阅读说明：本技术 一种吸附用的插层石墨烯共混聚氨酯开孔海绵的制备方法 (Preparation method of intercalated graphene blended polyurethane open-cell sponge for adsorption ) 是由 葛存旺 商赛男 韩欣雨 陈宾旺 何婷婷 苏林燕 杜妍妍 秦天 李康 李华灵 于 2021-08-31 设计创作，主要内容包括：本发明涉及石墨烯应用领域,具体公开了一种吸附用的插层石墨烯共混聚氨酯开孔海绵的制备方法,包括以下步骤：S1、插层石墨烯纳米片的制备：利用鳞片石墨制备出氧化石墨,然后经过水热插层二元醇制备出插层石墨烯纳米片；S2、石墨烯分散液的制备；S3、发泡海绵的制备：将S2中制备的石墨烯分散液与助剂、异氰酸酯通过泵混合发泡得到发泡海绵；S4、海绵成品的制备：将S3中得到的发泡海绵先冷却,然后熟化定型,再经过爆破、裁剪、烘干除味得到海绵成品,即插层石墨烯共混聚氨酯开孔海绵。本发明适应大规模生产的要求,制备中保证了石墨烯的分散,爆破后石墨烯充分的得到暴露和利用,本发明回弹性优,疏水能力强,能较好的吸附室内有害气体。(The invention relates to the field of graphene application, and particularly discloses a preparation method of an intercalation graphene blended polyurethane open-cell sponge for adsorption, which comprises the following steps: s1, preparation of intercalated graphene nanosheets: preparing graphite oxide by using flake graphite, and then preparing an intercalated graphene nanosheet by hydrothermal intercalation dihydric alcohol; s2, preparing a graphene dispersion liquid; s3, preparation of a foaming sponge: mixing and foaming the graphene dispersion liquid prepared in the step S2 with an auxiliary agent and isocyanate through a pump to obtain a foaming sponge; s4, preparing a finished sponge product: and (3) cooling the foamed sponge obtained in the step S3, curing and shaping, blasting, cutting, drying and deodorizing to obtain a finished sponge product, namely the layered graphene blended polyurethane open-cell sponge. The method meets the requirement of large-scale production, ensures the dispersion of the graphene in preparation, fully exposes and utilizes the exploded graphene, and has the advantages of excellent rebound resilience, strong hydrophobic capability and better capability of adsorbing indoor harmful gas.)

1. A preparation method of an intercalated graphene blended polyurethane open-cell sponge for adsorption is characterized by comprising the following steps:

s1, preparation of intercalated graphene nanosheets: preparing graphite oxide by using flake graphite, and then preparing an intercalated graphene nanosheet by hydrothermal intercalation dihydric alcohol;

s2, preparation of graphene dispersion liquid: dispersing the intercalated graphene nanosheets prepared in the S1 in polyether polyol with high viscosity, and dispersing in a sand mill to obtain graphene dispersion liquid;

s3, preparation of a foaming sponge: mixing and foaming the graphene dispersion liquid prepared in the step S2 with an auxiliary agent and isocyanate through a pump to obtain a foaming sponge;

s4, preparing a finished sponge product: and (3) cooling the foamed sponge obtained in the step S3, curing and shaping, blasting, cutting, drying and deodorizing to obtain a finished sponge product, namely the layered graphene blended polyurethane open-cell sponge.

2. The preparation method of the intercalated graphene blended polyurethane open-cell sponge for adsorption according to claim 1, wherein the intercalated graphene nanosheets of S1 are prepared by an oxidation method, namely, graphene oxide is prepared by an improved Hummers method under the condition of ice-water bath, then dihydric alcohol is added, and hydrothermal treatment is carried out for 4 hours at 200 ℃ to obtain few-layer graphene oxide nanosheets, namely, intercalated graphene nanosheets, of which the dihydric alcohol is intercalated.

3. The method for preparing the intercalated graphene blended polyurethane open-cell sponge for adsorption according to claim 2, wherein the improved Hummers method comprises the following steps:

t1, preparing 200-mesh crystalline flake graphite, sodium nitrate and potassium permanganate with the mass ratio of 1:3:3, and evenly dividing the sodium nitrate and the potassium permanganate into three parts;

t2, adding sodium nitrate and potassium permanganate into a reactor filled with 200-mesh flake graphite for three times respectively, and stirring while adding;

t3, heating to 90 ℃ after stirring for 1h, refluxing at constant temperature for 1h, and centrifugally washing with hydrogen peroxide (30%) and 10% hydrochloric acid for three times after the solution turns dark brown.

4. The method for preparing the intercalated graphene blended polyurethane open-cell sponge for adsorption according to claim 2, wherein the diol is ethylene glycol or 1, 4-butanediol.

5. The preparation method of the intercalated graphene blended polyurethane open-cell sponge for adsorption according to claim 1, wherein the content of graphene nanosheets in S2 is 3-5%.

6. The method for preparing the intercalated graphene blended polyurethane open-cell sponge for adsorption according to claim 1, wherein the auxiliary agent in S3 comprises an organic amine catalyst, a tin catalyst, a silicone foam stabilizer and water.

7. The method for preparing the intercalated graphene blended polyurethane open-cell sponge for adsorption according to claim 6, wherein the auxiliary agent, the graphene dispersion liquid and the isocyanate in the step S3 are mixed according to parts by weight and foamed through a pump, and the raw materials comprise, by weight, 60-100 parts of the graphene dispersion liquid, 0.1-0.3 part of an organic amine catalyst, 0.1-0.3 part of a tin catalyst, 1-3 parts of an organic silicon foam stabilizer, 3-6 parts of water and 30-50 parts of toluene diisocyanate.

Technical Field

The invention belongs to the field of graphene application, and particularly relates to a preparation method of an intercalation graphene blended polyurethane open-cell sponge for adsorption.

Background

Graphene is a two-dimensional carbon material which can stably exist in an external environment, and a single-layer graphite sheet layer with carbon atoms arranged in a hexagonal grid shape has a thickness of only one atom size, has a large specific surface area, is one of materials with the highest known strength, has good toughness, can be bent, and is known as the king and black gold of a new material. With the development of graphene preparation technology, the preparation cost of graphene is greatly reduced, so that the graphene is widely applied.

Graphene is prepared into graphene sponge for adsorption by means of a 3D sponge multi-pore channel form and a functionalized sponge structure, the graphene sponge is poor in binding capacity with the sponge in a main physical adsorption method and low in reuse rate in the existing preparation method, the pore channel structure of the sponge is blocked by a resin wrapping method, the adsorption performance of the sponge is not favorably exerted, the graphene is not uniformly distributed in a material prepared by a graphene direct mixing foaming method, and a closed pore structure formed by foaming is not favorable for adsorption.

Therefore, it is required to develop a method for preparing a graphene sponge capable of improving its adsorption performance.

Disclosure of Invention

The invention aims to provide a preparation method of an intercalated graphene blended polyurethane open-cell sponge for adsorption, which comprises the steps of preparing few-layer lamellar intercalated graphene suitable for being applied to the sponge, dispersing the few-layer intercalated graphene into polyether polyol by using a sand mill, and ensuring that graphene can be uniformly dispersed; the opening blasting process is carried out after the foaming material is cured, so that the graphene is fully exposed, the exposed area of the graphene is increased, and the utilization rate of the graphene is improved; the preparation method disclosed by the invention has the advantages of being green, convenient, high in atomic yield, suitable for large-scale industrial production and the like, and the modified sponge material is good in graphene dispersibility, large in addition amount, excellent in sponge resilience, strong in hydrophobic capacity, good in adsorption effect on toluene and ketone gases with heavy air, and capable of being applied to air purification materials.

In order to solve the technical problem, the invention provides a preparation method of an intercalation graphene blended polyurethane open-cell sponge for adsorption, which comprises the following steps:

s1, preparation of intercalated graphene nanosheets: preparing graphite oxide by using flake graphite, and then preparing an intercalated graphene nanosheet by hydrothermal intercalation dihydric alcohol;

s2, preparation of graphene dispersion liquid: dispersing the intercalated graphene nanosheets prepared in the S1 in polyether polyol with high viscosity, and dispersing in a sand mill to obtain graphene dispersion liquid;

s3, preparation of a foaming sponge: mixing and foaming the graphene dispersion liquid prepared in the step S2 with an auxiliary agent and isocyanate through a pump to obtain a foaming sponge;

s4, preparing a finished sponge product: and (3) cooling the foamed sponge obtained in the step S3, curing and shaping, blasting, cutting, drying and deodorizing to obtain a finished sponge product, namely the layered graphene blended polyurethane open-cell sponge.

Preferably, the S1 intercalated graphene nanosheet is prepared by an oxidation method, namely, under the ice-water bath condition, graphene oxide is prepared by an improved Hummers method, then dihydric alcohol is added, and hydrothermal treatment is carried out for 4 hours at the temperature of 200 ℃ to obtain a dihydric alcohol intercalated few-layer graphene oxide nanosheet, namely, the intercalated graphene nanosheet.

Preferably, the improved Hummers method comprises the steps of:

t1, preparing 200-mesh crystalline flake graphite, sodium nitrate and potassium permanganate with the mass ratio of 1:3:3, and evenly dividing the sodium nitrate and the potassium permanganate into three parts;

t2, adding sodium nitrate and potassium permanganate into a reactor filled with 200-mesh flake graphite for three times respectively, and stirring while adding;

t3, heating to 90 ℃ after stirring for 1h, refluxing at constant temperature for 1h, and centrifugally washing with hydrogen peroxide (30%) and 10% hydrochloric acid for three times after the solution turns dark brown.

Preferably, the diol is ethylene glycol or 1, 4-butanediol.

Preferably, the content of the graphene nanoplatelets in the S2 is 3-5%.

Preferably, the assistant in S3 includes an organic amine catalyst, a tin-based catalyst, a silicone foam stabilizer, and water.

Preferably, the assistant, the graphene dispersion liquid and the isocyanate in the step S3 are mixed according to parts by weight and foamed through a pump, and the raw materials respectively comprise, by weight, 60-100 parts of the graphene dispersion liquid, 0.1-0.3 part of an organic amine catalyst, 0.1-0.3 part of a tin catalyst, 1-3 parts of an organic silicon foam stabilizer, 3-6 parts of water and 30-50 parts of toluene diisocyanate.

The invention has the beneficial effects that: the invention meets the requirement of large-scale production, the few-layer intercalated graphene can ensure the dispersion of the graphene, the pore channel of the sponge is fully exposed after blasting, the adsorption performance is conveniently exerted, the invention has better indoor harmful gas adsorption performance, and has better application prospect in the adsorption material market.

Drawings

In order to more clearly illustrate the technical solution of the present invention, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

Fig. 1 is a flow diagram of the preparation of an intercalated graphene blended polyurethane open-cell sponge of the present invention;

FIG. 2 is a scanning electron microscope photograph of a few-layer intercalated graphene prepared by the Hummers method in combination with the hydrothermal method in example 1 of the present invention;

fig. 3 is an optical microscope image of an intercalated graphene blended polyurethane open-cell sponge prepared in example 1 of the present invention;

fig. 4 is a schematic contact angle diagram of an intercalated graphene blended polyurethane open-cell sponge prepared in example 1 of the present invention;

FIG. 5 is a graph of the adsorption performance of paraxylene and cyclohexanone of an intercalated graphene blended polyurethane open-cell sponge prepared in example 1 of the present invention;

fig. 6 is a graph of the adsorption performance of intercalated graphene blended polyurethane open-cell sponges on cyclohexanone and ethanol prepared in example 1 of the present invention;

FIG. 7 is a scanning electron microscope photograph of a few-layer intercalated graphene prepared by the Hummers method in combination with the hydrothermal method in example 2 of the present invention;

fig. 8 is an optical microscope image of an intercalated graphene blended polyurethane open-cell sponge prepared in example 2 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the specification of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the embodiment provides a preparation method of an intercalated graphene blended polyurethane open-cell sponge, and the preparation flow is shown in fig. 1.

S1, preparation of intercalated graphene nanosheets: preparing 200-mesh crystalline flake graphite, sodium nitrate and potassium permanganate with the mass ratio of 1:3:3 under the ice-water bath condition, evenly dividing the sodium nitrate and the potassium permanganate into three parts respectively, adding the sodium nitrate and the potassium permanganate into a reactor filled with the 200-mesh crystalline flake graphite for three times respectively, and stirring while adding; heating to 90 ℃ after stirring for 1h, refluxing at constant temperature for 1h, and after the solution becomes dark brown, centrifugally washing with hydrogen peroxide (30%) and 10% hydrochloric acid for three times respectively to obtain graphene oxide; and then adding ethylene glycol, and carrying out hydrothermal treatment for 4h at the temperature of 200 ℃ to obtain ethylene glycol intercalated few-layer graphene oxide nanosheets, namely layered graphene nanosheets.

S2, preparation of graphene dispersion liquid: dispersing the intercalated graphene nanosheets prepared by S1 into polyether polyol in a sand mill, wherein the content of the graphene nanosheets is controlled to be 3-5%.

S3, preparation of a foaming sponge: mixing and foaming the graphene dispersion liquid prepared in the step S2, an auxiliary agent and isocyanate according to parts by weight through a pump to obtain a foaming sponge; specifically, the raw materials comprise, by weight, 60-100 parts of a graphene dispersion liquid, 0.1-0.3 part of a triethylene diamine catalyst, 0.1-0.3 part of a stannous octoate (T-9) catalyst, 1-3 parts of ethoxy modified trisiloxane (IOTA-2000), 3-6 parts of water, and 30-50 parts of toluene diisocyanate (2, 4-position about 80%, 2, 6-position about 20%).

(4) Preparing a finished sponge product: and cooling the foamed sponge obtained in the step S3, curing and shaping to obtain stable foamed sponge, blasting to obtain the intercalation graphene blended polyurethane open-cell sponge, cutting to obtain flaky foamed cotton, drying and deodorizing to obtain a finished foamed cotton product, wherein pore passages of the sponge are fully exposed, and the adsorption performance of the sponge is conveniently exerted.

Fig. 2 and 3 are scanning electron micrographs of few-layer intercalated graphene prepared by the Hummers method in combination with the hydrothermal method and optical micrographs of graphene-blended polyurethane open-cell sponge under the conditions of the example.

Fig. 4 shows that the contact angle of the intercalated graphene blended polyurethane open-cell sponge prepared in example 1 is 148 ± 2.3 °.

Fig. 5 shows the adsorption performance of paraxylene and cyclohexanone of the intercalated graphene blended polyurethane open-cell sponge prepared in example 1, and the test conditions are as follows: 304 mg/xylene, 216 mg/cyclohexanone, wind speed 3.6m/s, 75% RH.

Fig. 6 is a graph of the adsorption performance of the intercalated graphene blended polyurethane open-cell sponge prepared in example 1 on cyclohexanone and ethanol, and the test conditions are as follows: 146 mg/cyclohexanone, 1242 mg/absolute ethyl alcohol, 1.1m/s, 75% RH.

Example 2:

substantially the same as example 1, but inserting few-layered graphene oxide nanoplatelets of graphite with 1, 4-butanediol, the obtained few-layered graphene oxide nanoplatelets with intercalation have smaller specific surface, as shown in fig. 7 and 8, which are scanning electron microscope images of few-layered inserted graphene and optical microscope images of the obtained graphene sponge.

It is to be understood that the above embodiments are merely illustrative for clarity of description and are not restrictive. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible within the scope of the invention as claimed.