Metal organic framework material modified waterborne polyurethane sizing agent as well as preparation method and application thereof

Abstract

The invention provides a metal organic framework material modified waterborne polyurethane sizing agent as well as a preparation method and application thereof, and belongs to the technical field of carbon fibers. The preparation method of the sizing agent comprises the following steps: performing a first reaction on polyhydric alcohol, diisocyanate and a hydrophilic chain extender to obtain a first reaction solution, performing a second reaction on the first reaction solution, a small molecule chain extender and an amino-functionalized metal organic framework material to obtain a second reaction solution, and adding a neutralizing agent into the second reaction solution to perform a neutralization reaction; the metal organic framework material comprises a zeolite imidazate framework material. The zeolite imidazate framework material serving as a metal organic framework material has many active groups and can construct a coating coarse structure, and the zeolite imidazate framework material is combined to the waterborne polyurethane, so that the surface of the waterborne polyurethane contains many active groups; therefore, after the waterborne polyurethane is used as the sizing agent to perform sizing treatment on the carbon fibers, the interface bonding force between the carbon fibers and a resin matrix is improved.

Description

Technical Field

[0001] The present application relates to the field of carbon fiber technology, and in particular to a metal organic framework material modified waterborne polyurethane sizing agent, a preparation method thereof, and an application thereof. Background Art

[0002] Carbon fiber is prone to breakage and fuzzing during production, affecting the processability of the carbon fiber and the performance of its composite materials. Sizing significantly improves wear resistance, but most carbon fiber sizing agents have poor wettability and low interfacial shear strength, making them incompatible with thermoplastic resin matrices. The resulting composite carbon fibers are unable to meet strength requirements, limiting the development of thermoplastic resin-based composite carbon fibers. Summary of the Invention

[0003] The present application provides a metal organic framework material modified waterborne polyurethane sizing agent and its preparation method and application, which can be used to improve the interfacial bonding strength between carbon fiber and resin matrix.

[0004] The embodiment of the present application is implemented as follows:

[0005] In the first aspect, the present application provides an example of a preparation method for a metal-organic framework material modified water-based polyurethane sizing agent, which includes: firstly subjecting a polyol, a diisocyanate and a hydrophilic chain extender to a first reaction to obtain a first reaction liquid, then subjecting the first reaction liquid, a small molecule chain extender and an amino-functionalized metal-organic framework material to a second reaction to obtain a second reaction liquid, and then adding a neutralizer to the second reaction liquid for a neutralization reaction; the metal-organic framework material includes a zeolite imidazole ester skeleton material.

[0006] In the above technical solution, the preparation method of the metal-organic framework material modified waterborne polyurethane sizing agent of the present application first prepolymerizes a polyol, a diisocyanate and a hydrophilic chain extender through a first reaction, and then the prepolymerized first reaction liquid, the small molecule chain extender and the amino-functionalized metal-organic framework material through a second reaction to prepare a metal-organic framework material modified waterborne polyurethane. The zeolite imidazolate skeleton material as a metal-organic framework material has many active groups and can construct a rough structure of the coating. The zeolite imidazolate skeleton material is combined with the waterborne polyurethane to make the surface of the waterborne polyurethane contain more active groups, thereby improving the interfacial bonding strength between the carbon fiber and the resin matrix after the waterborne polyurethane is used as a sizing agent to sizing the carbon fiber.

[0007] In some possible embodiments, the zeolitic imidazolate framework material includes at least one of ZIF-7, ZIF-8, ZIF-11, ZIF-20, and ZIF-67.

[0008] In the above technical solution, the above zeolite imidazolate framework material can be used to be combined with waterborne polyurethane so that the surface of the waterborne polyurethane contains more active groups.

[0009] In some possible embodiments, the mass ratio of the polyol, diisocyanate, hydrophilic chain extender, small molecule chain extender and amino-functionalized metal organic framework material is 4-10:5-15:2-10:0.1-1.5:0.05-1.

[0010] In some possible embodiments, the temperature of the first reaction is 75°C to 90°C, the time of the first reaction is 1h to 3h, and / or; the temperature of the second reaction is 50°C to 75°C, the time of the second reaction is 2h to 3h; and / or; the temperature of the neutralization reaction is 30°C to 40°C, and the time of the neutralization reaction is 20min to 60min.

[0011] In some possible embodiments, the polyol includes at least one of polycaprolactone polyol, polytetramethylene ether glycol and polycarbonate diol, and / or; the diisocyanate includes at least one of isophorone diisocyanate, toluene diisocyanate and hexamethylene diisocyanate, and / or; the hydrophilic chain extender includes at least one of dihydroxymethylbutyric acid, dihydroxymethylbutyric acid and ethylene dihydroxyethanesulfonate, and / or; the small molecule chain extender includes at least one of 1,4-butanediol, dimethylolpropane and ethylene glycolamine, and / or; the neutralizer includes triethylamine and / or dimethylethanolamine.

[0012] In some possible embodiments, the amino-functionalized metal organic framework material is prepared by reacting the metal organic framework material and an amino-containing silane coupling agent in an organic solvent at a reaction temperature of 70° C. to 80° C. for a reaction time of 2 h to 6 h.

[0013] In the above technical solution, the amino-containing silane coupling agent can be combined with the metal organic framework material to functionalize the amino groups of the metal organic framework material, and then can be combined with the waterborne polymer.

[0014] In a second aspect, the present application provides an example of a metal-organic framework material modified waterborne polyurethane sizing agent, which is prepared according to the preparation method of the metal-organic framework material modified waterborne polyurethane sizing agent in the above embodiment.

[0015] In the above technical scheme, the surface of the metal organic framework material modified water-based polyurethane sizing agent of the present application contains a large number of active groups such as hydroxyl groups and amino groups. After the water-based polyurethane is used as a sizing agent to sizing the carbon fiber, on the one hand, the number of active groups on the surface of the carbon fiber can be increased, and on the other hand, the surface roughness of the carbon fiber can be increased, thereby improving the interfacial shear strength of the carbon fiber, and then improving the interfacial bonding force between the carbon fiber and the resin matrix.

[0016] In the third aspect, the present application provides an example of a metal-organic framework material modified waterborne polyurethane sizing agent prepared by the preparation method of the metal-organic framework material modified waterborne polyurethane sizing agent in the above embodiment, or the use of the metal-organic framework material modified waterborne polyurethane sizing agent in the above embodiment in the preparation of carbon fiber.

[0017] In the above technical scheme, the metal organic framework material modified water-based polyurethane sizing agent of the present application can be used in the preparation of carbon fiber. On the one hand, it can increase the surface active groups of the carbon fiber, and on the other hand, it can increase the surface roughness of the carbon fiber, thereby improving the interfacial shear strength of the carbon fiber, and then improving the interfacial bonding force between the carbon fiber and the resin matrix.

[0018] In some possible implementation schemes, before sizing the carbon fibers with a waterborne polyurethane sizing agent modified with a metal organic framework material, the carbon fibers are first subjected to an electrochemical oxidation treatment.

[0019] In the above technical solution, the electrochemical oxidation treatment can impart active groups to the carbon fiber surface, thereby improving the interfacial shear strength of the carbon fiber, and further improving the interfacial bonding force between the carbon fiber and the resin matrix.

[0020] In some possible implementation schemes, the electrochemical oxidation treatment stage is 1, the amount of electricity is 30C / g to 60C / g, and the treatment time is 30s to 60s. DETAILED DESCRIPTION

[0021] The embodiments of the present application will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.

[0022] The following is a detailed description of a metal organic framework material modified waterborne polyurethane sizing agent and its preparation method and application in accordance with an embodiment of the present application:

[0023] The present application provides a method for preparing a metal organic framework material modified waterborne polyurethane sizing agent, which comprises the following steps:

[0024] S1. Preparation of amino-functionalized metal-organic framework materials

[0025] The ZIF-8 material is first dissolved in an organic solvent, and then a silane coupling agent containing an amino group is added. After reacting at a temperature of 70°C to 80°C for 2h to 6h, an amino-functionalized metal-organic framework material is obtained by separation and drying.

[0026] Among them, metal-organic framework materials include zeolitic imidazolate framework materials (Zeolitic Imidazolate Frameworks, abbreviated as ZIFs).

[0027] Optionally, the zeolitic imidazolate framework material includes at least one of ZIF-7, ZIF-8, ZIF-11, ZIF-20 and ZIF-67.

[0028] The zeolite imidazolate framework material can be used to be combined with waterborne polyurethane so that the surface of the waterborne polyurethane contains more active groups.

[0029] Organic solvents include methanol.

[0030] Silane coupling agents containing amino groups include 3-aminopropyltriethoxysilane.

[0031] As an example, the reaction temperature of the metal organic framework material and the amino-containing silane coupling agent can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, and the reaction time can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.

[0032] The amino-containing silane coupling agent can be combined with the metal organic framework material to functionalize the amino group of the metal organic framework material, and then can be combined with the waterborne polymer.

[0033] S2. Preparation of Metal-Organic Framework Material Modified Waterborne Polyurethane Sizing Agent

[0034] First, polyol, diisocyanate and hydrophilic chain extender are subjected to a first reaction to obtain a first reaction liquid, and then the first reaction liquid, small molecule chain extender and amino-functionalized metal organic framework material are subjected to a second reaction to obtain a second reaction liquid. Then, a neutralizer is added to the obtained second reaction liquid for neutralization reaction, and finally, deionized water is added and emulsified with high-speed stirring to obtain a metal organic framework material modified waterborne polyurethane sizing agent.

[0035] The mass ratio of the polyol, the diisocyanate, the hydrophilic chain extender, the small molecule chain extender and the amino-functionalized metal organic framework material is 4-10:5-15:2-10:0.1-1.5:0.05-1.

[0036] Optionally, the mass proportion of polyol in the raw material is 4wt% to 10wt%, the mass proportion of diisocyanate in the raw material is 5wt% to 15wt%, the mass proportion of hydrophilic chain extender in the raw material is 2wt% to 10wt%, the mass proportion of small molecule chain extender in the raw material is 0.1wt% to 1.5wt%, the mass proportion of amino-functionalized metal organic framework material in the raw material is 0.05wt% to 1wt%, the mass proportion of deionized water in the raw material is 60wt% to 80wt%, and the mass of the neutralizer is 70% to 100% of the mass of the hydrophilic chain extender.

[0037] As an example, the mass proportion of the polyol in the raw material can be 4wt%, 6wt%, 8wt% or 10wt%, the mass proportion of the diisocyanate in the raw material can be 5wt%, 7wt%, 10wt%, 12wt% or 15wt%, the mass proportion of the hydrophilic chain extender in the raw material can be 2wt%, 4wt%, 6wt%, 8wt% or 10wt%, and the mass proportion of the small molecule chain extender in the raw material can be 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%. wt%, 1wt%, 1.2wt% or 1.5wt%, the mass proportion of the amino-functionalized metal organic framework material in the raw material can be 0.05wt%, 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt% or 1wt%, the mass proportion of deionized water in the raw material can be 60wt%, 65wt%, 70wt%, 75wt% or 80wt%, and the mass of the neutralizer can be 70%, 80%, 90% or 100% of the mass of the hydrophilic chain extender.

[0038] Optionally, the polyol includes at least one of polycaprolactone polyol, polytetramethylene ether diol, and polycarbonate diol.

[0039] Optionally, the diisocyanate includes at least one of isophorone diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.

[0040] Optionally, the hydrophilic chain extender includes at least one of dimethylolbutanoic acid, dimethylolbutanoic acid, and ethylene dihydroxyethanesulfonate.

[0041] Optionally, the small molecule chain extender includes at least one of 1,4-butanediol, dimethylolpropane and ethylene glycolamine.

[0042] Optionally, the neutralizing agent comprises triethylamine and / or dimethylethanolamine.

[0043] The temperature of the first reaction is 75° C. to 90° C., and the time of the first reaction is 1 h to 3 h.

[0044] As an example, the temperature of the first reaction may be 75° C., 80° C., 85° C., or 90° C., and the time of the first reaction may be 1 h, 1.5 h, 2 h, 2.5 h, or 3 h.

[0045] The temperature of the second reaction is 50° C. to 75° C., and the time of the second reaction is 2 h to 3 h.

[0046] As an example, the temperature of the second reaction may be 50° C., 55° C., 60° C., 65° C., 70° C., or 75° C., and the time of the second reaction may be 2 h, 2.5 h, or 3 h.

[0047] The temperature of the neutralization reaction is 30° C. to 40° C., and the time of the neutralization reaction is 20 min to 60 min.

[0048] As an example, the temperature of the neutralization reaction may be 30° C., 32° C., 35° C., 38° C., or 40° C., and the time of the neutralization reaction may be 20 min, 30 min, 40 min, 50 min, or 60 min.

[0049] The preparation method of the metal-organic framework material modified waterborne polyurethane sizing agent of the present application first prepolymerizes a polyol, a diisocyanate and a hydrophilic chain extender through a first reaction, and then the prepolymerized first reaction liquid, a small molecule chain extender and an amino-functionalized metal-organic framework material through a second reaction to prepare a metal-organic framework material modified waterborne polyurethane. The zeolite imidazolate skeleton material as a metal-organic framework material has many active groups and can construct a rough structure of the coating. The zeolite imidazolate skeleton material is combined with the waterborne polyurethane to make the surface of the waterborne polyurethane contain more active groups, thereby improving the interfacial bonding strength between the carbon fiber and the resin matrix after the waterborne polyurethane is used as a sizing agent to sizing the carbon fiber.

[0050] The present application provides an example of a metal-organic framework material modified waterborne polyurethane sizing agent, which is prepared according to the preparation method of the metal-organic framework material modified waterborne polyurethane sizing agent in the above embodiment.

[0051] The surface of the metal-organic framework material modified water-based polyurethane sizing agent of the present application contains a large number of active groups such as hydroxyl groups and amino groups. After the carbon fiber is sizing treated with the water-based polyurethane as a sizing agent, on the one hand, the number of active groups on the surface of the carbon fiber can be increased, and on the other hand, the surface roughness of the carbon fiber can be increased, thereby improving the interfacial shear strength of the carbon fiber, and then improving the interfacial bonding force between the carbon fiber and the resin matrix.

[0052] The present application provides an example of a metal-organic framework material-modified waterborne polyurethane sizing agent prepared by the preparation method of the metal-organic framework material-modified waterborne polyurethane sizing agent in the above embodiment, or the use of the metal-organic framework material-modified waterborne polyurethane sizing agent in the above embodiment in the preparation of carbon fiber.

[0053] Before sizing carbon fibers with a waterborne polyurethane sizing agent modified with a metal-organic framework, the carbon fibers are electrochemically oxidized. This electrochemical oxidation treatment imparts surface active groups to the carbon fibers, thereby increasing their interfacial shear strength and, in turn, their interfacial bonding strength with the resin matrix.

[0054] Optionally, the electrochemical oxidation treatment stage is 1, the amount of electricity is 30C / g to 60C / g, and the treatment time is 30s to 60s.

[0055] As an example, the amount of electricity for electrochemical oxidation treatment may be 30 C / g, 40 C / g, 50 C / g, or 60 C / g, and the treatment time may be 30 s, 40 s, 50 s, or 60 s.

[0056] The metal organic framework material modified waterborne polyurethane sizing agent of the present application can be used in the preparation of carbon fibers. On the one hand, it can increase the number of active groups on the surface of the carbon fibers, and on the other hand, it can increase the surface roughness of the carbon fibers, thereby improving the interfacial shear strength of the carbon fibers, and further improving the interfacial bonding force between the carbon fibers and the resin matrix.

[0057] The following is a further detailed description of a metal organic framework material modified waterborne polyurethane sizing agent of the present application, its preparation method and application in conjunction with the examples.

[0058] Example 1

[0059] The present invention provides a metal organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as an application of the metal organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber, which comprises the following steps:

[0060] S1. Preparation of amino-functionalized metal-organic framework materials

[0061] 200 mg of ZIF-8 was added to 30 mL of methanol solvent for dissolution, and then 0.25 mL of 3-aminopropyltriethoxysilane was added. The mixture was reacted at 75° C. for 5 h, and amino-functionalized ZIF-8 was obtained by separation and drying.

[0062] S2. Preparation of Metal-Organic Framework Material Modified Waterborne Polyurethane Sizing Agent

[0063] First, 14wt% of isophorone diisocyanate, 10wt% of polytetramethylene glycol and 3wt% of dihydroxymethylbutyric acid were reacted at 85°C for 2.5h to obtain a first reaction liquid, and then the first reaction liquid, 0.5wt% of 1,4-butanediol and 0.5wt% of amino-functionalized ZIF-8 were reacted at 65°C for 2.5h to obtain a second reaction liquid. Then, 2wt% of triethylamine was added to the obtained second reaction liquid for neutralization reaction, and finally 70wt% of deionized water was added and emulsified at high speed to obtain a metal organic framework material modified waterborne polyurethane sizing agent.

[0064] S3. Electrochemical oxidation treatment

[0065] The carbon fibers after high-temperature carbonization were subjected to a primary electrochemical oxidation treatment with a treatment charge of 30 C / g and a treatment time of 30 s.

[0066] S4, sizing

[0067] The electrochemically oxidized carbon fiber is impregnated into the prepared metal organic framework material modified waterborne polyurethane sizing agent to obtain sized carbon fiber.

[0068] Example 2

[0069] The embodiments of the present application provide a metal-organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as the use of the metal-organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber. Based on Example 1, the ZIF-8 material in step S1 is changed to ZIF-67, and the other materials remain unchanged.

[0070] Example 3

[0071] The embodiments of the present application provide a metal-organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as the use of the metal-organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber. Based on Example 1, the ZIF-8 material in step S1 is changed to ZIF-7, and the other materials remain unchanged.

[0072] Example 4

[0073] The embodiments of the present application provide a metal-organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as the use of the metal-organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber. Based on Example 1, the amount of amino-functionalized ZIF-8 in step S2 is changed to 0.05wt%, and the other aspects remain unchanged.

[0074] Example 5

[0075] The embodiments of the present application provide a metal-organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as the use of the metal-organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber. Based on Example 1, the amount of amino-functionalized ZIF-8 in step S2 is changed to 1wt%, and the other parameters remain unchanged.

[0076] Example 6

[0077] The embodiments of the present application provide a metal-organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as an application of the metal-organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber. Based on Example 1, the processing power in step S3 is changed to 60C / g and the processing time is 60s.

[0078] Example 7

[0079] The embodiments of the present application provide a metal organic framework material modified waterborne polyurethane sizing agent and a preparation method thereof, as well as the use of the metal organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber. Based on Example 1, it does not have the S3 electrochemical oxidation treatment step.

[0080] Comparative Example 1

[0081] The comparative example of the present application provides a water-based polyurethane sizing agent and a preparation method thereof, as well as an application of the water-based polyurethane sizing agent in the preparation of carbon fiber, which comprises the following steps:

[0082] S1. Preparation of waterborne polyurethane sizing agent

[0083] First, 14wt% of isophorone diisocyanate, 10wt% of polytetramethylene glycol and 3wt% of dihydroxymethylbutyric acid are reacted at 85°C for 2.5h to obtain a first reaction liquid, and then the first reaction liquid is reacted with 0.5wt% of 1,4-butanediol at 65°C for 2.5h to obtain a second reaction liquid. Then, 2wt% of triethylamine is added to the obtained second reaction liquid for neutralization reaction, and finally, 70.5wt% of deionized water is added and emulsified at high speed to obtain a waterborne polyurethane sizing agent.

[0084] S2. Sizing

[0085] The carbon fibers are impregnated into the prepared waterborne polyurethane sizing agent to obtain sized carbon fibers.

[0086] Comparative Example 2

[0087] The comparative example of the present application provides a water-based polyurethane sizing agent and a preparation method thereof, as well as an application of the water-based polyurethane sizing agent in the preparation of carbon fiber, which comprises the following steps:

[0088] S1. Preparation of waterborne polyurethane sizing agent

[0089] First, 14wt% of isophorone diisocyanate, 10wt% of polytetramethylene glycol and 3wt% of dihydroxymethylbutyric acid are reacted at 85°C for 2.5h to obtain a first reaction liquid, and then the first reaction liquid is reacted with 0.5wt% of 1,4-butanediol at 65°C for 2.5h to obtain a second reaction liquid. Then, 2wt% of triethylamine is added to the obtained second reaction liquid for neutralization reaction, and finally, 70.5wt% of deionized water is added and emulsified at high speed to obtain a waterborne polyurethane sizing agent.

[0090] S2. Electrochemical oxidation treatment

[0091] The carbon fibers after high-temperature carbonization were subjected to a primary electrochemical oxidation treatment with a treatment charge of 30 C / g and a treatment time of 30 s.

[0092] S3, sizing

[0093] The carbon fibers are impregnated into the prepared waterborne polyurethane sizing agent to obtain sized carbon fibers.

[0094] Comparative Example 3

[0095] The comparative example of the present application provides a water-based polyurethane sizing agent and a preparation method thereof, as well as an application of the water-based polyurethane sizing agent in the preparation of carbon fiber, which comprises the following steps:

[0096] S1. Preparation of waterborne polyurethane sizing agent

[0097] First, 14wt% of isophorone diisocyanate, 10wt% of polytetramethylene glycol and 3wt% of dihydroxymethylbutyric acid are reacted at 85°C for 2.5h to obtain a first reaction liquid, and then the first reaction liquid, 0.5wt% of 1,4-butanediol and 0.5wt% of ZIF-8 are reacted at 65°C for 2.5h to obtain a second reaction liquid. Then, 2wt% of triethylamine is added to the obtained second reaction liquid for neutralization reaction, and finally 70wt% of deionized water is added and emulsified at high speed to obtain a waterborne polyurethane sizing agent.

[0098] S2. Electrochemical oxidation treatment

[0099] The carbon fibers after high-temperature carbonization were subjected to a primary electrochemical oxidation treatment with a treatment charge of 30 C / g and a treatment time of 30 s.

[0100] S3, sizing

[0101] The electrochemically oxidized carbon fibers are impregnated into the prepared aqueous polyurethane sizing agent to obtain sized carbon fibers.

[0102] Test Example 1

[0103] The interfacial shear strength (IFSS) of the carbon fibers of Examples 1-7 and Comparative Examples 1-3 was measured using a microbead debonding method: a single carbon fiber was secured to a reinforcing sheet, and a resin droplet was dispensed onto the fiber. The resin droplet was then removed from the carbon fiber by moving the fixture of the microbead debonding apparatus. The test results are shown in Tables 1-2.

[0104] Table 1 Interface shear strength of carbon fibers of Examples 1 to 7

[0105] project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 IFSS / MPa 74 66 68 65 70 75 62

[0106] It can be seen from Examples 1 to 7 that after the carbon fiber is treated with the sizing agent prepared according to the preparation method of the metal organic framework material modified water-based polyurethane sizing agent of the present application, the interfacial shear strength of the carbon fiber is 62 MPa to 75 MPa; from the comparison between Example 1 and Example 7, it can be seen that Example 1 has an S3 electrochemical oxidation treatment step, and Example 7 does not have an S3 electrochemical oxidation treatment step. The interfacial shear strength of the carbon fiber after being treated with the sizing agent of Example 1 is higher than the interfacial shear strength of the carbon fiber after being treated with the sizing agent of Example 7.

[0107] Table 2 Interface shear strength of carbon fibers of Example 1 and Comparative Examples 1 to 3

[0108] project Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 IFSS / MPa 74 46 57 60

[0109] From the comparison between Comparative Example 1 and Example 1, it can be seen that the water-based polyurethane in Comparative Example 1 has neither been modified with amino-functionalized ZIF-8 nor the carbon fiber has been electrochemically oxidized. The interfacial shear strength of the carbon fiber in Comparative Example 1 is much lower than the interfacial shear strength of the carbon fiber in Example 1.

[0110] From the comparison between Comparative Example 2 and Example 1, it can be seen that the waterborne polyurethane of Comparative Example 2 has not been modified with amino-functionalized ZIF-8, and the interfacial shear strength of the carbon fiber of Comparative Example 2 is much lower than the interfacial shear strength of the carbon fiber of Example 1.

[0111] From the comparison between Comparative Example 3 and Example 1, it can be seen that the ZIF-8 in Comparative Example 3 is not amination-treated, and the interfacial shear strength of the carbon fiber in Comparative Example 3 is lower than that of the carbon fiber in Example 1.

[0112] The foregoing description is merely a specific embodiment of the present application and is not intended to limit the present application. Persons skilled in the art will readily appreciate that various modifications and variations are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A method for preparing a metal organic framework material modified waterborne polyurethane sizing agent, characterized in that: The preparation method of the metal-organic framework material modified waterborne polyurethane sizing agent comprises: firstly subjecting a polyol, a diisocyanate and a hydrophilic chain extender to a first reaction to prepare a first reaction liquid; then subjecting the first reaction liquid, a small molecule chain extender and an amino-functionalized metal-organic framework material to a second reaction to prepare a second reaction liquid; and then adding a neutralizing agent to the second reaction liquid for a neutralization reaction; The metal organic framework material includes a zeolite imidazolate framework material.

2. The method for preparing a metal organic framework modified waterborne polyurethane sizing agent according to claim 1, wherein: The zeolite imidazolate framework material includes at least one of ZIF-7, ZIF-8, ZIF-11, ZIF-20 and ZIF-67.

3. The method for preparing a metal organic framework modified waterborne polyurethane sizing agent according to claim 1, wherein: The mass ratio of the polyol, the diisocyanate, the hydrophilic chain extender, the small molecule chain extender and the amino-functionalized metal organic framework material is 4-10:5-15:2-10:0.1-1.5:0.05-1.

4. The method for preparing a metal organic framework modified waterborne polyurethane sizing agent according to claim 1, wherein: The temperature of the first reaction is 75° C. to 90° C., the time of the first reaction is 1 h to 3 h, and / or; The temperature of the second reaction is 50° C. to 75° C., and the time of the second reaction is 2 h to 3 h; and / or; The temperature of the neutralization reaction is 30° C. to 40° C., and the time of the neutralization reaction is 20 min to 60 min.

5. The method for preparing a metal organic framework modified waterborne polyurethane sizing agent according to claim 1, wherein: The polyol comprises at least one of polycaprolactone polyol, polytetramethylene ether diol and polycarbonate diol, and / or; The diisocyanate includes at least one of isophorone diisocyanate, toluene diisocyanate and hexamethylene diisocyanate, and / or; The hydrophilic chain extender includes at least one of dimethylolbutanoic acid, dimethylolbutanoic acid and ethylene dihydroxyethanesulfonate, and / or; The small molecule chain extender includes at least one of 1,4-butanediol, dimethylolpropane and ethylene glycolamine, and / or; The neutralizing agent includes triethylamine and / or dimethylethanolamine.

6. The method for preparing a metal organic framework modified waterborne polyurethane sizing agent according to claim 1, characterized in that: The amino-functionalized metal organic framework material is prepared by reacting the metal organic framework material and an amino-containing silane coupling agent in an organic solvent, the reaction temperature is 70° C. to 80° C., and the reaction time is 2 h to 6 h.

7. A metal organic framework material modified waterborne polyurethane sizing agent, characterized in that: The metal organic framework material modified waterborne polyurethane sizing agent is prepared according to the preparation method of the metal organic framework material modified waterborne polyurethane sizing agent according to any one of claims 1 to 6.

8. Use of a metal-organic framework material-modified waterborne polyurethane sizing agent prepared by the preparation method of a metal-organic framework material-modified waterborne polyurethane sizing agent according to any one of claims 1 to 6 or a metal-organic framework material-modified waterborne polyurethane sizing agent according to claim 7 in the preparation of carbon fibers.

9. Use of the metal organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber according to claim 8, characterized in that: Before using the metal organic framework material modified waterborne polyurethane sizing agent to sizing carbon fibers, the carbon fibers are first subjected to electrochemical oxidation treatment.

10. Use of the metal organic framework material modified waterborne polyurethane sizing agent in the preparation of carbon fiber according to claim 9, characterized in that: The electrochemical oxidation treatment has one stage, an electric quantity of 30C / g to 60C / g, and a treatment time of 30s to 60s.