阅读说明：本技术 一种环氧松香改性纤维素气凝胶吸油材料及其制备方法 (Epoxy rosin modified cellulose aerogel oil absorption material and preparation method thereof ) 是由 黄旭娟 丁正青 王宇晴 樊歆璐 李静秋 蔡照胜 于 2020-11-24 设计创作，主要内容包括：本发明公开了一种环氧松香改性纤维素气凝胶吸油材料及其制备方法,通过将纤维素置于碱溶液中,通过剪切得到稳定分散的纤维素水分散液；将所得的纤维素水分散液通过有机溶剂置换得到稳定分散的纤维素有机溶剂分散液；将所得纤维素有机溶剂分散液与环氧松香混合均匀,加入催化剂,在20～35℃下反应0.5～2h；将所得的产品经干燥处理得到所需环氧松香改性纤维素气凝胶吸油材料。本发明以天然产物松香和纤维素为原料,通过简单的制备方法,得到具有疏水性的气凝胶吸油材料。(The invention discloses an epoxy rosin modified cellulose aerogel oil absorption material and a preparation method thereof, wherein cellulose is placed in an alkali solution, and a stably dispersed cellulose water dispersion is obtained by shearing; replacing the obtained cellulose aqueous dispersion liquid with an organic solvent to obtain a stably dispersed cellulose organic solvent dispersion liquid; uniformly mixing the obtained cellulose organic solvent dispersion liquid with epoxy rosin, adding a catalyst, and reacting for 0.5-2 h at the temperature of 20-35 ℃; and drying the obtained product to obtain the required epoxy rosin modified cellulose aerogel oil absorption material. According to the invention, the natural products rosin and cellulose are used as raw materials, and the aerogel oil absorption material with hydrophobicity is obtained by a simple preparation method.)

1. An epoxy rosin modified cellulose aerogel oil absorption material is characterized by comprising the following raw materials in parts by weight:

1-5 parts of cellulose;

1-40 parts of epoxy rosin;

0.001-0.05 part of catalyst.

2. The epoxy rosin modified cellulose aerogel oil absorbing material as claimed in claim 1, wherein the cellulose is at least one of bacterial cellulose, pulp cellulose, microcrystalline cellulose or nanocellulose.

3. The epoxy rosin modified cellulose aerogel oil absorbing material as claimed in claim 1 or 2, wherein the epoxy rosin is at least one of dehydroabietyl glycidyl ether or polyethylene glycol dehydroabietyl glycidyl ether, and the epoxy value of the epoxy rosin is in the range of 40% to 80%.

4. The epoxy rosin modified cellulose aerogel oil absorbing material of claim 3, wherein the catalyst is SnCl₄、ZnCl₂、AlCl₃、TiCl₄Or SbCl₅At least one of (1).

5. The preparation method of the epoxy rosin modified cellulose aerogel oil absorption material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:

(1) placing cellulose in an alkali solution, and shearing to obtain a stably dispersed cellulose water dispersion;

(2) replacing the cellulose aqueous dispersion obtained in the step (1) with an organic solvent to obtain a stably dispersed cellulose organic solvent dispersion;

(3) uniformly mixing the cellulose organic solvent dispersion liquid obtained in the step (2) with epoxy rosin, adding a catalyst, and reacting at the temperature of 20-35 ℃ for 0.5-2 h;

(4) and (4) drying the product obtained in the step (3) to obtain the required epoxy rosin modified cellulose aerogel oil absorption material.

6. The method for preparing the epoxy rosin modified cellulose aerogel oil absorbing material as claimed in claim 5, wherein the alkali solution in step (1) is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide or triethylamine solution; the concentration of the alkali solution is 0.20-1.25 mol/L.

7. The preparation method of the epoxy rosin modified cellulose aerogel oil absorption material as claimed in claim 5, wherein the mass usage amount of the cellulose relative to the alkali solution in the step (1) is 0.005-0.060 g/mL.

8. The preparation method of the epoxy rosin modified cellulose aerogel oil absorption material as claimed in claim 5, wherein the shear rate in the step (1) is 4000-12000 rpm/min, and the shear time is 2-6 h.

9. The method for preparing the epoxy rosin modified cellulose aerogel oil absorbing material as claimed in claim 5, wherein the organic solvent in step (2) is at least one of DMSO or DMF.

10. The epoxy rosin modified cellulose aerogel oil absorption material as claimed in any one of claims 1 to 4 or the epoxy rosin modified cellulose aerogel oil absorption material prepared by the method as claimed in any one of claims 5 to 9, wherein the density of the epoxy rosin modified cellulose aerogel oil absorption material is 0.0420-1.720 g/cm³The contact angle of the oil absorption material and water is 130-151 degrees, and the oil absorption multiple can reach 23-38 times.

Technical Field

The invention relates to the technical field of material preparation, in particular to an epoxy rosin modified cellulose aerogel oil absorption material and a preparation method thereof.

Background

In recent years, with the rapid development of world industry, offshore oil resources are developed, and the problem of crude oil leakage caused by oil extraction and transportation is also increased. These problems can be addressed by biological and chemical methods, but physical adsorption is a better method of treating marine oil spills. However, most of the oil absorption materials in the society at present have the defects of low oil absorption efficiency, pollution source, inconvenient secondary treatment, high cost and the like. Therefore, the prepared novel green and environment-friendly oil absorption material has great economic benefit and environmental benefit.

Cellulose is one of the most abundant biomass resources in the world, and has the advantages of no pollution, degradability and the like. Due to the polyhydroxy on the surface of the cellulose, the hydrophobic oil absorption material is obtained by easily modifying the cellulose.

Patent CN 103980530A discloses a preparation method of a seaweed cellulose aerogel oil absorption material, which is characterized in that purified seaweed cellulose is extracted from enteromorpha, and is mechanically ground into seaweed nano cellulose microfibrils to obtain seaweed cellulose hydrogel. After the alginate cellulose aerogel is obtained through freeze drying, Phenyltriethoxysilane (PTES) is used for modification, and the modified alginate cellulose aerogel is stored for 0.5-5 hours at the temperature of 90-100 ℃ to obtain the hydrophobic alginate cellulose aerogel oil absorption material. Although the invention mainly utilizes natural seaweed cellulose, so that the main raw material is environment-friendly, the hydrophobic modification of the invention still needs a large amount of petroleum-based raw materials.

Rosin is a characteristic biomass resource of forestry which is abundant in China, the annual output can reach 40-80 ten thousand tons, and a series of derivatives which are obtained by taking rosin as a raw material through chemical modification are widely applied to the fields of essence, spice, medicine, chemical industry and the like. The phenanthrene ring framework structure of the rosin enables the rosin to have certain rigidity and good hydrophobicity, so that the rosin can be applied to a plurality of hydrophobic modified materials.

Therefore, the method has huge resource advantages by using cellulose and epoxy rosin as raw materials and developing and utilizing the full-bio-based oil absorption material.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defects of low efficiency and pollution of the oil absorption material in the prior art, so that the epoxy rosin modified cellulose aerogel oil absorption material and the preparation method thereof are provided.

In order to solve the technical problems, the invention provides an epoxy rosin modified cellulose aerogel oil absorption material which comprises the following raw materials in parts by weight:

1-5 parts of cellulose;

1-40 parts of epoxy rosin;

0.001-0.05 part of catalyst.

Preferably, the cellulose is at least one of bacterial cellulose, pulp cellulose, microcrystalline cellulose or nanocellulose.

Preferably, the epoxy rosin is at least one of dehydroabietyl glycidyl ether or polyethylene glycol dehydroabietyl glycidyl ether, and the epoxy value of the epoxy rosin is in a range of 40% to 80%.

Preferably, the catalyst is SnCl₄、ZnCl₂、AlCl₃、TiCl₄Or SbCl₅At least one of (1).

Meanwhile, the invention also provides a preparation method of the epoxy rosin modified cellulose aerogel oil absorption material, which comprises the following steps:

(1) placing cellulose in an alkali solution, and shearing to obtain a stably dispersed cellulose water dispersion;

(2) replacing the cellulose aqueous dispersion obtained in the step (1) with an organic solvent to obtain a stably dispersed cellulose organic solvent dispersion;

(3) uniformly mixing the cellulose organic solvent dispersion liquid obtained in the step (2) with epoxy rosin, adding a catalyst, and reacting at the temperature of 20-35 ℃ for 0.5-2 h;

(4) and (4) drying the product obtained in the step (3) to obtain the required epoxy rosin modified cellulose aerogel oil absorption material.

Preferably, the alkali solution in the step (1) is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide or triethylamine solution; the concentration of the alkali solution is 0.20-1.25 mol/L.

Preferably, the mass dosage of the cellulose relative to the alkali solution in the step (1) is 0.005-0.060 g/mL.

Preferably, the shearing rate in the step (1) is 4000-12000 rpm/min, and the shearing time is 2-6 h.

Preferably, the organic solvent in step (2) is at least one of dimethyl sulfoxide (DMSO) or N, N-Dimethylformamide (DMF).

The density of the epoxy rosin modified cellulose aerogel oil absorption material or the epoxy rosin modified cellulose aerogel oil absorption material prepared by the preparation method is 0.0420-1.720 g/cm³The contact angle with water is 130-151 DEG, and the oil absorption multiple can reach 23-38.

The technical scheme of the invention has the following advantages:

1. the epoxy rosin modified cellulose aerogel oil absorption material provided by the invention has the density of 0.0420-1.720 g/cm³The contact angle with water is 130-151 degrees, the oil absorption multiple can reach 38 times, the rosin epoxidized by chemical reaction is polymerized on the surface of a cellulose chain to coat the surface of cellulose, the surface roughness is improved, the goal of hydrophobic modification of the cellulose is achieved, the obtained epoxy rosin modified cellulose aerogel oil absorption material has excellent hydrophobic property and large contact angle, and the hydrophobic property and the oil absorption property are still maintained after the epoxy rosin modified cellulose aerogel oil absorption material is soaked in water for 48 hours.

2. According to the preparation method of the epoxy rosin modified cellulose aerogel oil absorption material, provided by the invention, natural products rosin and cellulose are used as raw materials, and the hydrophobic aerogel oil absorption material is obtained through a simple preparation method.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in 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 some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

Fig. 1 is a scanning electron microscope image of an epoxy rosin modified bacterial cellulose aerogel material in example 1 of the present invention.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

Weighing 2g of bacterial cellulose in a 250mL beaker, adding 100mL of 0.6mol/L NaOH solution, and shearing by a high-speed shearing machine at a speed of 8000rpm/min for 5h to obtain the stably dispersed bacterial cellulose aqueous dispersion. The obtained cellulose aqueous dispersion was subjected to dimethyl sulfoxide solvent substitution to obtain a stably dispersed 0.02g/mL bacterial cellulose dimethyl sulfoxide solution cellulose dispersion. The resultant bacterial cellulose dimethyl sulfoxide solution was added to a cellulose dispersion solution of 2g of dehydroabietyl glycidyl ether (epoxy value: 60%), stirred, and then 0.050g of SnCl was added to the system₄And (3) reacting for 1h at 25 ℃ by using a catalyst. After the reaction is finished, the epoxy rosin modified bacterial cellulose aerogel oil absorption material is obtained by freeze drying, and the density of the epoxy rosin modified bacterial cellulose aerogel oil absorption material is 0.042 g-cm³The contact angle was 151 °.

The scanning electron microscope image of the obtained epoxy rosin modified bacterial cellulose aerogel material is shown in fig. 1, and it can be seen from the image that the prepared epoxy rosin modified cellulose aerogel has uniform pore diameter and uniform wall thickness.

Wherein, the preparation of the dehydroabietyl glycidyl ether is obtained by the following method:

57.25g of dehydroabietyl alcohol was dissolved in 300mL of 1, 2-dichloroethane, and 4.58g of BF was added₃Stirring after ethyl ether, slowly dropwise adding 18.50g of epoxy chloropropane into the reaction material at 0 ℃ by using a constant-pressure dropping funnel, and stirring and reacting for 8 hours at 70 ℃. After the reaction, the reaction solution was distilled under reduced pressure until no liquid was distilled off, and a viscous liquid was obtained as a dark red brown oil. Adding 50mL of 1, 2-dichloroethane solvent into the distilled material for dilution, preparing 20g of NaOH solution with the mass fraction of 40% at the same time, adding the NaOH solution into a reaction bottle, stirring the solution at 30 ℃ for 3.5h, performing suction filtration to remove a byproduct NaCl after cyclization is finished, washing the solution with supersaturated salt water to be neutral, and separating out an oil phase. And finally, drying the mixture by using anhydrous sodium sulfate, and removing the 1, 2-dichloroethane by evaporation under reduced pressure to obtain dehydroabietyl glycidyl ether (DAGE).

The prepared epoxy rosin modified bacterial cellulose aerogel oil absorption material is prepared into an oil absorption material with the size of 1 x 1cm, the oil absorption material is placed into a mixture of oil spilling and water with the area of 50 x 50cm, 10g of oil spilling is added, 0.042g of the prepared oil absorption material is added, and the saturated oil absorption rate reaches 38 times of the self weight.

Example 2

Weighing 4g of pulp cellulose in a 250mL beaker, adding 100mL of 1mol/L NaOH solution, and shearing for 6h at 12000rpm/min by a high-speed shearing machine to obtain the stably dispersed bacterial cellulose aqueous dispersion. A stably dispersed 0.02g/mL solution of microfibrillated cellulose in DMF was obtained by DMF solvent displacement. To the obtained organic solvent system was added 8g of polyethylene glycol dehydroabietyl glycidyl ether (epoxy value: 70%), and stirred with a magneton. Then, 0.05g of SnCl was added to the system₄And (3) reacting for 30min at 35 ℃ by using a catalyst. After the reaction is finished, drying to obtain the epoxy rosin modified paper pulp cellulose aerogel oil absorption material with the density of 0.082g/cm³The contact angle was 142 °.

The preparation of the polyethylene glycol dehydroabietyl glycidyl ether is obtained by the following method:

reference is made to the synthesis of dehydroabietyl polyoxyethylene ether "Zhouyanhong, Wenying, Xihui, etc.. Studies on the synthesis of abietyl alcohol polyoxyethylene ether and on the relationship between its structure and its performance [ J ]. forest chemical and industry, 2003, 24(001):7-11.

80g of the prepared dehydroabietyl polyoxyethylene ether, 300mL of 1, 2-dichloroethane and 4.50g of BF were mixed₃Adding diethyl ether into a four-neck flask with a thermometer, a condenser and a stirrer, slowly dropwise adding 10.06g of epoxy chloropropane at room temperature, heating the material to the set temperature after the dropwise adding is finished, reacting for a period of time, and removing unreacted epoxy chloropropane and 1, 2-dichloroethane by reduced pressure distillation; adding 100mL of 40% NaOH solution into the reaction system, reacting for 5h at 40 ℃, then sequentially filtering, washing to be neutral, drying by anhydrous sodium sulfate, and concentrating under reduced pressure to obtain the final product. The reaction scheme is as follows:

the prepared paper pulp cellulose aerogel oil absorption material modified by the epoxy rosin is prepared into an oil absorption material with the size of 1 x 1cm, the oil absorption material is placed into a mixture of oil spilling and water with the area of 50 x 50cm, 10g of oil spilling is added, 0.082g of the prepared oil absorption material is added, and the saturated oil absorption rate reaches 29 times of the self weight.

Example 3

Weighing 1g of microcrystalline cellulose in a 250mL beaker, adding 100mL of 1mol/L NaOH solution, and shearing for 2h at 8000rpm/min by a high-speed shearing machine to obtain the stably dispersed bacterial cellulose water dispersion. A stably dispersed 0.01g/mL solution of microfibrillated cellulose in DMSO was obtained by DMSO solvent displacement. To the obtained organic solvent system was added 4g of polyethylene glycol dehydroabietyl glycidyl ether (epoxy value: 80%), and stirred with a magneton. Then, 0.005g of SnCl was added to the system₄And (3) reacting for 1h at 30 ℃ by using a catalyst. After the reaction is finished, drying to obtainThe epoxy rosin modified microcrystalline cellulose aerogel oil absorption material has the density of 1.410g/cm³The contact angle was 149 °.

The prepared epoxy rosin modified microcrystalline cellulose aerogel oil absorption material is prepared into an oil absorption material with the size of 1 x 1cm, the oil absorption material is placed into a mixture of oil spilling and water with the area of 50 x 50cm, 10g of oil spilling is added, 1.410g of the prepared oil absorption material is added, and the saturated oil absorption rate reaches 30 times of the self weight.

Example 4

Weighing 1g of nano-cellulose in a 250mL beaker, adding 100mL of 0.20mol/L NaOH solution, and shearing for 4h at 8000rpm/min by a high-speed shearing machine to obtain the stably dispersed bacterial cellulose aqueous dispersion. A stably dispersed 0.01g/mL solution of microfibrillated cellulose in DMF was obtained by DMF solvent displacement. To the obtained organic solvent system was added 1g of polyethylene glycol dehydroabietyl glycidyl ether (epoxy value: 40%), and stirred with a magneton. Then, 0.001g of TiCl was added to the system₄And (3) reacting for 2 hours at the temperature of 30 ℃ by using a catalyst. After the reaction is finished, drying to obtain the epoxy rosin modified microcrystalline cellulose aerogel oil absorption material with the density of 0.980g/cm³The contact angle was 142 °.

Preparing the prepared epoxy rosin modified microcrystalline cellulose aerogel oil absorption material into an oil absorption material with the size of 1 multiplied by 1cm, placing the oil absorption material into a mixture of oil spill and water with the area of 50 multiplied by 50cm, adding 10g of oil spill, and adding 0.980g/cm of the prepared oil absorption material³The saturated oil absorption rate is 28 times of the self weight.

Example 5

Weighing 2g of bacterial cellulose in a 250mL beaker, adding 100mL of 1.25mol/L NaOH solution, and shearing for 6h at 12000rpm/min by a high-speed shearing machine to obtain the stably dispersed bacterial cellulose aqueous dispersion. The obtained cellulose aqueous dispersion was subjected to dimethyl sulfoxide solvent substitution to obtain a stably dispersed 0.02g/mL bacterial cellulose dimethyl sulfoxide solution cellulose dispersion. The resultant bacterial cellulose dimethyl sulfoxide solution was added to a cellulose dispersion of 16g of dehydroabietyl glycidyl ether (epoxy value: 80%), stirred, and then 0.050g of SnCl was added to the system₄And (3) reacting for 1h at 30 ℃ by using a catalyst. Reaction junctionAfter that, the epoxy rosin modified bacterial cellulose aerogel oil absorption material is obtained by freeze drying, and the density is 1.720g/cm³The contact angle was 130 °.

The prepared epoxy rosin modified bacterial cellulose aerogel oil absorption material is prepared into an oil absorption material with the size of 1 x 1cm, the oil absorption material is placed into a mixture of oil spilling and water with the area of 50 x 50cm, 10g of oil spilling is added, 1.72g of the prepared oil absorption material is added, and the saturated oil absorption rate reaches 23 times of the self weight.

Comparative example 1

Weighing 2g of bacterial cellulose in a 250mL beaker, adding 100mL of 1.25mol/L NaOH solution, and shearing for 6h at 12000rpm/min by a high-speed shearing machine to obtain the stably dispersed bacterial cellulose aqueous dispersion. The obtained cellulose aqueous dispersion was subjected to dimethyl sulfoxide solvent substitution to obtain a stably dispersed 0.02g/mL bacterial cellulose dimethyl sulfoxide solution cellulose dispersion. Freeze drying to obtain bacterial cellulose aerogel oil absorption material with density of 0.988g/cm³The measurement of the contact angle is meaningless due to the strong water absorption.

The prepared bacterial cellulose aerogel oil absorption material is prepared into an oil absorption material with the size of 1 x 1cm, the oil absorption material is placed into a mixture of oil spilling and water with the area of 50 x 50cm, 10g of oil spilling is added, 0.988g of the prepared oil absorption material is added, and the saturated oil absorption rate reaches 2 times of the self weight.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. 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 therefrom are within the scope of the invention.