CN114656691A - Preparation method of cellulose porous sponge with lower density - Google Patents

Preparation method of cellulose porous sponge with lower density Download PDF

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Publication number
CN114656691A
CN114656691A CN202111584109.0A CN202111584109A CN114656691A CN 114656691 A CN114656691 A CN 114656691A CN 202111584109 A CN202111584109 A CN 202111584109A CN 114656691 A CN114656691 A CN 114656691A
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cellulose
porous sponge
relatively low
sodium sulfate
low density
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顾紫敬
李祥
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Jiangsu Hengfu New Material Technology Co ltd
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Jiangsu Hengfu New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/044—Elimination of an inorganic solid phase
    • C08J2201/0444—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention provides a preparation method of a cellulose porous sponge with lower density. The cellulose porous sponge with lower density is prepared by taking sodium hydroxide/urea aqueous solution as a solvent, anhydrous sodium sulfate as a pore-forming agent and cellulose as a raw material. The structure and performance difference of the cellulose porous sponge using cellulose and absorbent cotton as raw materials are compared, and the structure and performance difference of the consumption of different pore-forming agents, namely anhydrous sodium sulfate, on the cellulose porous sponge are also compared. Finally, the optimal amount of anhydrous sodium sulfate serving as a pore-forming agent is selected to prepare the cellulose porous sponge with lower density, and the technical indexes are achieved: the density is less than 0.1g/cm3, and the porosity is more than 90%.

Description

Preparation method of cellulose porous sponge with lower density
Technical Field
The invention provides a preparation method of a cellulose porous sponge with lower density, which takes sodium hydroxide/urea aqueous solution as a solvent, anhydrous sodium sulfate as a pore-forming agent and cellulose as a raw material to prepare the cellulose porous sponge with lower density. The structure and performance difference of the cellulose porous sponge which takes cellulose and absorbent cotton as raw materials are compared, and the structure and performance difference of the consumption of different pore-forming agents, namely anhydrous sodium sulfate, on the cellulose porous sponge are also compared. Finally, the optimal raw materials and the appropriate amount of the pore-forming agent anhydrous sodium sulfate are selected, and finally, the cellulose porous sponge with lower density is realized, and the technical indexes are achieved: density less than 0.1g/cm3The porosity is greater than 90%.
Background
Currently, organic synthetic polymer sponges are most commonly used in daily life, such as polyurethane, polyester, and polyvinyl alcohol sponges. The production technology of the sponge is mature, but the sponge has poor degradability, low recycling rate and high energy consumption. Therefore, the preparation of novel environment-friendly sponge is a research focus at present, such as starch sponge materials, chitosan composite sponge and the like. Cellulose is a natural high molecular material with the most abundant reserves on the earth, and the cellulose has strong biodegradability and can be recycled. But at present, the utilization rate of cellulose resources is low, only about 11 percent of natural lignocellulose raw materials are used for paper making, building, crop product production and the like, and the rest most of the natural lignocellulose raw materials participate in the carbon cycle of an ecological system, so that the natural lignocellulose raw materials still have great application potential. The cellulose sponge has good hydrophilicity and strong degradability, and the degradation product has no pollution to the environment, has good use value and ecological benefit, and has become one of the most promising sponge materials.
Cellulose molecules contain a large amount of hydroxyl groups, and hydrogen bonds are easily formed between the cellulose molecules and water, so that the cellulose sponge has strong water absorption capacity. However, the huge hydrogen bond network structure existing in cellulose molecules and among the molecules enables the melting point of cellulose to be higher than the decomposition temperature of the cellulose, and the melting processing of the cellulose is not easy to realize, so that the dissolving regeneration method is the main preparation method of the existing cellulose sponge. The process flow for preparing the cellulose sponge by the direct dissolution method of the cellulose is relatively simple, and the environmental pollution is less. The sodium hydroxide/urea dissolving system has good dissolving effect and low price, and is more beneficial to realizing the industrial production of the cellulose sponge.
Disclosure of Invention
The invention provides a preparation method of a cellulose porous sponge with lower density, which takes sodium hydroxide/urea aqueous solution as a solvent, anhydrous sodium sulfate as a pore-forming agent and cellulose as a raw material to prepare the cellulose porous sponge with lower density.
In order to achieve the purpose, the invention adopts the following technical scheme:
a porous cellulose sponge with low density is prepared from cellulose, sodium hydroxide, urea, sodium sulfate and deionized water.
The cellulose porous sponge with low density selects cellulose as a main raw material and absorbent cotton as a comparison raw material.
The cellulose porous sponge with lower density comprises the following steps:
1. firstly, preparing aqueous solution with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively.
2. Adding 3-5% of the total mass of raw materials (cellulose or absorbent cotton) into the aqueous solution prepared in the step 1, and uniformly stirring to form a transparent cellulose solution.
3. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, and respectively using the amount of the pore-forming agent anhydrous sodium sulfate which is 0.5, 1, 1.5 and 2 times of the mass of the cellulose suspension, and recording as M0.5、M1、M1.5And M2。
4. And (3) injecting the mixed solution into a mold, and then aging and molding for 48 hours at the temperature of-15 to-20 ℃.
5. After aging, the sample prepared in 4 was washed with deionized water at 40-60 ℃ in order to remove the pore-forming agent, anhydrous sodium sulfate.
6. And finally, placing the material prepared in the step 5 into an oven, and drying at the temperature of 40-60 ℃.
7. In the preparation process, the cellulose sponges with different structures and performances can be obtained by changing the consumption of the raw materials and the pore-forming agent anhydrous sodium sulfate.
The specific implementation mode is as follows:
example 1
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. Adding raw material cellulose with the total mass of 3-5% into the aqueous solution, and uniformly stirring to form a transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, and uniformly mixing, wherein the dosage is respectively 0.5 times of the mass of the cellulose suspension and is marked as M0.5. Then the mixed solution is injected into a mould and then is placed under the condition of subzero 15-subzero 20 ℃ for aging and molding for 48 hours. After aging and forming, washing the sample with deionized water at 40-60 ℃ for the purpose ofThe pore former sodium sulfate anhydride was removed. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Example 2
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. Adding cellulose raw material with 3-5% of total mass into the above aqueous solution, and stirring uniformly to form transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, wherein the dosage is 1 time of the mass of the cellulose suspension respectively and is marked as M1. Then the mixed solution is injected into a mould and then is placed under the condition of minus 15 ℃ to minus 20 ℃ for aging and molding for 48 hours. After aging and forming, the sample is washed with deionized water at 40-60 ℃ in order to remove the pore former, anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Example 3
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. Adding cellulose raw material with 3-5% of total mass into the above aqueous solution, and stirring uniformly to form transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, wherein the dosage is respectively 1.5 times of the mass of the cellulose suspension, and is marked as M1.5. Then the mixed solution is injected into a mould and then is placed under the condition of subzero 15-subzero 20 ℃ for aging and molding for 48 hours. After aging, the sample was washed with deionized water at 40-60 ℃ in order to remove the porogen anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Example 4
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. Adding cellulose raw material with 3-5% of total mass into the above aqueous solution, and stirring uniformly to form transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, wherein the dosage is respectively 2 times of the mass of the cellulose suspension, and is marked as M2. Then the mixed solution is injected into the moldThe mixture is placed at the temperature of minus 15 to minus 20 ℃ for aging and molding for 48 hours. After aging and forming, the sample is washed with deionized water at 40-60 ℃ in order to remove the pore former, anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Comparative example 1
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. And (3) adding absorbent cotton accounting for 3-5% of the total mass into the aqueous solution, and uniformly stirring to form a transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, and respectively using the amount of the pore-forming agent anhydrous sodium sulfate which is 0.5 time of the mass of the cellulose suspension and is marked as M0.5. Then the mixed solution is injected into a mould and then is placed under the condition of minus 15 ℃ to minus 20 ℃ for aging and molding for 48 hours. After aging, the sample was washed with deionized water at 40-60 ℃ in order to remove the porogen anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Comparative example 2
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. And (3) adding absorbent cotton accounting for 3-5% of the total mass into the aqueous solution, and uniformly stirring to form a transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, and respectively using the amount of the pore-forming agent anhydrous sodium sulfate which is 1 time of the mass of the cellulose suspension and recording as M1. Then the mixed solution is injected into a mould and then is placed under the condition of subzero 15-subzero 20 ℃ for aging and forming for 48 hours. After aging, the sample was washed with deionized water at 40-60 ℃ in order to remove the porogen anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Comparative example 3
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. And (3) adding absorbent cotton accounting for 3-5% of the total mass into the aqueous solution, and uniformly stirring to form a transparent cellulose solution. Subsequently adding a certain mass of pore-forming agent anhydrous into the suspensionSodium sulfate, homogeneously mixed, in an amount of 1.5 times the mass of the cellulose suspension, respectively, and designated as M1.5. Then the mixed solution is injected into a mould and then is placed under the condition of minus 15 ℃ to minus 20 ℃ for aging and molding for 48 hours. After aging, the sample was washed with deionized water at 40-60 ℃ in order to remove the porogen anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
Comparative example 4
Firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively. And (3) adding absorbent cotton accounting for 3-5% of the total mass into the aqueous solution, and uniformly stirring to form a transparent cellulose solution. Then adding a certain mass of pore-forming agent anhydrous sodium sulfate into the suspension, uniformly mixing, and respectively using the amount of the pore-forming agent anhydrous sodium sulfate which is 2 times of the mass of the cellulose suspension and recording as M2. Then the mixed solution is injected into a mould and then is placed under the condition of subzero 15-subzero 20 ℃ for aging and molding for 48 hours. After aging, the sample was washed with deionized water at 40-60 ℃ in order to remove the porogen anhydrous sodium sulfate. Finally, the prepared material is placed in an oven and dried at the temperature of 40-60 ℃.
In order to determine the structure and the performance of the porous cellulose sponge, the finally prepared sample is tested for density, porosity, micro-morphology, mechanical property and the like.
The test method is as follows:
1. density: the dried cellulose sponge was cut into a regular cube, and the length, width and height were measured with a vernier caliper. The volume of the sample was calculated by averaging 3 measurements at different positions for each size. And accurately weighing the weight, and measuring the density of the cellulose sponge according to a density formula.
2. Porosity: the porosity was calculated by mass-volume method according to the following formula, wherein the density of the raw cellulose was 1.5g/cm3
θ/％＝[1-m0/(Vρs)]×100
3. Mechanical properties: and (3) measuring the tensile strength of the sponge sample by adopting an electronic universal material testing machine, and repeatedly measuring each group for 5 times to obtain an average value.
The experimental results are as follows:
1. density of
Amount of pore former used Fiber (g/cm)3) Absorbent cotton (g/cm)3)
M0.5 0.102 0.092
M1 0.965 0.091
M1.5 0.902 0.086
M2 0.887 0.083
2. Porosity of the material
Figure BDA0003427343700000061
Figure BDA0003427343700000071
3. Mechanical properties
Figure BDA0003427343700000072

Claims (9)

1. A cellulosic porous sponge having a relatively low density, characterized by: the detergent is mainly prepared from raw materials such as cellulose, sodium hydroxide, urea, sodium sulfate, deionized water and the like.
2. A cellulosic porous sponge having a relatively low density, characterized by: cellulose is selected as a main raw material, absorbent cotton is selected as a comparison raw material, and the structure and the performance of two original final samples are compared.
3. A cellulosic porous sponge having a relatively low density, characterized by: firstly, preparing aqueous solutions with the mass fractions of sodium hydroxide and urea being 6-8% and 10-14%, respectively.
4. A cellulosic porous sponge having a relatively low density, characterized by: adding cellulose with the total mass of 3-5% into the aqueous solution prepared in the step 1, and uniformly stirring to form a transparent cellulose solution.
5. A cellulosic porous sponge having a relatively low density, characterized by: adding a certain mass of pore-forming agent anhydrous sodium sulfate to the suspension of claim 4, uniformly mixing, and respectively using 0.5, 1, 1.5 and 2 times of the mass of the cellulose suspension, and recording as M0.5、M1、M1.5And M2。
6. A cellulose porous sponge having a relatively low density, characterized by: the mixed solution of claim 3 is injected into a mold and then aged at-15 to-20 ℃ for 48 hours.
7. A cellulosic porous sponge having a relatively low density, characterized by: after aging, the sample prepared in claim 4 is washed with deionized water at 40-60 ℃ in order to remove the pore former anhydrous sodium sulfate.
8. A cellulosic porous sponge having a relatively low density, characterized by: finally, the material obtained in claim 7 is placed in an oven and dried at 40-60 ℃.
9. A cellulosic porous sponge having a relatively low density, characterized by: in the preparation process, cellulose sponges with different structures and performances can be obtained by changing the consumption of raw materials and pore-forming agent anhydrous sodium sulfate.
CN202111584109.0A 2021-12-22 2021-12-22 Preparation method of cellulose porous sponge with lower density Pending CN114656691A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504327A (en) * 2011-10-22 2012-06-20 桂林理工大学 Method for preparing cellulose sponge by utilizing sisal hemp wastes hemp bran and hemp head
CN110577666A (en) * 2018-06-07 2019-12-17 淮安市冰青建设工程管理有限公司 Environment-friendly cellulose sponge material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504327A (en) * 2011-10-22 2012-06-20 桂林理工大学 Method for preparing cellulose sponge by utilizing sisal hemp wastes hemp bran and hemp head
CN110577666A (en) * 2018-06-07 2019-12-17 淮安市冰青建设工程管理有限公司 Environment-friendly cellulose sponge material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘洁等: "成孔剂Na2SO4的用量对纤维素海绵性能的影响", 《纤维素科学与技术》 *

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