Composite material and preparation method thereof

Abstract

The invention discloses a composite material and a preparation method thereof, and relates to the technical field of building materials. The preparation method comprises the following steps: providing a first mixed solution and 1, 3-cyclohexanedimethanol, mixing, and carrying out a first reaction to obtain a first prepolymer solution; providing a second mixed solution and polytetramethylene ether glycol, mixing, and carrying out a second reaction to obtain a second prepolymer solution; the first mixed solution and the second mixed solution both comprise diphenylmethane diisocyanate; providing a third mixed solution, mixing the third mixed solution with the first prepolymer solution and the second prepolymer solution, and carrying out a third reaction to obtain a supramolecular polymer; the third mixed solution comprises a chain extender; providing a wear-resistant agent, an antioxidant and glass fibers, and mixing with the supramolecular polymer to obtain the composite material. The composite material obtained by the method provided by the invention has high strength, excellent impact toughness, high wear resistance and self-repairing capability, and has wide prospects in high-end application scenarios such as polyurethane doors and windows, curtain wall keels, photovoltaic brackets and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building materials, in particular to a composite material and a preparation method thereof. BACKGROUND

[0002] Building energy consumption accounts for 30% of total social energy consumption, and among them, the energy consumption of doors and windows accounts for 50%. Traditional aluminum alloy doors and windows have poor thermal insulation performance due to high thermal conductivity (thermal conductivity coefficient of about 160 W / (m·K)), and new materials are urgently needed to replace them. Polyurethane composite material combines thermoplastic polyurethane with glass fiber reinforcement, and has the characteristics of lightweight, high strength and low energy consumption, becoming the core material of door and window industry innovation.

[0003] However, the existing polyurethane composite material is difficult to simultaneously have high strength and high toughness, and the wear resistance needs to be further improved. Most of them are thermosetting resin matrix, cannot be recycled, and lack self-repairing ability and other functions. These shortcomings seriously limit the application expansion of the composite material in the door and window industry. SUMMARY

[0004] Therefore, the present application provides a composite material and a preparation method thereof.

[0005] The present application is implemented in the following manner. In a first aspect, the present application provides a preparation method of a composite material, comprising the following steps:

[0006] A first mixed solution and 1,3-cyclohexane dimethanol are provided, mixed, a first reaction is performed, and a first prepolymer solution is obtained; the first mixed solution comprises diphenylmethane diisocyanate;

[0007] A second mixed solution and polytetramethylene ether glycol are provided, mixed, a second reaction is performed, and a second prepolymer solution is obtained; the second mixed solution comprises diphenylmethane diisocyanate;

[0008] A third mixed solution is provided, mixed with the first prepolymer solution and the second prepolymer solution, a third reaction is performed, and a supramolecular polymer is obtained; the third mixed solution comprises a chain extender;

[0009] An anti-wear agent, an antioxidant and glass fiber are provided, mixed with the supramolecular polymer, and a composite material is obtained.

[0010] Optionally, in some embodiments of the present application, in the first mixed solution, the mass fraction of the diphenylmethane diisocyanate is 10% to 40%;

[0011] The first mixed solution further comprises a first solvent; the first solvent is selected from one or more of N,N-dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylacetamide;

[0012] The first mixed solution and 1,3-cyclohexane dimethanol are mixed, and further comprising: adding a first catalyst; the first catalyst is selected from one or more of dibutyltin dilaurate, dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylenediamine.

[0013] Optionally, in some embodiments of the present application, in the first reaction, the mass ratio of the diphenylmethane diisocyanate and the 1,3-cyclohexane dimethanol is (10-50):(5-25);

[0014] The reaction temperature of the first reaction is 20-80℃;

[0015] The reaction time of the first reaction is 2-8h.

[0016] Optionally, in some embodiments of the present application, in the second mixed solution, the mass fraction of the diphenylmethane diisocyanate is 1-10%;

[0017] The second mixed solution further comprises a second solvent; the second solvent is selected from one or more of N,N-dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide;

[0018] The second mixed solution and polytetramethylene ether glycol are mixed, and further comprising: adding a second catalyst; the second catalyst is selected from one or more of dibutyltin dilaurate, dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylenediamine.

[0019] Optionally, in some embodiments of the present application, in the second reaction, the mass ratio of the diphenylmethane diisocyanate and the polytetramethylene ether glycol is (1-6):(2-30);

[0020] The reaction temperature of the second reaction is 20-80℃;

[0021] The reaction time of the second reaction is 2-8h.

[0022] Optionally, in some embodiments of the present application, in the third mixed solution, the mass fraction of the chain extender is 5-20%;

[0023] The chain extender is selected from one or more of ethylenediamine, adipic dihydrazide, isophthalic dihydrazide, oxalic dihydrazide;

[0024] The third mixed solution further comprises a third solvent; the third solvent is selected from one or more of N,N-dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide.

[0025] Optionally, in some embodiments of the present application, in the third reaction, the mass ratio of the first prepolymer, the second prepolymer and the chain extender is (10-40):(2-15):(1-10).

[0026] The reaction temperature of the third reaction is 20-80℃; and the reaction time of the third reaction is 2-20 minutes.

[0027] Optionally, in some embodiments of the present application, the antioxidant is selected from poly(dipropylene glycol) phenyl phosphite.

[0028] The wear-resistant agent is selected from one or more of molybdenum disulfide, tungsten disulfide, boron nitride and silicon dioxide.

[0029] Optionally, in some embodiments of the present application, the mass ratio of the supramolecular polymer, the wear-resistant agent and the antioxidant is (40-70):(2-10):(0.1-0.8).

[0030] In the composite material, the mass fraction of the glass fiber is 20%-60%.

[0031] In a second aspect, the embodiments of the present application further provide a composite material prepared by the above preparation method.

[0032] The preparation method of the composite material provided by the present application adopts rigid dihydric alcohol (1,3-cyclohexane dimethanol) and flexible long-chain dihydric alcohol (polytetramethylene ether glycol, PTMEG) as dihydric alcohol components, adopts high-activity and high-rigidity diphenyl methane diisocyanate (MDI) to end-cap the dihydric alcohol, adopts adipic dihydrazide as a chain extender, a multi-level and multi-hydrogen bond cross-linking system is formed between each unit, a double-continuous phase separation nanostructure is formed between the rigid dihydric alcohol component and the flexible long-chain dihydric alcohol component due to the difference in compatibility, the supramolecular polymer prepared has high strength, high hardness and high impact toughness; at the same time, the dissociation and recombination of the multi-level and multi-hydrogen bond endow the supramolecular polymer with self-repairing ability; in addition, the synthesized supramolecular polymer is blended by extrusion, a wear-resistant agent is added to improve the wear resistance, and glass fiber is added to further improve the strength and surface hardness of the composite material, and endow high wear resistance.

[0033] The composite material obtained by the preparation method provided by the present application has high strength, excellent impact toughness, high wear resistance and self-repairing ability, and has broad prospects in accelerating the replacement of traditional door and window products by polyurethane doors and windows, and extending to high-end application scenarios such as curtain wall keel and photovoltaic support. BRIEF DESCRIPTION OF DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments will be briefly introduced. Obviously, the drawings in the following description only represent some of the embodiments of the present application, and for those skilled in the art, other drawings can be obtained without creative labor on the basis of these drawings.

[0035] Figure 1 is a flow chart of a preparation method of a composite material provided by the embodiments of the present application. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present application will be described clearly and completely in the following description with reference to the drawings of the embodiments of the present application. Obviously, the described embodiments only represent some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0037] In the present application, the orientation words such as "upper" and "lower" generally refer to the upper and lower in the actual use or working state of the device, and specifically refer to the direction of the drawing surface in the drawings. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The words first, second, third, etc. are only used as labels, and do not impose numerical requirements or establish sequences.

[0038] In the present application, "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B, which can represent the following cases: A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural.

[0039] In the present application, "at least one" means one or more, and "multiple" means two or more. "One or more", "at least one of the following", or similar expressions, means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0040] Various embodiments of the present application can exist in a range of forms; it should be understood that the description in a range form is merely for the convenience and brevity, and should not be understood as a hard limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values in the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single values in the range, such as 1, 2, 3, 4, 5 and 6, which is applicable to any range. In addition, whenever a numerical range is indicated in this document, it refers to any cited number (fraction or integer) in the indicated range.

[0041] The structural formula and molecular weight of some chemical reagents used in the present application are described as follows:

[0042] 1,3-cyclohexane dimethanol: , molecular weight = 144.21;

[0043] Polytetramethylene ether glycol-2000 (PTMEG-2000): , n is an integer from 20 to 30, number average molecular weight = 2000;

[0044] Diphenyl methane diisocyanate (MDI): , molecular weight = 250.26;

[0045] Adipic dihydrazide: , molecular weight = 174.2;

[0046] 3-ureidopropyl trimethoxysilane: , molecular weight = 222.31.

[0047] The technical solutions of the present application are as follows:

[0048] In a first aspect, referring to Figure 1 The present application provides a preparation method of a composite material, comprising the following steps:

[0049] Step S11, providing a first mixed solution and 1,3-cyclohexane dimethanol, mixing, carrying out a first reaction, to obtain a first prepolymer solution; the first mixed solution includes diphenyl methane diisocyanate;

[0050] Step S12, providing a second mixed solution and polytetramethylene ether glycol, mixing, carrying out a second reaction, to obtain a second prepolymer solution; the second mixed solution includes diphenyl methane diisocyanate;

[0051] Step S13, providing a third mixed solution, mixing with the first prepolymer solution and the second prepolymer solution, carrying out a third reaction to obtain a supramolecular polymer; the third mixed solution comprises a chain extender;

[0052] Step S14, providing a wear-resistant agent, an antioxidant and glass fibers, and mixing with the supramolecular polymer to obtain a composite material.

[0053] The preparation method of the composite material provided in the application adopts rigid dihydric alcohol (1,3-cyclohexane dimethanol) and flexible long-chain dihydric alcohol (polytetramethylene ether glycol, PTMEG) as dihydric alcohol components, adopts high-activity and high-rigidity diphenyl methane diisocyanate (MDI) to end-cap the dihydric alcohol, adopts adipic dihydrazide as a chain extender, a multi-level and multi-hydrogen bond cross-linking system is formed between each unit, a double-continuous phase separation nanostructure is formed between the rigid dihydric alcohol component and the flexible long-chain dihydric alcohol component due to the difference in compatibility, and the prepared supramolecular polymer has high strength, high hardness and high impact toughness; at the same time, the dissociation and recombination of the multi-level and multi-hydrogen bond endow the supramolecular polymer with self-repairing ability; in addition, the synthesized supramolecular polymer is blended by extrusion, a wear-resistant agent is added to improve wear resistance, and glass fibers are added to further improve the strength and surface hardness of the composite material and endow it with high wear resistance.

[0054] The composite material obtained by the preparation method provided in the application has high strength, excellent impact toughness, high wear resistance and self-repairing ability, and has broad prospects in aspects of replacing traditional door and window products with accelerated polyurethane doors and windows and extending to high-end application scenarios such as curtain wall keel and photovoltaic support.

[0055] In the step S11,

[0056] In some embodiments, in the first mixed solution, the mass fraction of the diphenyl methane diisocyanate is 10% to 40%, for example, can be 10%, 18%, 20%, 23%, 32%, 36%, 40% or a range between any two of the above values, etc. Within the range of the mass fraction as described above, it is beneficial to the uniform dispersion of the diphenyl methane diisocyanate; wherein the mass fraction of the diphenyl methane diisocyanate refers to the ratio of the mass of the diphenyl methane diisocyanate to the mass of the first mixed solution.

[0057] In some embodiments, the first mixed solution further comprises a first solvent; further, the first solvent is selected from one or more of N,N-dimethylformamide (DMF), dioxane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide.

[0058] In some embodiments, in the first reaction, the mass ratio of the diphenylmethane diisocyanate and the 1,3-cyclohexanedimethanol is (10-50):(5-25), which can be 10:5.2, 15:7, 24:10, 30:14.4, 36:16, 42:22, 50:24 or a range between any two of the above ratios, etc. Within the range of the mass ratio as described above, the ratio of the diphenylmethane diisocyanate and the 1,3-cyclohexanedimethanol is appropriate, which is conducive to the sufficient reaction of the diphenylmethane diisocyanate and the 1,3-cyclohexanedimethanol.

[0059] In some embodiments, the providing the first mixed solution and the 1,3-cyclohexanedimethanol and mixing further comprises: adding a first catalyst.

[0060] Further, the first catalyst is selected from one or more of dibutyltin dilaurate, dimethylcyclohexylamine, N,N-dimethylbenzylamine, and triethylenediamine.

[0061] In some embodiments, the reaction temperature of the first reaction is 20-80°C, which can be 20°C, 40°C, 60°C, 80°C or a range between any two of the above values; the reaction time of the first reaction is 2-8h, which can be 2h, 3h, 6h, 8h or a range between any two of the above values; under the reaction conditions as described above, the first reaction is facilitated to proceed sufficiently, thereby improving the reaction yield.

[0062] In some embodiments, the first prepolymer solution comprises a first prepolymer, and the end group of the first prepolymer is an isocyanate group provided by the diphenylmethane diisocyanate.

[0063] In some embodiments, the first prepolymer has the following formula:

[0064] .

[0065] Further, the synthesis route of the reaction of the diphenylmethane diisocyanate and the 1,3-cyclohexanedimethanol to generate the first prepolymer is as follows:

[0066] .

[0067] In the step S12:

[0068] In some embodiments, the mass fraction of the diphenylmethane diisocyanate in the second mixture is 1% to 10%, for example, 1%, 4%, 6%, 7%, 9%, 10%, or a range between any two of the aforementioned values, etc. Within the range of the mass fraction as described above, the uniform dispersion of the diphenylmethane diisocyanate is facilitated; wherein the mass fraction of the diphenylmethane diisocyanate refers to the ratio of the mass of the diphenylmethane diisocyanate to the mass of the second mixture.

[0069] In some embodiments, the second solvent is further included in the second mixture; further, the second solvent is selected from one or more of N,N-dimethylformamide (DMF), dioxane, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylacetamide.

[0070] In some embodiments, the mass ratio of the diphenylmethane diisocyanate to the polytetramethylene ether glycol in the second reaction is (1 to 6) : (2 to 30), for example, 1:5.2, 1.5:7, 2.5:10, 3:14.4, 3.6:18, 4:22, 6:28, or a range between any two of the aforementioned values, etc. Within the range of the mass ratio as described above, the proportion of the diphenylmethane diisocyanate to the polytetramethylene ether glycol is appropriate, and the sufficient reaction of the diphenylmethane diisocyanate and the polytetramethylene ether glycol is facilitated.

[0071] In some embodiments, the providing the second mixture and the polytetramethylene ether glycol, mixing, further comprises: adding a second catalyst.

[0072] Further, the second catalyst is selected from one or more of dibutyltin dilaurate, dimethylcyclohexylamine, N,N-dimethylbenzylamine, and triethylenediamine.

[0073] In some embodiments, the reaction temperature of the second reaction is 20°C to 80°C, for example, 20°C, 40°C, 60°C, 80°C, or a range between any two of the aforementioned values; the reaction time of the second reaction is 2h to 8h, for example, 2h, 3h, 6h, 8h, or a range between any two of the aforementioned values; under the reaction conditions as described above, the sufficient progress of the second reaction is facilitated, and the reaction yield is improved.

[0074] In some embodiments, the second prepolymer solution includes a second prepolymer, and the second prepolymer is an isocyanate group-terminated prepolymer.

[0075] In some embodiments, the structure of the second prepolymer is as shown in the following formula:

[0076] .

[0077] Further, the synthesis route of the reaction of the diphenylmethane diisocyanate and the polytetramethylene ether glycol to generate the second prepolymer is shown in the following formula:

[0078] ;

[0079] wherein m is an integer of 20-30.

[0080] In the step S13:

[0081] In some embodiments, in the third mixed solution, the mass fraction of the chain extender is 5%-20%, for example, can be 5%, 9.8%, 12%, 16%, 18%, 20% or a range between any two of the above values, etc. Within the range of the mass fraction as described above, it is beneficial for the uniform dispersion of the chain extender; wherein the mass fraction of the chain extender refers to the ratio of the mass of the chain extender to the mass of the third mixed solution.

[0082] In some embodiments, the chain extender is selected from one or more of ethylenediamine, adipic dihydrazide, isophthalic dihydrazide, and 1,4-butanediol.

[0083] In some embodiments, the third mixed solution further comprises a third solvent; further, the third solvent is selected from one or more of N,N-dimethylformamide (DMF), dioxane, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylacetamide.

[0084] In some embodiments, in the third reaction, the mass ratio of the first prepolymer, the second prepolymer and the chain extender is (10-40):(2-15):(1-10), for example, can be 12:3.25:1, 17:4.75:1.5, 22:6.26:2.18, 33:9:3.4, 38:11:6 or a range between any two of the above values, etc. Within the range of the mass ratio as described above, the proportions of the first prepolymer, the second prepolymer and the chain extender are appropriate, which is beneficial for the sufficient chain extension polymerization of the first prepolymer and the second prepolymer.

[0085] In some embodiments, the reaction temperature of the third reaction is 20°C-80°C, for example, can be 20°C, 40°C, 60°C, 80°C or a range between any two of the above values; the reaction time of the third reaction is 2min-20min, for example, can be 2min, 3min, 5min, 14min, 18min, 20min or a range between any two of the above values; under the reaction conditions as described above, it is beneficial for the sufficient performance of the third reaction, and improves the reaction efficiency of the third reaction.

[0086] In some embodiments, the providing the third mixed solution, mixing with the first prepolymer solution and the second prepolymer solution, and performing the third reaction further comprise: removing the solvent in the reaction system.

[0087] In some embodiments, the removing the solvent in the reaction system can be achieved by conventional technical means in the art; such as vacuum drying, reduced pressure drying, or adding a drying machine, etc.; when vacuum drying is adopted, the reaction liquid of the third reaction can be poured into a tetrafluoroethylene tray for the vacuum drying, the time of the vacuum drying can be 8h~20h, and the temperature of the vacuum drying can be 60℃~90℃.

[0088] In some embodiments, the structure of the supramolecular polymer is as shown in the following formula:

[0089] .

[0090] wherein R1 represents a rigid 1,3-cyclohexane dimethanol constructed polyurethane segment, is , R2 represents a long chain flexible polytetramethylene ether glycol part, is wherein m is an integer of 20~30; 0.7 and 0.3 represent the molar content of the rigid 1,3-cyclohexane dimethanol constructed polyurethane segment and the long chain flexible polytetramethylene ether glycol constructed polyurethane segment, respectively, which are 0.7mol and 0.3mol; and n is an integer of 100~150.

[0091] In the step S14:

[0092] In some embodiments, before performing the step S14, the supramolecular polymer can also be crushed to facilitate the mixing of the supramolecular polymer.

[0093] In some embodiments, the antioxidant is selected from poly(dipropylene glycol) phenyl phosphite (antioxidant 2103).

[0094] In some embodiments, the wear-resistant agent is selected from one or more of molybdenum disulfide, tungsten disulfide, boron nitride, and silicon dioxide.

[0095] In some embodiments, the providing the wear-resistant agent, the antioxidant, and the glass fiber, and mixing with the supramolecular polymer to obtain a composite material can be: first mixing the wear-resistant agent, the antioxidant, and the supramolecular polymer to obtain a premixed intermediate; and then mixing the glass fiber with the premixed intermediate to obtain a composite material.

[0096] In some embodiments, the mass ratio of the supramolecular polymer, the wear-resistant agent and the antioxidant is (40-70):(2-10):(0.1-0.8), for example, it can be 40:2:0.1, 46.3:2.7:0.2, 54.2:3.8:0.3, 66.3:5:0.4, 70:8.4:0.6 or a range between any two of the above ratios, etc. Within the range of the mass ratio as described above, the proportions of the supramolecular polymer, the wear-resistant agent and the antioxidant are suitable, which is conducive to the sufficient mixing of the supramolecular polymer and the wear-resistant agent, and meanwhile the antioxidant can effectively delay oxidation.

[0097] In some embodiments, in the composite material, the mass fraction of the glass fiber is 20%-60%, for example, it can be 20%, 30%, 40%, 50%, 60% or a range between any two of the above values, etc. Within the range of the mass fraction as described above, the content of the glass fiber is suitable, which is conducive to the sufficient combination of the interface between the glass fiber and the polyurethane matrix of the supramolecular polymer. The mass fraction of the glass fiber refers to the ratio of the mass of the glass fiber to the mass of the composite material.

[0098] In some embodiments, the composite material can be obtained by mixing the glass fiber with the premixed intermediate after the glass fiber is infiltrated by a 3-ureidopropyl trimethoxysilane / acetone solution.

[0099] It should be noted that the urea group of 3-ureidopropyl trimethoxysilane can form strong hydrogen bonding with the polyurethane matrix in the supramolecular polymer, thereby enhancing the interface combination between the glass fiber and the polyurethane matrix of the supramolecular polymer.

[0100] In some embodiments, the mixing of the wear-resistant agent, the antioxidant and the supramolecular polymer can be realized by a blender to obtain the premixed intermediate; further, the mixing of the glass fiber and the premixed intermediate can be realized by an extruder to obtain the composite material.

[0101] The preparation method of the composite material provided in the embodiment of the application adopts rigid dihydric alcohol (1,3-cyclohexane dimethanol) and flexible long-chain dihydric alcohol (polytetramethylene ether glycol, PTMEG) as the dihydric alcohol component, adopts high-activity and high-rigidity diphenyl methane diisocyanate (MDI) to end-cap the dihydric alcohol, adopts adipic dihydrazide as a chain extender, a multi-stage and multi-hydrogen bond cross-linking system is formed between units, a bi-continuous phase separation nanostructure is formed between the rigid dihydric alcohol component and the flexible long-chain dihydric alcohol component due to the difference in compatibility, and the prepared supramolecular polymer has high strength, high hardness and high impact toughness; at the same time, the dissociation and recombination of the multi-stage and multi-hydrogen bond endows the supramolecular polymer with self-repairing capability; in addition, the synthesized supramolecular polymer is blended by extrusion, and a wear-resistant agent is added to improve the wear resistance, and glass fibers are added to further improve the strength and surface hardness of the composite material, and endow high wear resistance.

[0102] In a second aspect, the application provides a composite material, which is prepared by the above preparation method.

[0103] The composite material provided in the application has high strength, excellent impact toughness, high wear resistance and self-repairing capability, and has broad prospects in replacing traditional door and window products with accelerated polyurethane doors and windows, extending to high-end application scenarios such as curtain wall keels and photovoltaic supports, etc.

[0104] The application will be specifically described below through specific embodiments. The following embodiments are only part of the embodiments of the application and are not a limitation on the application.

[0105] Embodiment 1

[0106] The embodiment provides a composite material, and a preparation method of the composite material agent includes the following steps:

[0107] Step 1: 30 g of diphenyl methane diisocyanate and 100 g of anhydrous DMF are taken into a 250 ml three-necked flask, the temperature is raised to 60 DEG C, stirring is started to make the MDI completely dissolved, and a first mixed solution is obtained; 14.4 g of 1,3-cyclohexane dimethanol and 1 drop of dibutyl tin dilaurate are further added, nitrogen is introduced for protection, and the reaction is carried out at 60 DEG C for 3 h, so that a DMF solution of the first prepolymer with isocyanate groups at the end, i.e., a first prepolymer solution, is obtained; in the first prepolymer solution, the mass fraction of the first prepolymer is 30.75 wt%;

[0108] Step 2: 2.5 g of diphenylmethane diisocyanate and 50 g of anhydrous DMF were taken into a 100 ml three-necked flask, warmed to 60℃, and stirred to completely dissolve the MDI to obtain a second mixed solution; 10 g of polytetramethylene ether glycol-2000 (PTMEG-2000) and 1 drop of dibutyl tin dilaurate were added, and the nitrogen gas was passed to protect the flow, and the reaction was carried out at 60℃ for 3 h to obtain a DMF solution of the isocyanate group terminated second prepolymer, i.e. the second prepolymer solution; in the second prepolymer solution, the mass fraction of the second prepolymer was 20wt%;

[0109] Step 3: 72.2 g of the first prepolymer solution obtained in step 1 (the mass of the first prepolymer was 22.20 g) and 13.9 g of the second prepolymer solution obtained in step 2 (the mass of the second prepolymer was 2.78 g) were taken; 1.93 g of adipic dihydrazide was dissolved in 20 g of anhydrous DMF to obtain a third mixed solution, and the chain extension reaction was carried out at 60℃; after 5 min, the reaction solution was poured into a tetrafluoroethylene tray and placed in a vacuum oven at 80℃ under vacuum for 12 h to remove the DMF, thereby obtaining a supramolecular polymer;

[0110] Step 4: The supramolecular polymer prepared in step 3 was crushed into small particles by a high-speed crusher and reserved. The crushed supramolecular polymer particles, high-purity molybdenum disulfide powder (3000 mesh, purchased from Henan Xinjiut New Material Technology Co., Ltd.) and antioxidant 2103 were premixed in a moderate-speed mixer at a mass ratio of 56.8:3:0.2, and then added into the feeding port of the extruder; a 3-ureidopropyl trimethoxysilane / acetone solution with a mass fraction of 2wt% was prepared, and continuous glass fibers (TCR735, purchased from Taishan Glass Fiber Co., Ltd.) were immersed in the 3-ureidopropyl trimethoxysilane / acetone solution (the immersion time was 1 min) and then fed into the extruder through the glass fiber port; the rotation speed of the extruder and the feeding amount of the glass fibers were controlled so that the mass fraction of the glass fibers in the final composite material was 40wt%, thereby obtaining a composite material. The specific settings of the temperature zones of the extruder were as follows: zone 1: 230℃, zone 2: 230℃, zone 3: 235℃, zone 4: 235℃, zone 5: 240℃, zone 6: 245℃, zone 7: 240℃, zone 8: 235℃, zone 9: 230℃, zone 10: 230℃, the rotation speed of the screw was 300 r / min, and the length-diameter ratio was 48:1.

[0111] Example 2

[0112] This example is basically the same as example 1, except that the amount of the second prepolymer solution used in step 3 is 31.3 g (the mass of the second prepolymer is 6.26 g); and the amount of adipic dihydrazide is 2.18 g.

[0113] Example 3

[0114] This example is basically the same as Example 1, except that the amount of the second prepolymer solution in step 3 is 53.7 g (the mass of the second prepolymer is 10.74 g); and the amount of adipic dihydrazide is 2.49 g.

[0115] Example 4

[0116] This example is basically the same as Example 1, except that in step 4, the supermolecular polymer particles, high-purity molybdenum disulfide powder, and antioxidant 2103 are in a mass ratio of 66.8:3:0.2; and the mass proportion of glass fiber in the final composite material is 30wt%.

[0117] Example 5

[0118] This example is basically the same as Example 1, except that in step 4, the supermolecular polymer particles, high-purity molybdenum disulfide powder, and antioxidant 2103 are in a mass ratio of 46.8:3:0.2; and the mass proportion of glass fiber in the final composite material is 50wt%.

[0119] Example 6

[0120] This example is basically the same as Example 1, except that in step 4, the supermolecular polymer particles, high-purity molybdenum disulfide powder, and antioxidant 2103 are in a mass ratio of 54.8:5:0.2; and the mass proportion of glass fiber in the final composite material is 40wt%.

[0121] Comparative Example 1

[0122] This example is basically the same as Example 1, except that in step 4, a commercial hard polyurethane (TPU ETE70DT3, purchased from Lubrizol Advanced Materials Company) is used to replace the supermolecular polymer.

[0123] Comparative Example 2

[0124] This example is basically the same as Example 1, except that in step 4, the glass fiber is directly introduced into the extruder without being immersed in the 3-ureidopropyl trimethoxysilane / acetone solution.

[0125] The composite materials provided in Examples 1-6 and the composite materials provided in Comparative Examples 1-2 are subjected to mechanical property and wear resistance tests, and the test results are shown in Table 1.

[0126] The tensile strength test is performed according to the standard ASTM D638.

[0127] The bending strength and bending modulus test is performed according to the standard ASTM D790.

[0128] The unnotched Charpy impact strength (3.2 mm) test is performed according to the standard ASTM D4812.

[0129] Taber abrasion test was performed according to standard ASTM D3389 with H-18 wheel, load of 1 kg, rotation speed of 60 rpm, and 1000 cycles.

[0130] Self-repairing experiment was performed by cutting the tensile or impact sample with a blade under heating and softening, then butting the broken section, and dropping 2 drops of DMF at the interface to promote molecular chain movement and mutual diffusion at the broken section, and placing at 60°C for 24 h to obtain a complete tensile or impact sample.

[0131] Table 1

[0132] Name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Tensile strength (MPa) 201 185 174 149 227 192 164 156 Flexural strength (MPa) 284 271 259 208 323 279 226 225 Flexural modulus (GPa) 12.7 12.2 11.4 8.3 17.4 12.4 10.5 11.9 Unnotched impact strength (J / m) 1043 1135 1287 1421 924 1096 607 828 Wear amount (mg / 1000 turns) 23 27 30 55 14 19 46 29 Tensile strength after self-repair (MPa) 182 159 157 126 184 156 - 129 Unnotched impact strength after self-repair (J / m) 845 967 1133 1197 748 887 - 686

[0133] From the above test data, compared with Comparative Example 1, the composite material prepared in the application contains both rigid and flexible diol components, which form a bicontinuous phase separation nanostructure due to the difference in compatibility, and after chain extension of adipic hydrazide, a rich multi-level and multi-hydrogen bond crosslinking network is formed in the polyurethane molecular chain, so the composite material has high strength, high hardness, high impact toughness and high wear resistance; by adjusting the relative content of rigid diol and flexible diol, the mechanical properties of the polyurethane composite material can be easily adjusted; at the same time, the dissociation and recombination of the multi-level and multi-hydrogen bond in the composite material endows the supramolecular plastic with excellent self-repairing ability, and the self-repairing efficiency of all examples is greater than 80%; from the wear amount of Comparative Example 2 and Example 6, it can be seen that the self-lubricating effect of molybdenum disulfide is remarkable in improving the wear resistance of the composite material. In addition, from the performance data of Comparative Example 2 and Comparative Example 2, it can be seen that the surface treatment of glass fiber with 3-ureidopropyl trimethoxysilane is also very critical to the final performance improvement of the composite material, because the urea group of 3-ureidopropyl trimethoxysilane can form strong hydrogen bond with the polyurethane matrix, and the interfacial bonding between the glass fiber and the polyurethane matrix is enhanced. The prepared polyurethane composite material has high strength, excellent impact toughness, high wear resistance and self-repairing ability, and has broad prospects in accelerating the replacement of traditional door and window products with polyurethane door and window, and extending to high-end application scenarios such as curtain wall keel, photovoltaic support, etc.

[0134] The composite material provided by the application has high strength, excellent impact toughness, high wear resistance and self-repairing ability, and has broad prospects in accelerating the replacement of traditional door and window products with polyurethane door and window, and extending to high-end application scenarios such as curtain wall keel, photovoltaic support, etc.

[0135] The technical solutions provided by the embodiments of the present application are described in detail above, and the principles and implementation manners of the present application are described by applying specific examples. The above description of the embodiments is only used to help understand the method of the present application and its core idea; meanwhile, for those skilled in the art, the specific implementation manners and application ranges will be changed according to the idea of the present application. In conclusion, the content of the specification should not be understood as a limitation of the present application.

Claims

1. A method for preparing a composite material, characterized in that, Includes the following steps: A first mixture and 1,3-cyclohexanediethanol are provided, mixed, and subjected to a first reaction to obtain a first prepolymer solution; the first mixture includes diphenylmethane diisocyanate. A second mixture and polytetramethylene ether glycol are provided, mixed, and subjected to a second reaction to obtain a second prepolymer solution; The second mixture includes diphenylmethane diisocyanate; A third mixture is provided, which is mixed with the first prepolymer solution and the second prepolymer solution to carry out a third reaction, thereby obtaining a supramolecular polymer; The third mixture includes a chain extender; Abrasion resistant agent, antioxidant and glass fiber are provided and mixed with the supramolecular polymer to obtain a composite material.

2. The preparation method according to claim 1, characterized in that, In the first mixture, the mass fraction of the diphenylmethane diisocyanate is 10% to 40%; The first mixture further includes a first solvent; the first solvent is selected from one or more of N,N-dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylacetamide. The provision of the first mixture and 1,3-cyclohexanediethanol, the mixing of which further includes: adding a first catalyst; the first catalyst is selected from one or more of dibutyltin dilaurate, dimethylcyclohexylamine, N,N-dimethylbenzylamine, and triethylenediamine.

3. The preparation method according to claim 1, characterized in that, In the first reaction, the mass ratio of the diphenylmethane diisocyanate to the 1,3-cyclohexanediethanol is (10~50):(5~25). The reaction temperature of the first reaction is 20℃~80℃; The reaction time for the first reaction is 2 to 8 hours.

4. The preparation method according to claim 1, characterized in that, In the second mixture, the mass fraction of the diphenylmethane diisocyanate is 1% to 10%; The second mixture also includes a second solvent; the second solvent is selected from one or more of N,N-dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylacetamide. The provision of the second mixture and polytetramethylene ether glycol, the mixing of which further includes: adding a second catalyst; the second catalyst is selected from one or more of dibutyltin dilaurate, dimethylcyclohexylamine, N,N-dimethylbenzylamine, and triethylenediamine.

5. The preparation method according to claim 1, characterized in that, In the second reaction, the mass ratio of the diphenylmethane diisocyanate to the polytetramethylene ether diol is (1~6):(2~30); The reaction temperature for the second reaction is 20℃~80℃; The reaction time for the second reaction is 2 to 8 hours.

6. The preparation method according to claim 1, characterized in that, In the third mixture, the chain extender has a mass fraction of 5% to 20%. The chain extender is selected from one or more of ethylenediamine, adipamide, isophthalic acid dihydrazide, and oxalohydrazide; The third mixture also includes a third solvent; the third solvent is selected from one or more of N,N-dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylacetamide.

7. The preparation method according to claim 1, characterized in that, In the third reaction, the mass ratio of the first prepolymer, the second prepolymer, and the chain extender is (10~40):(2~15):(1~10). The reaction temperature of the third reaction is 20℃~80℃; the reaction time of the third reaction is 2min~20min.

8. The preparation method according to claim 1, characterized in that, The antioxidant is selected from poly(dipropylene glycol) phenyl phosphite; The wear-resistant agent is selected from one or more of molybdenum disulfide, tungsten disulfide, boron nitride, and silicon dioxide.

9. The preparation method according to claim 1, characterized in that, The mass ratio of the supramolecular polymer, the wear-resistant agent, and the antioxidant is (40~70):(2~10):(0.1~0.8). In the composite material, the mass fraction of glass fiber is 20% to 60%.

10. A composite material, characterized in that, The composite material is prepared by any one of the preparation methods described in claims 1-9.

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