Nucleating agent composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of nucleating agents, and particularly discloses a nucleating agent composition and a preparation method and application thereof.The nucleating agent composition comprises polytetrafluoroethylene and multi-layer graphene, the polytetrafluoroethylene is interspersed in multi-layer graphene sheets, and the polytetrafluoroethylene is obtained through plasma surface treatment in a nitrogen-containing gas atmosphere. According to the preparation method, polytetrafluoroethylene and graphene are effectively combined, the multilayer graphene retains excellent properties of graphene, and compared with an inert graphene surface, after the multilayer graphene is combined with the polytetrafluoroethylene subjected to surface treatment, the polytetrafluoroethylene can be intercalated into the multilayer graphene, so that agglomeration of the graphene is inhibited; therefore, the dispersity in a matrix is promoted; meanwhile, the advantages of the high-molecular nucleating agent and the inorganic nucleating agent are exerted, and the mechanical property and the thermal property of the product are improved.

Description

Technical Field

[0001] The present application relates to the technical field of nucleating agents, and more specifically, to a nucleating agent composition, a preparation method thereof, and an application thereof. Background Art

[0002] Nucleating agents are applicable to incompletely crystalline plastics such as polyethylene and polypropylene. By changing the crystallization behavior of the resin, accelerating the crystallization rate, increasing the crystallization density, and promoting the refinement of grain size, new functional additives can be achieved to shorten the molding cycle, improve the transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and other physical and mechanical properties of products. Nucleating agents can be mainly classified into inorganic, organic, and polymer types from the chemical structure. Inorganic nucleating agents mainly include talcum powder, calcium oxide, graphene, calcium carbonate, etc.; organic nucleating agents mainly include carboxylate metal salts, phosphate metal salts, sorbitol benzylidene derivatives, etc.; polymer nucleating agents mainly include alkali metal salts of polyester oligomers, wholly aromatic polyester powders, polytetrafluoroethylene powders, etc.

[0003] In recent years, with the increasing demand for new products of high-efficiency nucleating agents, the development difficulty of high-efficiency nucleating agents has become greater and the R & D speed has become slower. Therefore, it is particularly important to compound and modify different nucleating agents to prepare a more efficient nucleating agent composition through the synergistic effect between different nucleating agents. Therefore, the development of a new nucleating agent composition is of great significance to the development of nucleating agents. Summary of the Invention

[0004] In order to develop a new nucleating agent composition to improve the crystallization effect on resins, the present application provides a nucleating agent composition, a preparation method thereof, and an application thereof.

[0005] In the first aspect, the present application provides a nucleating agent composition, adopting the following technical solution:

[0006] A nucleating agent composition includes polytetrafluoroethylene and multi-layer graphene. The polytetrafluoroethylene is interspersed in the multi-layer graphene sheets and is obtained by plasma treatment of the polytetrafluoroethylene in an atmosphere of nitrogen-containing gas.

[0007] By adopting the above technical solution, polytetrafluoroethylene, as a polymer nucleating agent, has a high specific surface area, which provides more crystallization nucleation interfaces and excellent heterogeneous nucleation effect, thus significantly promoting the crystallization kinetics of the resin; graphene, as an inorganic nucleating agent, has excellent mechanical properties, and the mechanical properties of the resin can be improved by adding a very small amount of graphene. In this application, polytetrafluoroethylene and graphene are effectively combined. Since multi-layer graphene not only retains the excellent properties of graphene, but also compared with the inert graphene surface, after it is combined with surface-treated polytetrafluoroethylene, polytetrafluoroethylene can be inserted into the interlayer gaps of multi-layer graphene, inhibiting the agglomeration of graphene itself, thereby promoting its dispersibility in the matrix; at the same time, the advantages of polymer nucleating agents and inorganic nucleating agents are exerted to improve the mechanical properties and thermal properties of the products.

[0008] In a specific feasible embodiment, the mass ratio of the polytetrafluoroethylene to the multi-layer graphene is (6 - 8):(2 - 4).

[0009] By adopting the above technical solution, optimizing the mass ratio of polytetrafluoroethylene and graphene, the obtained nucleating agent composition has a better crystallization effect on the resin.

[0010] In a specific feasible embodiment, the preparation method of the multi-layer graphene is: putting expanded graphite into an ethanol solution and performing ultrasonic treatment to obtain multi-layer graphene.

[0011] By adopting the above technical solution, the appearance of expanded graphite is worm-like, composed of many adhered and stacked graphite flakes, and there are many honeycomb-like fine pores between the flakes. In this application, expanded graphite is used to prepare multi-layer graphene, which enables polytetrafluoroethylene to be inserted into the interlayer spacing of multi-layer graphene; at the same time, ultrasonic waves are generated by mechanical vibration, can propagate in the liquid, and cause the rapid expansion of tiny bubbles in the liquid. The shock wave generated by ultrasonic expansion can apply an expansion force to the interlayer of two-dimensional materials. When the shock wave propagates to the pores of two-dimensional materials, a local high-pressure area is generated, which not only causes the expanded graphite to be peeled off to form multi-layer graphene, but also expands the interlayer spacing of multi-layer graphene, so that multi-layer graphene is expanded.

[0012] In a specific feasible embodiment, the expanded graphite is obtained by subjecting graphite to oxidation treatment and then high-temperature expansion.

[0013] By adopting the above technical solution, using an oxidant to react with graphite to form an ionic compound stored in the pores of graphite to expand the pores of graphite, which is beneficial for polytetrafluoroethylene to be inserted into the lamellae of multi-layer graphene, improving the binding property between the two.

[0014] In a specific feasible embodiment, the polytetrafluoroethylene is obtained by plasma treatment in an atmosphere of nitrogen-containing gas and in the presence of polyethylene glycol.

[0015] By adopting the above technical solution, when the inventor was looking for a suitable polymer nucleating agent, it was considered that polytetrafluoroethylene has excellent heterogeneous nucleation effect, but the compatibility of polytetrafluoroethylene is poor and it is easy to agglomerate in the system, which is not conducive to better dispersion in graphene; introducing polyethylene glycol on the surface of polytetrafluoroethylene can effectively improve the surface activity of polytetrafluoroethylene, and through plasma treatment, on the one hand, grafting of polytetrafluoroethylene and polyethylene glycol is realized, and on the other hand, the change of the surface structure of polytetrafluoroethylene and polyethylene glycol improves the adhesion, which is beneficial to the adhesion of polytetrafluoroethylene on graphene and further improves the combination of the two.

[0016] In a specific feasible embodiment, the nucleating agent composition further includes a sorbitol nucleating agent, and the sorbitol nucleating agent is one or more of bis-1,3:2,4-(4'-propylbenzylidene)-1-propyl sorbitol, 1,3:2,4-dibenzylidene sorbitol, 1,3:2,4-di(p-methylbenzylidene) sorbitol, and 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol.

[0017] By adopting the above technical solution, the sorbitol nucleating agent first forms a dimer through intermolecular hydrogen bonds. This dimer has a stable V-shaped structure and can well accommodate the resin with a helical structure, restricting the movement of the resin molecules with a helical structure. On the one hand, it reduces the probability of its returning to the random coil, and on the other hand, it reduces the crystallization free energy, thereby promoting the nucleation of the resin. In this application, by adding a sorbitol nucleating agent as an organic nucleating agent, its π-π bond with the hydrogen bond and interaction of multi-layer graphene, and the multi-layer graphene and the sorbitol nucleating agent are mutually dispersed, improving the uniformity of its dispersion in the matrix resin, doubling the nucleation sites of the matrix resin, accelerating the crystallization process of the matrix resin, and increasing the crystallinity; at the same time, the sorbitol nucleating agent can modify the surface of multi-layer graphene through hydrogen bond interaction, adjust its compatibility with the resin, and further improve the nucleation effect of the nucleating agent composition. Through the synergistic effect of the three, the mechanical properties and thermodynamic properties of the product are jointly improved.

[0018] In the second aspect, the present application provides a preparation method of a nucleating agent composition, adopting the following technical solution:

[0019] A preparation method of a nucleating agent composition is: adding multi-layer graphene into deionized water and ultrasonicating to obtain a suspension, adding polytetrafluoroethylene and mixing, washing and drying to make polytetrafluoroethylene adsorbed in the multi-layer graphene to obtain the nucleating agent composition.

[0020] By adopting the above technical solution, the preparation method is simple, and due to the synergistic effect between graphene and polytetrafluoroethylene, the prepared nucleating agent composition has the advantage of being more efficient than a single nucleating agent.

[0021] In a specific feasible embodiment, the preparation method of the nucleating agent composition includes the following steps:

[0022] Add multi-layer graphene into deionized water and ultrasonically obtain a suspension, then add polytetrafluoroethylene and mix. Wash and dry to make the polytetrafluoroethylene adsorbed in the graphene to obtain the nucleating agent composition A;

[0023] Modify the nucleating agent composition A with a silane coupling agent and then disperse it in water to obtain the mixed solution A;

[0024] Add the sorbitol-based nucleating agent into an alcohol solvent and dissolve to obtain the mixed solution B; the mass ratio of the sorbitol-based nucleating agent to the nucleating agent composition A is (35 - 75):(25 - 65);

[0025] Add the mixed solution B into the mixed solution A, ultrasonically disperse and then spray dry to obtain the nucleating agent composition.

[0026] By adopting the above technical solution, the graphene and the polytetrafluoroethylene nucleating agent composition A are modified and then compounded with the sorbitol-based nucleating agent to obtain the nucleating agent composition. Compared with the single sorbitol-based nucleating agent or the nucleating agent composition A, under the same usage amount, the compounded nucleating agent has better mechanical properties and thermal properties; at the same time, the preparation process is simple, and it also has good dispersion and nucleation effects.

[0027] In a specific feasible embodiment, the silane coupling agent is an amino silane coupling agent.

[0028] By adopting the above technical solution, the nucleating agent obtained by compounding graphene and polytetrafluoroethylene is modified with an amino silane coupling agent. This unique "two-terminal group" structure enables the silane coupling agent to build a "molecular bridge" between the nucleating agent composition A and the sorbitol-based nucleating agent, improving the performance and connectivity of the nucleating agent composition; one side of the amino silane coupling agent can react with active groups such as hydroxyl or carboxyl groups on the surface of graphene to form stable chemical bonds, improving the dispersion of graphene; the amino group on the other side improves the binding force between the nucleating agent composition A and the sorbitol nucleating agent through bonding, thus significantly improving the nucleation effect of the nucleating agent composition.

[0029] In the third aspect, the present application provides an application of a nucleating agent composition, adopting the following technical solution.

[0030] Use of the above nucleating agent composition in the preparation of semi-crystalline resins, wherein the semi-crystalline resins are one or more of polypropylene, polyethylene, polylactic acid, and polyurethane.

[0031] By adopting the above technical solution, the nucleating agent composition can be directly blended during the processing of semi-crystalline resins, and can endow the semi-crystalline resins with more excellent mechanical properties and processing properties.

[0032] In summary, the present application has the following beneficial effects:

[0033] 1. In the present application, polytetrafluoroethylene is interspersed in multi-layer graphene sheets to form a nucleating agent composition. Through the synergistic effect between different nucleating agents, a nucleating agent composition that is more efficient than a single nucleating agent is prepared;

[0034] 2. In the present application, polytetrafluoroethylene is modified by polyethylene glycol, which not only facilitates the dispersion of polytetrafluoroethylene in graphene, but also facilitates the attachment of polytetrafluoroethylene to graphene, improves the binding property between the two, and thus improves the nucleating property;

[0035] 3. In the present application, a sorbitol-based nucleating agent is added to the nucleating agent composition, and it interacts with the inorganic nucleating agent graphene and the polymer nucleating agent polytetrafluoroethylene, and the mechanical properties and thermodynamic properties of the product are jointly improved. Specific Embodiments

[0036] The present application will be further described in detail below with reference to examples and comparative examples. The raw materials involved in the present application can all be obtained commercially.

[0037] Examples

[0038] Example 1

[0039] In this example, the nucleating agent composition was prepared according to the following steps:

[0040] (1) Preparation of multi-layer graphene:

[0041] Preparation of expanded graphite: Mix 1 ml of 98 wt% concentrated sulfuric acid, 0.1 ml of hydrogen peroxide solution, and 0.1 ml of ammonium persulfate solution to form a treatment solution. While stirring the treatment solution, add 2 g of graphite in small amounts continuously. After reacting for 30 minutes, add a large amount of water (water temperature < 10 °C) and stir continuously to achieve the purpose of activation. Activate at room temperature for 24 h; convey the activated graphite to a dryer for drying to obtain pretreated graphite, the drying temperature is 120 - 160 °C, and the moisture content ≤ 5%; granulate the pretreated graphite with a granulator, and control the average mesh number at 200 - 300 mesh; calcine the granulated material at a temperature of 600 - 800 °C to obtain expanded graphite;

[0042] Place the above expanded graphite in a 75 wt% ethanol solution. Under the ultrasonic cavitation effect in a 40 KHz ultrasonic environment, the air between the graphite layers rapidly expands, breaking and dispersing into multi-layer graphene;

[0043] Preparation of polytetrafluoroethylene: Place the polytetrafluoroethylene sheet to be treated into a plasma generating device, and perform plasma surface modification in the ammonia atmosphere area. The treatment power is 200 W, the treatment time is 15 min. After drying and grinding, surface-modified polytetrafluoroethylene with an average particle size of 3 nm is obtained.

[0044] (2) Place 3 g of the above multi-layer graphene in 1 L of deionized water, and ultrasonicate for 3 h to obtain a multi-layer graphene suspension; add 7 g of the above polytetrafluoroethylene to the suspension, and stir magnetically at a constant temperature of 70 °C for 1 h to form a mixed solution. After the reaction ends, centrifuge and separate, and wash the product with distilled water and dry to constant weight to obtain a nucleating agent composition.

[0045] Example 2

[0046] The difference between this example and Example 1 is that in this example, (3) Place 4 g of the above multi-layer graphene in 1 L of deionized water, and ultrasonicate for 3 h to obtain a multi-layer graphene suspension; add 6 g of the above polytetrafluoroethylene to the suspension, and stir magnetically at a constant temperature of 70 °C for 1 h to form a mixed solution. After the reaction ends, centrifuge and separate, and wash the product with distilled water and dry to constant weight to obtain a nucleating agent composition.

[0047] Example 3

[0048] The difference between this example and Example 1 is that in this example, (3) Place 2 g of the above multi-layer graphene in 1 L of deionized water, and ultrasonicate for 3 h to obtain a multi-layer graphene suspension; add 8 g of the above polytetrafluoroethylene to the suspension, and stir magnetically at a constant temperature of 70 °C for 1 h to form a mixed solution. After the reaction ends, centrifuge and separate, and wash the product with distilled water and dry to constant weight to obtain a nucleating agent composition.

[0049] Example 4

[0050] In this example, the nucleating agent composition is prepared according to the following steps:

[0051] (1) Preparation of multi-layer graphene:

[0052] Preparation of expanded graphite: Mix 1 ml of 98 wt% concentrated sulfuric acid, 0.1 ml of hydrogen peroxide solution and 0.1 ml of ammonium persulfate solution to form a treatment solution. While stirring the treatment solution, gradually add 2 g of graphite in small amounts. After reacting for 30 min, add a large amount of water (water temperature < 10 °C) and continuously stir to achieve the purpose of activation. Activate at room temperature for 24 h; Transport the activated graphite to a dryer for drying to obtain pretreated graphite, with a drying temperature of 120 - 160 °C and water content ≤ 5%; Granulate the pretreated graphite with a granulator, and control the average mesh number to be 200 - 300 mesh; Roast the granulated material at a temperature of 600 - 800 °C to obtain expanded graphite;

[0053] Place the above expanded graphite in a 75 wt% ethanol solution, and utilize the ultrasonic cavitation effect in an ultrasonic environment of 40 KHz to rapidly expand the air between the graphite layers, break and disperse multilayer graphene;

[0054] Preparation of polytetrafluoroethylene: Immerse the nano-polytetrafluoroethylene powder to be treated in a polyethylene glycol / ethanol solution with a molecular weight of 1000, where the concentration of polyethylene glycol is 80%. After soaking at room temperature for 3 h, take it out and dry it at 75 °C to remove the solvent. Then place it in a plasma generating device and perform plasma surface modification in the ammonia atmosphere area, with a treatment power of 200 W and a treatment time of 15 min. Then wash it with deionized water to remove the polyethylene glycol that has not been grafted onto the polytetrafluoroethylene, and obtain surface-modified polytetrafluoroethylene with an average particle size of 3 nm after drying and grinding.

[0055] (2) Place 3 g of the above multilayer graphene in 1 L of deionized water and ultrasonicate for 3 h to obtain a multilayer graphene suspension; Add 7 g of the above polytetrafluoroethylene to the suspension and stir magnetically at a constant temperature of 70 °C for 1 h to form a mixed solution. After the reaction ends, perform centrifugal separation, and wash the product with distilled water and dry it to constant weight to obtain a nucleating agent composition.

[0056] Example 5

[0057] In this example, the nucleating agent composition is prepared according to the following steps:

[0058] (1) Preparation of multilayer graphene:

[0059] Preparation of expanded graphite: Mix 1 ml of 98 wt% concentrated sulfuric acid, 0.1 ml of hydrogen peroxide solution, and 0.1 ml of ammonium persulfate solution to form a treatment solution. While stirring the treatment solution, gradually add 2 g of graphite in small amounts. After reacting for 30 min, add a large amount of water (water temperature < 10 °C) and continuously stir to achieve the purpose of activation. Activate at room temperature for 24 h; transfer the activated graphite to a dryer for drying to obtain pretreated graphite, with a drying temperature of 120 - 160 °C and moisture content ≤ 5%; granulate the pretreated graphite using a granulator, and control the average mesh number at 200 - 300 meshes; calcine the granulated material at a temperature of 600 - 800 °C to obtain expanded graphite;

[0060] Place the above expanded graphite in a 75 wt% ethanol solution, and under the ultrasonic cavitation effect in a 40 KHz ultrasonic environment, rapidly expand the air between the graphite layers, break and disperse to obtain multi-layer graphene.

[0061] (2) Preparation of polytetrafluoroethylene: Immerse the polytetrafluoroethylene sheet to be treated in a polyethylene glycol / ethanol solution with a molecular weight of 1000, where the concentration of polyethylene glycol is 80%. After soaking at room temperature for 3 h, take it out and dry it at 75 °C to remove the solvent. Then place it in a plasma generating device and perform plasma surface modification in the ammonia atmosphere area, with a treatment power of 200 W and a treatment time of 15 min. Then wash it with deionized water to remove the polyethylene glycol that has not been grafted onto the polytetrafluoroethylene, and after drying and grinding, obtain surface-modified polytetrafluoroethylene with an average particle size of 3 nm.

[0062] (3) Place 3 g of the above multi-layer graphene in 1 L of deionized water and ultrasonicate for 3 h to obtain a multi-layer graphene suspension; add 7 g of the above polytetrafluoroethylene to the suspension and stir magnetically at a constant temperature of 70 °C for 1 h to form a mixed solution. After the reaction ends, perform centrifugal separation, wash the product with distilled water and dry it to a constant weight to obtain nucleating agent composition A.

[0063] (4) Disperse 6.5 g of nucleating agent composition A and 0.4 g of KH550 in a mixed solution of 300 ml of deionized water and 600 ml of ethanol, and then react at 80 °C for 4 h to obtain modified mixed solution A; add 3.5 g of 1,3:2,4 - bis(p - methylbenzylidene)sorbitol to anhydrous ethanol and stir until completely dissolved to obtain mixed solution B; add mixed solution B to mixed solution A, ultrasonically disperse for 30 min, mix well and then add it to a spray dryer for spray drying, with an inlet air temperature of 150 °C and an outlet air temperature of 80 °C to prepare the nucleating agent composition.

[0064] Example 6

[0065] The difference between this example and Example 5 is that in this example, (4) 4.5 g of nucleating agent composition A and 0.4 g of KH550 are dispersed in a mixed solution of 300 ml of deionized water and 600 ml of ethanol, and then reacted at 80 °C for 4 h to obtain a modified mixed solution A; 5.5 g of 1,3∶2,4-bis(p-methylbenzylidene)sorbitol is added to absolute ethanol and stirred until completely dissolved to obtain a mixed solution B; the mixed solution B is added to the mixed solution A, ultrasonically dispersed for 30 min, and after mixing, it is added to a spray dryer for spray drying, with an inlet air temperature of 150 °C and an outlet air temperature of 80 °C to obtain the nucleating agent composition.

[0066] Example 7

[0067] The difference between this example and Example 5 is that in this example, (4) 2.5 g of nucleating agent composition A and 0.4 g of KH550 are dispersed in a mixed solution of 300 ml of deionized water and 600 ml of ethanol, and then reacted at 80 °C for 4 h to obtain a modified mixed solution A; 7.5 g of 1,3∶2,4-bis(p-methylbenzylidene)sorbitol is added to absolute ethanol and stirred until completely dissolved to obtain a mixed solution B; the mixed solution B is added to the mixed solution A, ultrasonically dispersed for 30 min, and after mixing, it is added to a spray dryer for spray drying, with an inlet air temperature of 150 °C and an outlet air temperature of 80 °C to obtain the nucleating agent composition.

[0068] Comparative example

[0069] Comparative example 1

[0070] The nucleating agent in this comparative example is multi-layer graphene, and the preparation method of multi-layer graphene is as follows:

[0071] Preparation of expanded graphite: 1 ml of 98 wt% concentrated sulfuric acid is mixed with 0.1 ml of hydrogen peroxide solution and 0.1 ml of ammonium persulfate solution to form a treatment solution. While stirring the treatment solution, 2 g of graphite is added in small amounts continuously. After reacting for 30 min, a large amount of water (water temperature < 10 °C) is added and stirred continuously to achieve the purpose of activation, and activation is carried out at room temperature for 24 h; the activated graphite is transported to a dryer for drying to obtain pretreated graphite, with a drying temperature of 120 - 160 °C and a moisture content ≤ 5%; the pretreated graphite is granulated by a granulator, and the average mesh number is controlled at 200 - 300 mesh; the granulated material is calcined at a temperature of 600 - 800 °C to obtain expanded graphite;

[0072] The above expanded graphite is placed in a 75 wt% ethanol solution, and under a 40 KHz ultrasonic environment, the ultrasonic cavitation effect is used to rapidly expand the air between the graphite layers, break and disperse multi-layer graphene.

[0073] Comparative example 2

[0074] The nucleating agent in this comparative example is polytetrafluoroethylene powder, and the preparation method of the polytetrafluoroethylene powder is as follows: the polytetrafluoroethylene to be treated is dried and ground to obtain polytetrafluoroethylene powder with an average particle size of 3 nm.

[0075] Comparative Example 3

[0076] The nucleating agent in this comparative example is a mixture formed by uniformly mixing 4 g of multi-layer graphene and 6 g of nano-polytetrafluoroethylene powder. (The preparation method of multi-layer graphene is the same as that in Comparative Example 1, and the preparation method of polytetrafluoroethylene is the same as that in Comparative Example 2)

[0077] Comparative Example 4

[0078] The nucleating agent in this comparative example is a mixture formed by uniformly mixing 1.95 g of multi-layer graphene, 4.55 g of nano-polytetrafluoroethylene powder and 3.5 g of 1,3:2,4-bis(p-methylbenzylidene)sorbitol. (The preparation method of multi-layer graphene is the same as that in Comparative Example 1, and the preparation method of polytetrafluoroethylene is the same as that in Comparative Example 2)

[0079] Application

[0080] 1.5 g of the nucleating agent of each of the examples and comparative examples was respectively added to 1000 g of block copolymer polypropylene J641. After mixing and stirring evenly in a high-speed mixer, it was melt-extruded and pelletized by a twin-screw extruder, and then injection-molded into standard sample strips, which were used as subsequent test samples. The extrusion temperature was 280 ± 10 °C, and the temperatures of each section of the injection molding machine were 300 - 350 °C.

[0081] Performance Detection Test Method

[0082] The tests were carried out according to GB 2918-1998 (Standard Environment for Conditioning and Testing of Plastic Specimens) under the conditions of (23 ± 2) °C and a relative humidity (RH) of (50 ± 5)%, and the specimen conditioning time was 48 h.

[0083] I. Mechanical Property Tests

[0084] According to the "GB / T 1843-1996 Test Method for Izod Impact Strength of Plastics", the impact strength of the sample strips prepared from each of the examples and comparative examples was tested, and the test results are shown in Table 1.

[0085] According to the "GB / T 9341-2000 Determination of Flexural Properties of Plastics", the flexural modulus of the sample strips prepared from each of the examples and comparative examples was tested, and the test results are shown in Table 1.

[0086] II. Thermal Property Tests

[0087] According to the "GB / T1634-2004 Determination of Heat Deflection Temperature of Plastics", the heat deflection temperature of the sample strips prepared from each of the examples and comparative examples was tested, and the test results are shown in Table 1.

[0088] Table 1 Performance Detection Data Sheet of Examples 1-7 and Comparative Examples 1-4

[0089]

[0090] Combining Example 1 and Comparative Examples 1-3 and referring to Table 1, it can be seen that the mechanical properties and thermal properties of Example 1 are superior to those of Comparative Examples 1-3. This shows that by interspersing polytetrafluoroethylene in multi-layer graphene sheets in this application, not only does it play the synergistic effect of polytetrafluoroethylene and graphene as nucleating agents, which is more efficient than a single nucleating agent, but it also inhibits the agglomeration of graphene itself, thereby promoting its dispersibility in the resin and improving the mechanical properties and thermal properties of the product.

[0091] Combining Example 1 and 4 and referring to Table 1, it can be seen that by introducing polyethylene glycol on the surface of polytetrafluoroethylene in this application, the surface activity of polytetrafluoroethylene can be effectively improved. And through plasma treatment, on the one hand, the grafting of polytetrafluoroethylene and polyethylene glycol is realized, and on the other hand, the change in the surface structure of polytetrafluoroethylene and polyethylene glycol improves the adhesiveness, which is beneficial to the attachment of polytetrafluoroethylene on graphene, further improving the combination of polytetrafluoroethylene and multi-layer graphene, thereby improving the mechanical properties and thermal properties of the product.

[0092] Combining Example 5 and Comparative Example 4 and referring to Table 1, it can be seen that for the nucleating agent composition prepared in this application, after intercalating polytetrafluoroethylene in multi-layer graphene and then effectively combining it with a sorbitol-based nucleating agent, the formed nucleating agent composition can fully exert the nucleating effects of the three. Compared with the nucleating agent combination formed by simply mixing polytetrafluoroethylene, multi-layer graphene and sorbitol-based nucleating agent, it has a better crystallization effect on the resin, improving the mechanical properties and thermal properties of the product.

[0093] This specific embodiment is only an explanation of this application and is not a limitation of this application. Those skilled in the art can make modifications without creative contributions to this embodiment according to needs after reading this specification, but as long as it is within the scope of the claims of this application, it is protected by the patent law.

Claims

1. A nucleating agent composition, characterized in that The invention comprises polytetrafluoroethylene and multilayer graphene, wherein the polytetrafluoroethylene is interspersed in the multilayer graphene sheet, and the polytetrafluoroethylene is obtained by plasma treatment in a nitrogen-containing atmosphere.

2. The nucleating agent composition according to claim 1, characterized in that The mass ratio of the polytetrafluoroethylene and the multilayer graphene is (6-8): (2-4).

3. The nucleating agent composition according to claim 2, characterized in that The preparation method of the multilayer graphene is as follows: expanding graphite is placed in an ethanol solution and ultrasonically treated to obtain the multilayer graphene.

4. The nucleating agent composition according to claim 3, characterized in that The expanded graphite is obtained by oxidizing graphite and then expanding it at high temperature.

5. The nucleating agent composition according to claim 1, characterized in that The polytetrafluoroethylene is obtained by plasma treatment in the presence of nitrogen-containing gas atmosphere and polyethylene glycol.

6. The nucleating agent composition according to claim 5, characterized in that The nucleating agent composition also includes a sorbitol nucleating agent, and the sorbitol nucleating agent is one or more of di-1,3:2,4-(4′-propylbenzylidene)-1-propyl sorbitol, 1,3:2,4-dibenzylidene sorbitol, 1,3:2,4-di(p-methylbenzylidene) sorbitol, and 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol.

7. The method for preparing the nucleating agent composition according to any one of claims 1 to 5, characterized in that: The multilayer graphene is added to deionized water and ultrasonically obtained into a suspension, and polytetrafluoroethylene is added and mixed, and then washed and dried, so that the polytetrafluoroethylene is interspersed in the multilayer graphene sheet to obtain the nucleating agent composition.

8. The method for preparing the nucleating agent composition according to claim 7, characterized in that: The following steps are involved: Multilayer graphene is added to deionized water and ultrasonically obtained into a suspension, and polytetrafluoroethylene is added and mixed, and then washed and dried to allow polytetrafluoroethylene to be interspersed in the multilayer graphene sheets to obtain a nucleating agent composition A; The nucleating agent composition A is modified by using a silane coupling agent and then dispersed in water to obtain a mixed solution A; Adding a sorbitol nucleating agent into an alcohol solvent and dissolving the mixture to obtain a mixed solution B; the mass ratio of the sorbitol nucleating agent to the nucleating agent composition A is (35-75): (25-65); The mixed solution B is added to the mixed solution A, and then ultrasonically dispersed and spray-dried to obtain the nucleating agent composition.

9. The method for preparing the nucleating agent composition according to claim 8, characterized in that: The silane coupling agent is an aminosilane coupling agent.

10. The use of the nucleating agent composition according to any one of claims 1 to 9, characterized in that: Used in the preparation of semi-crystalline resin, wherein the semi-crystalline resin is one or more of polypropylene, polyethylene, polylactic acid, and polyurethane.

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