain comparative sample 1.
[0173] Self-repairing function test:
[0174] The self-repairing samples 1-6 and the comparative sample 1 were scratched with a blade, and then placed in an oven at 100℃ for 1h and 2h, and the repair degree of each sample was observed.
[0175] The test results are shown in Table 1:
[0176] Table 1
[0177]
[0178] According to the detection results of the self-repairing samples 1-6, the comparative sample 1 and Table 1, it can be seen that the self-repairing samples added with the compounds prepared in Examples 1-6 can realize self-repairing performance. This is because the compound includes isocyanate groups and functional groups. The isocyanate groups can react with active groups in the curing substrate, which can improve the crosslinking density of the curing network. The functional groups play a role in molecular re-linking, which is conducive to realizing the self-repairing of the material, thereby filling the micro-crack defects of the damaged material.
[0179] According to the detection results of the self-repairing samples 1-3 and Table 1, it can be seen that the furan derivative in the self-repairing sample 2 is selected as furfurylamine. The active hydrogen in the -NH- group contained in furfurylamine can react with the epoxy substrate, playing a role in molecular linking and auxiliary curing. The furan derivative in the self-repairing sample 3 is selected as furfuryl acid. The molecule has a large polarity, which can prolong the repair time of the self-repairing sample 3 on the basis of having self-repairing function.
[0180] In addition, it is again emphasized that the specific structures of R1, R2, R3, and R4 in the present application can be arbitrarily selected according to the performance requirements of the product. For example, when an alkyl group is selected, the flexibility of the substrate to be cured can be improved; when an alkyl group containing a silicon-oxygen bond is selected, the high and low temperature resistance of the substrate to be cured can be improved; when a halogen-containing substituent group is selected, the flame retardance of the substrate to be cured can be improved; when a cyclohexyl group is selected, the weather resistance of the substrate to be cured can be improved; and when an aromatic ring is selected, the heat resistance and mechanical properties of the substrate to be cured can be improved. Based on the above selection, a series of auxiliary curing agents with different properties can be developed modularly, and the self-repairing function is also possessed.
[0181] Figure 9 and Figure 10 is a comparison chart before and after repairing the self-repairing sample 1. Before repairing, there are obvious scratches, and after repairing, the scratches disappear, and the surface is smooth and clean. It can be seen that the self-repairing curing material of the present application can effectively repair the micro-crack defects on the surface of the epoxy substrate.
[0182] The above provides a detailed introduction to the compound, the preparation method and the application of the embodiment of the present application. In this paper, specific examples are applied to explain the principles and implementation modes of the present application. The above embodiment is only used to help understand the method and the core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, the specific implementation mode and the application range will be changed; in summary, the content of the specification should not be understood as a limitation of the present application.
Claims
1. A compound, characterized in that, The compound includes isocyanate groups and functional groups; The functional group has a structure as shown in Formula I or Formula II:
2. The compound according to claim 1, characterized in that, The compound has the structure shown in Formula III: R1 or R4 is independently selected from C1 to C50 substituted or unsubstituted straight-chain or branched alkyl or alkenyl groups, C1 to C75 substituted or unsubstituted cyclohexyl groups, or C1 to C100 substituted or unsubstituted aromatic cycloyl groups. R2 is independently selected from C0 to C50 substituted or unsubstituted straight-chain or branched alkyl or alkenyl groups, C0 to C75 substituted or unsubstituted cyclohexyl groups, or C0 to C100 substituted or unsubstituted aromatic cycloyl groups. R3 is independently selected from -O-, -S-, -COO-, -NH-, or -CONH-.
3. The compound according to claim 1, characterized in that, The compound has the structure shown in Formula IV: R1 or R4 is independently selected from C1 to C50 substituted or unsubstituted straight-chain or branched alkyl or alkenyl groups, C1 to C75 substituted or unsubstituted cyclohexyl groups, or C1 to C100 substituted or unsubstituted aromatic cycloyl groups. R2 is independently selected from C0 to C50 substituted or unsubstituted straight-chain or branched alkyl or alkenyl groups, C0 to C75 substituted or unsubstituted cyclohexyl groups, or C0 to C100 substituted or unsubstituted aromatic cycloyl groups. R3 is independently selected from -O-, -S-, -COO-, -NH-, or -CONH-.
4. The compound according to claim 2 or 3, characterized in that, R1, R2, or R4 is independently selected from at least one of the following chemical structures:
5. The compound according to claim 2 or 3, characterized in that, The raw materials for the compound include at least furan derivatives, bismaleimide derivatives, and isocyanate derivatives.
6. The compound according to claim 5, characterized in that, The furan derivatives include any one of furan alcohols, furan acids, furfuryl mercaptans, furanamines, and furanamides.
7. The compound according to claim 5, characterized in that, The bismaleimide derivatives include any one of alkyl bismaleimides, cyclohexyl bismaleimides, aryl bismaleimides, and heterocyclic bismaleimides.
8. The compound according to claim 5, characterized in that, The isocyanate derivatives include any one of alkyl isocyanates, cyclohexyl isocyanates, and aromatic cycloisocyanates.
9. The compound according to claim 1, characterized in that, The functional group is a self-healing group.
10. A method for preparing the compound according to any one of claims 1-3, characterized in that, Includes the following steps: Synthetic intermediates containing functional groups: Reaction of furan derivatives with bismaleimide derivatives yields intermediates containing functional groups; Synthetic compounds: The intermediate containing a functional group is reacted with an isocyanate derivative to obtain the compound.
11. The method for preparing the compound according to claim 10, characterized in that, In the synthetic intermediate containing functional groups: Under inert gas protection, furan derivatives and bismaleimide derivatives are dissolved in a first solvent and reacted to obtain an intermediate containing a functional group.
12. The method for preparing the compound according to claim 10, characterized in that, In the synthesized compound: The isocyanate derivative is dissolved in a second solvent to obtain a first solution; An intermediate containing a functional group is added to the first solution to carry out the reaction. After the reaction is complete, the solvent is removed to obtain the compound.
13. The application of a compound as described in any one of claims 1-9 in a self-healing curing material.