Hyperbranched structure nano dispersant and preparation method and application thereof

Abstract

The invention relates to the technical field of dispersing agent preparation, in particular to a hyperbranched structure nano dispersing agent and a preparation method and application of the hyperbranched structure nano dispersing agent. The preparation method comprises the following steps: reacting 1, 2, 3, 4, 6-tetra-O-tert-valeryl-beta-D-galactopyranosamine with resveratrol oxide to obtain a product, and carrying out hot pressing on the product to obtain a nano-scale product. The prepared hyperbranched structure nano dispersant can be used for preparing graphene slurry, the addition amount is 0.5-5 wt%, graphene can have good dispersing performance in a water-based or oil-based system, the production process is simple, and industrialization is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of dispersant preparation, and in particular to a hyperbranched structure nano dispersant and a preparation method and application thereof. Background Art

[0002] Graphene is a single-layer two-dimensional lattice material composed of carbon atoms. It has extremely high electrical conductivity, thermal conductivity and mechanical strength. Therefore, graphene has broad application prospects in biomedicine, energy storage, new sensors and other fields. However, the surface of graphene is relatively smooth and has a large specific surface area, so it is difficult to interact with water molecules or organic solvents. In addition, graphene has a honeycomb structure and there are π-π conjugated interactions between a large number of ring structures. Therefore, it is difficult to disperse in water or organic solvents. These defects greatly limit the application scenarios of graphene.

[0003] Hyperbranched dispersants are a type of commonly used additives that can disperse graphene in water and oil systems. Structurally, hyperbranched dispersants are a type of polymer material composed of multi-branched central atoms and multiple anchor points on the branches, which can anchor graphene and promote the dispersion of graphene.

[0004] Patent CN108948851B provides a hyperbranched dispersant and a preparation method thereof, wherein 1,3,5-trihydroxycyclohexane is used as a central atom to prepare a hyperbranched dispersant with a large molecular weight. The central atom used has the advantages of simple structure, simple production process, high purity and low cost. The hyperbranched dispersant has good wettability and dispersibility for pigments and good compatibility with various resins. However, a catalyst precursor and 1,3,5-trihydroxycyclohexane need to be synthesized before synthesizing the hyperbranched dispersant, and the preparation process is relatively complicated, making it difficult to produce on an industrial scale.

[0005] Patent CN101475687B provides an amphiphilic hyperbranched polymer with a specific topological structure, which is obtained by condensation polymerization of primary amine RNH2 and its derivatives with multi-acrylate functional monomers to obtain a hyperbranched polymer containing a poly(ester-amine) structure. The polymer can be applied to the fields of new polymer surfactants, pigment wetting dispersants, and dissolving dispersants for organic and inorganic substances. However, there is only a covalent bond force between the dispersant and graphene, and the interaction force is small, resulting in a poor dispersion effect on graphene.

[0006] Therefore, the market is in urgent need of developing a hyperbranched nanodispersant that can stably disperse graphene in aqueous and oily systems and has a simple production process. Summary of the invention

[0007] In view of the problems existing in the prior art, the purpose of the present invention is to develop a hyperbranched structure nanodispersant that can stably disperse graphene in aqueous and oily systems and has a simple production process.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides a hyperbranched nanodispersant, the structural formula of the hyperbranched nanodispersant is as follows:

[0010]

[0011] Among them, R is * is the connection site.

[0012] The present application develops a hyperbranched nano-dispersant, which contains hydrophilic amino groups, hydroxyl groups and ether bond groups, and hydrophobic ester groups and tert-butyl groups, giving the hyperbranched nano-dispersant amphiphilic properties. In addition, the hyperbranched nano-dispersant contains multiple benzene ring groups. Compared with conventional dispersants, the multiple benzene rings can generate extremely strong π-π forces with graphene, and the multiple ester groups can generate extremely strong covalent bond forces with graphene, which can further enhance the adsorption of the dispersant to graphene.

[0013] The second aspect of the present invention provides a method for preparing a hyperbranched structure nanodispersant, comprising the following steps:

[0014] A1, adding multifunctional acrylate, 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine, a catalyst and anhydrous ethanol into a reaction container, reacting at 55-65° C. for 30-60 min, washing, filtering and drying to obtain a prepolymer;

[0015] A2, adding the prepolymer obtained in step A1, resveratrol oxide and azobisisobutyronitrile to methanol, heating to 60-80° C. to react for 2-4 hours, washing, filtering and drying to obtain a hyperbranched structure dispersant;

[0016] A3. Add the hyperbranched structure dispersant obtained in step A2 into a single screw extruder and extrude it at a temperature of 170-180° C., then put it into a hot press mold and hot-press for 6-8 minutes to obtain a hyperbranched structure nano dispersant.

[0017] In some embodiments, the hot pressing is performed at a temperature of 110-120° C. and a pressure of 16-18 MPa.

[0018] In the present application, a multifunctional acrylate is first subjected to Michael addition reaction with 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosylgalactosamine, and then reacted with oxidized resveratrol through double bond polymerization to obtain a hyperbranched structure dispersant. Finally, the hyperbranched structure dispersant is hot-pressed into a nanoscale, so that the hyperbranched structure dispersant is easily soluble in an aqueous or oily system, thereby improving the adsorption of graphene.

[0019] In some embodiments, the multifunctional acrylate is one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0020] Preferably, the multifunctional acrylate is pentaerythritol triacrylate.

[0021] In some embodiments, the catalyst is one or more of sodium ethoxide, sodium hydride, and sodium amide.

[0022] Preferably, the catalyst is sodium ethoxide.

[0023] In some embodiments, the number average molecular weight of the hyperbranched structure dispersant is 30,000-50,000.

[0024] The present application limits the number average molecular weight of the hyperbranched structure dispersant, which can provide a rich branched structure while making the dispersant have a higher solubility in the solvent, and is beneficial to improving the dispersibility of the hyperbranched structure nanodispersant.

[0025] In some embodiments, the mass ratio of the multifunctional acrylate to 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosylgalactosamine in step A1 is 1:(1.3-1.7).

[0026] The present application can ensure the dispersibility of the hyperbranched structure nanodispersant in aqueous and oily systems by selecting a specific ratio of multifunctional acrylate and 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine. This may be because the hydrophilicity of the ether bond, the interaction force between the ester group and graphene, and the hydrophobicity of the tert-butyl group can achieve a hydrophilic and lipophilic balance under this ratio, making the dispersant suitable for various systems.

[0027] In some embodiments, the mass ratio of the prepolymer to the oxidized resveratrol in step A2 is 1:(0.4-0.5).

[0028] The present application can improve the dispersibility of the hyperbranched nanodispersant by selecting a specific ratio of prepolymer and oxidized resveratrol. This may be because the multiple active groups left in the two segments of the molecular chain after the double bond polymerization reaction can transfer charges with graphene, thereby promoting the adsorption of the dispersant on graphene.

[0029] The third aspect of the present invention provides an application of a hyperbranched structure nano-dispersant, wherein the hyperbranched structure nano-dispersant is used in a method for preparing a graphene slurry, comprising the following steps: adding graphene, a solvent and a hyperbranched structure nano-dispersant into a reaction container and stirring at room temperature for 20-30 minutes, wherein the addition amount of the hyperbranched structure nano-dispersant is 0.5-5wt%, and the addition amount of the solvent is 80-90wt%.

[0030] In some embodiments, the solvent is ethylene glycol monobutyl ether.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention designs a hyperbranched nano-dispersant with amphiphilic properties. The hyperbranched nano-dispersant contains multiple benzene ring groups. Compared with conventional dispersants, multiple benzene rings can produce extremely strong π-π forces with graphene, which can further enhance the adsorption of the dispersant to graphene, thereby promoting the dispersion of graphene. In addition, by limiting the number average molecular weight of the hyperbranched nano-dispersant, the present application can provide a rich branched structure while making the solubility of the dispersant in the oily system higher, which is beneficial to improving the dispersibility of the hyperbranched nano-dispersant.

[0033] 2. The present invention reacts a multifunctional acrylate with 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosylgalactosamine and then with oxidized resveratrol to obtain a hyperbranched structure dispersant, and finally hot-presses the hyperbranched structure dispersant into a nanoscale, so that the hyperbranched structure dispersant is easily soluble in an aqueous or oily system, thereby improving the adsorption of graphene.

[0034] 3. The present invention can ensure the dispersibility of the hyperbranched structure nanodispersant in aqueous and oily systems by selecting a specific ratio of multifunctional acrylate and 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine, and improve the dispersibility of the hyperbranched structure nanodispersant by selecting a specific ratio of prepolymer and oxidized resveratrol. DETAILED DESCRIPTION

[0035] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0036] In the following examples and comparative examples, the compounds and related reagents used can be purchased from the market. The graphene particle size is 3-9 nm, purchased from Nangong Jiuxin New Material Technology Co., Ltd.; the model of the water-based epoxy resin is EP137, purchased from Shanghai Yantai E-Commerce Co., Ltd.; the acrylate varnish base material is purchased from Shanghai Shiying Chemical Co., Ltd.

[0037] Example 1

[0038] A method for preparing a hyperbranched structure nanodispersant comprises the following steps:

[0039] A1. Add 10 g of pentaerythritol triacrylate, 15 g of 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine, 0.01 g of sodium ethoxide and 50 g of anhydrous ethanol into a reaction container, stir at 60° C. for 45 min, wash, filter and dry to obtain a prepolymer;

[0040] A2, adding 20g of the prepolymer obtained in step A1, 9g of resveratrol oxide, and 0.01g of azobisisobutyronitrile to 50g of anhydrous methanol, heating to 70°C for reaction, washing, filtering, and drying to obtain a hyperbranched structure dispersant with a number average molecular weight of 40369;

[0041] A3. Add 25 g of the hyperbranched structure dispersant obtained in step A2 into a single screw extruder at an extrusion temperature of 175° C. and 95 r / min, and then place it into a hot press mold and hot press for 7 minutes at a temperature of 115° C. and a pressure of 17 MPa to obtain a hyperbranched structure nanodispersant.

[0042] Example 2

[0043] A method for preparing a hyperbranched structure nanodispersant comprises the following steps:

[0044] A1, add 10g of pentaerythritol triacrylate, 13g of 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine, 0.01g of sodium ethoxide and 50g of anhydrous ethanol into a reaction container, stir at 55°C for 60min, wash, filter and dry to obtain a prepolymer;

[0045] A2, adding 20g of the prepolymer obtained in step A1, 8g of resveratrol oxide, and 0.01g of azobisisobutyronitrile to 50g of anhydrous methanol, heating to 60°C for reaction, washing, filtering, and drying to obtain a hyperbranched structure dispersant with a number average molecular weight of 30478;

[0046] A3. Add 25 g of the hyperbranched structure dispersant obtained in step A2 into a single screw extruder and extrude it at a temperature of 170° C., then put it into a hot press mold and hot-press it for 6 minutes at a temperature of 110° C. and a pressure of 18 MPa to obtain a hyperbranched structure nanodispersant.

[0047] Example 3

[0048] A method for preparing a hyperbranched structure nanodispersant comprises the following steps:

[0049] A1. Add 10 g of pentaerythritol triacrylate, 15 g of 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine, 0.01 g of sodium ethoxide and 50 g of anhydrous ethanol into a reaction container, stir at 65° C. for 30 min, wash, filter and dry to obtain a prepolymer;

[0050] A2, adding 20g of the prepolymer obtained in step A1, 9g of resveratrol oxide, and 0.01g of azobisisobutyronitrile to 50g of anhydrous methanol, heating to 80°C for reaction, washing, filtering, and drying to obtain a hyperbranched structure dispersant with a number average molecular weight of 50372;

[0051] A3. Add 25 g of the hyperbranched structure dispersant obtained in step A2 into a single screw extruder and extrude it at a temperature of 180° C., then put it into a hot press mold and hot-press it for 8 minutes at a temperature of 120° C. and a pressure of 16 MPa to obtain a hyperbranched structure nano-dispersant.

[0052] Example 4

[0053] A method for preparing a hyperbranched nanodispersant, the specific implementation manner is the same as that of Example 1, except that the added amount of 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosylgalactosamine is 20 g.

[0054] Example 5

[0055] A method for preparing a hyperbranched nanodispersant, the specific implementation method is the same as that of Example 1, except that the amount of resveratrol oxide added is 7 g.

[0056] Example 6

[0057] A method for preparing a hyperbranched nanodispersant, the specific implementation method is the same as that of Example 1, except that the number average molecular weight of the hyperbranched nanodispersant is 25337.

[0058] Performance Testing

[0059] (1) Sample preparation

[0060] 1. The hyperbranched structure nanodispersant obtained in each embodiment is used to prepare a graphene slurry, comprising the following steps: 9g of graphene, 88g of ethylene glycol monobutyl ether and 3g of hyperbranched structure nanodispersant are added to a reaction vessel and stirred at room temperature for 25min to obtain a graphene slurry. The graphene slurry without the hyperbranched structure nanodispersant is used as a blank sample. Each graphene slurry is added to a water-based epoxy resin in an amount of 2.5wt%, and stirred at room temperature for 20min to obtain a water-based epoxy resin.

[0061] 2. Mix 1 g of the hyperbranched nanodispersant obtained in each example, 3 g of graphene and 97 g of acrylic varnish base material, and stir at room temperature for 20 min to obtain acrylic varnish. The acrylic varnish without the hyperbranched nanodispersant is used as a blank sample.

[0062] (2) Performance testing

[0063] 1. Take 100g of each water-based epoxy resin and place it in an oven at 50°C. After 4 days, observe the stratification of the water-based epoxy resin to determine the storage stability, and use a viscometer to test the viscosity of each water-based epoxy resin at 25°C to determine the dispersibility of the graphene slurry in the water-based system;

[0064] 2. Take 100g of each acrylic varnish and place it in an oven at 50°C. After 4 days, observe the stratification of the acrylic varnish to determine the storage stability, and use a viscometer to test the viscosity of each acrylic varnish at 25°C to determine the dispersibility of the graphene slurry in the oily system.

[0065] The test results are shown in Table 1:

[0066] Table 1

[0067]

[0068] It can be seen from the data in Table 1 that, compared with the blank sample, the water-based epoxy resin and acrylic varnish containing the hyperbranched structure nanodispersant prepared in Examples 1-3 have good storage stability and low viscosity, indicating that the hyperbranched structure nanodispersant prepared in Examples 1-3 can make graphene have good dispersibility in both water-based systems and oily systems. From the comparison between Example 4 and Example 1, it can be seen that after changing the ratio of 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosylgalactosamine, the hydrophilicity of the ether bond, the interaction force between the ester group and graphene, and the hydrophobicity of the tert-butyl group cannot achieve a hydrophilic and lipophilic balance under this ratio, resulting in the deterioration of the dispersibility of graphene in both water-based systems and oily systems, which makes the storage stability of water-based epoxy resin and acrylic varnish worse and the viscosity increased; from the comparison between Example 5 and Example 1, it can be seen that after changing the ratio of oxidized resveratrol, the active groups left in the two segments of the molecular chain after the double bond polymerization reaction are insufficient. Charge transfer occurs with graphene, and the adsorption of graphene by the hyperbranched nano-dispersant cannot be promoted, resulting in the deterioration of the dispersibility of graphene in both aqueous and oily systems, which causes the storage stability of water-based epoxy resin and acrylic varnish to deteriorate and the viscosity to increase; from the comparison of Example 6 with Example 1, it can be seen that by changing the number average molecular weight of the hyperbranched nano-dispersant, the dispersant cannot provide abundant branched structures, which reduces the dispersibility of the hyperbranched nano-dispersant, resulting in the deterioration of the dispersibility of graphene in both aqueous and oily systems, which causes the storage stability of water-based epoxy resin and acrylic varnish to deteriorate and the viscosity to increase.

[0069] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A hyperbranched nanodispersant, characterized in that: The structural formula of the hyperbranched nanodispersant is as follows: Among them, R is * is the connection site.

2. A method for preparing the hyperbranched structure nanodispersant according to claim 1, characterized in that: The following steps are involved: A1, adding multifunctional acrylate, 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosyl galactosamine, a catalyst and anhydrous ethanol into a reaction container, reacting at 55-65° C. for 30-60 min, washing, filtering and drying to obtain a prepolymer; A2, adding the prepolymer obtained in step A1, resveratrol oxide and azobisisobutyronitrile to methanol, heating to 60-80° C. to react for 2-4 hours, washing, filtering and drying to obtain a hyperbranched structure dispersant; A3. Add the hyperbranched structure dispersant obtained in step A2 into a single screw extruder and extrude it at a temperature of 170-180° C., then put it into a hot press mold and hot-press for 6-8 minutes to obtain a hyperbranched structure nano dispersant.

3. The method for preparing a hyperbranched structure nanodispersant according to claim 2, characterized in that: The temperature of the hot pressing is 110-120° C., and the pressure is 16-18 MPa.

4. The method for preparing a hyperbranched structure nanodispersant according to claim 2, characterized in that: The multifunctional acrylate is one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

5. The method for preparing a hyperbranched structure nanodispersant according to claim 2, characterized in that: The catalyst is one or more of sodium ethoxide, sodium hydride and sodium amide.

6. The hyperbranched structure nanodispersant according to claim 2, characterized in that: The number average molecular weight of the hyperbranched structure dispersant is 30,000-50,000.

7. The method for preparing a hyperbranched structure nanodispersant according to claim 2, characterized in that: The mass ratio of the multifunctional acrylate and 2,3,4,6-tetra-O-tert-valeryl-beta-D-pyranosylgalactosamine in step A1 is 1:(1.3-1.7).

8. The method for preparing a hyperbranched structure nanodispersant according to claim 2, characterized in that: The mass ratio of the prepolymer to the oxidized resveratrol in step A2 is 1:(0.4-0.5).

9. Use of the hyperbranched nanodispersant according to claim 1 or the hyperbranched nanodispersant prepared by the preparation method according to any one of claims 2 to 8, characterized in that: The method for preparing graphene slurry using the hyperbranched structure nano-dispersant comprises the following steps: adding graphene, solvent and hyperbranched structure nano-dispersant into a reaction container and stirring at room temperature for 20-30 minutes, wherein the addition amount of the hyperbranched structure nano-dispersant is 0.5-5wt%, and the addition amount of the solvent is 80-90wt%.

10. The use of the hyperbranched structure nanodispersant according to claim 9, characterized in that: The solvent is ethylene glycol monobutyl ether.

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