CN110577663A - Preparation method of environment-friendly cellulose sponge material - Google Patents
Preparation method of environment-friendly cellulose sponge material Download PDFInfo
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- CN110577663A CN110577663A CN201810579716.XA CN201810579716A CN110577663A CN 110577663 A CN110577663 A CN 110577663A CN 201810579716 A CN201810579716 A CN 201810579716A CN 110577663 A CN110577663 A CN 110577663A
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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
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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
- 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
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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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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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
- 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 belongs to the technical field of cellulose, and particularly relates to a preparation method of an environment-friendly cellulose sponge material. The preparation steps are as follows: 1) pretreating cellulose; 2) preparing a cellulose solution; 3) and (3) preparing a cellulose sponge material. The invention provides a preparation method of an environment-friendly cellulose sponge material, and the prepared cellulose sponge material has low production cost and light environment-friendly pressure and can replace a cellulose sulfonate method adopted by enterprises at present. The environment-friendly cellulose sponge material prepared by the invention has good mechanical property and high water absorption rate. The invention selects low-temperature forming, is beneficial to Na2SO4The formation of crystalline compounds, whereas under natural conditions the formation of cellulose sponges is slow. Na added in the invention2SO4The activity of hydrogen ions can be inhibited by utilizing the same ion effect of the cellulose and sulfuric acid so as to prevent the cellulose from being excessively degraded. The invention selects the aqueous solution system of NaOH/thiourea to have stronger performancethe dissolving capacity is gradually increased along with the decrease of the temperature.
Description
Technical Field
The invention belongs to the technical field of cellulose, and particularly relates to a preparation method of an environment-friendly cellulose sponge material.
Background
Foamed plastic has been used as daily necessities and industrial goods for decades and becomes an essential article in industrial production and people's life. The foam articles sold on the market at present are mainly made of polyurethane and polystyrene which are derived from petroleum products. The production process pollutes the environment, and the wastes are difficult to degrade, so that the long-term use of the detergent can cause certain harm to human bodies when the detergent is particularly used for human body sanitation, household washing and makeup. With the continuous decrease of petroleum resources, the raw material source of the petroleum resources is also a serious problem. After twenty-first century, people have further realized the environmental protection, and a new environmental protection type foamed plastic substitute is bound to be provided.
Plant cellulose is the most common natural resource in nature, not only has wide source, but also can be continuously regenerated through photosynthesis of plants, and the annual output of the world is up to 1000 hundred million tons. The cellulose is easily decomposed into carbon dioxide and water under natural conditions, and has no pollution to the environment. The cellulose sponge prepared from cellulose has the characteristics of quick water absorption, strong water retention, easy air drying, good wiping effect and the like, and is mainly used for cleaning products such as tableware cleaning, automobile cleaning and the like at present.
The most important in the production process of cellulose sponge is cellulose solvent, which is difficult to dissolve in most organic solvents due to the supermolecular structure of cellulose, especially when the degree of polymerization is high. The current cellulose dissolution processes can be divided into two broad categories: the first is a cellulose dissolving process by using the first half of the traditional viscose fiber production, namely a cellulose sulfonate method by adopting carbon disulfide reaction. The method pollutes the environment and corrodes equipment, but because the relative process is mature, the cost is lower, and some enterprises still adopt the method. The other type is a solvent method, which can be divided into a derivatization solvent and a non-derivatization solvent, and can also be divided into an aqueous phase solvent and a non-aqueous phase solvent. Among them, NaOH/CS has been used mainly in industry2The system and the NMMO/water solvent system, and in addition, a part of solvents also have better development prospects, such as ionic liquid, NaOH/urea or thiourea/water system and the like. The NaOH/thiourea solution is used as the cellulose solvent, so that the dissolving capacity is high, cellulose cannot be degraded in the solution, the pollution in the production process is low, and the raw material price is low. The cellulose solution is prepared by using NaOH/thiourea solution, and then wet spinning is carried out, so that the prepared fiber is similar to silk, and the mechanical property is superior to that of viscose fiber. Although the solvent is not too strong in dissolving power, the crystallinity of cellulose may be reduced by a cellulose pretreatment method to increase its solubility in the solvent. In addition, the cellulose is derived from plant, is discarded from daily cellulose products of human beings, is a large source of cellulose, is fully utilized, not only solves the problem of raw materials, but also reduces the production cost of the cellulose sponge。
Therefore, how to select a proper process and a cheap solvent to prepare the cellulose sponge with excellent performance has important significance for replacing the currently adopted cellulose sulfonate method of enterprises.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly cellulose sponge material with low production cost and light environment-friendly pressure, and the prepared cellulose sponge material has good mechanical property and high water absorption.
the technical scheme adopted for realizing the purpose of the invention is as follows: a preparation method of an environment-friendly cellulose sponge material comprises the following preparation steps:
1) Pretreatment of cellulose
Crushing the wood pulp board into particles with the particle size of less than 50 microns, then putting the particles into an aqueous solution of sodium hydroxide for soaking at room temperature for 2 hours, filtering, washing a filter cake with water, and then removing water to obtain pretreated cellulose;
2) Preparation of cellulose solution
Dissolving sodium hydroxide and thiourea in water to obtain a sodium hydroxide/thiourea solution, then putting the pretreated cellulose into the sodium hydroxide/thiourea solution, freezing at-5 ℃ for 2 hours, and then unfreezing at room temperature to obtain a cellulose solution;
3) preparation of cellulose sponge material
Adding a pore-forming agent sodium sulfate into the cellulose solution, stirring to obtain mixed slurry, and pouring the mixed slurry into a mold for low-temperature molding for 72 hours; and (3) after low-temperature forming, putting the obtained product into a coagulating bath of sulfuric acid and sodium sulfate for soaking at 70 ℃ for 1h, and filtering, washing and drying the obtained product after soaking to obtain the cellulose sponge material.
Preferably, in the step 2), the mass percentage concentration of the cellulose in the cellulose solution is 6%.
Preferably, in step 3), the amount of the pore-forming agent sodium sulfate is 40% of the weight of the cellulose solution.
preferably, in the step 3), the mass percentage of the sulfuric acid in the coagulation bath is 12%, and the concentration of the sodium sulfate is 220 g/L.
Preferably, in step 3), the particle size of the pore former sodium sulfate is less than 5 microns.
The technical advantages of the invention are as follows:
The invention provides a preparation method of an environment-friendly cellulose sponge material, and the prepared cellulose sponge material has low production cost and light environment-friendly pressure and can replace a cellulose sulfonate method adopted by enterprises at present.
the environment-friendly cellulose sponge material prepared by the invention has good mechanical property and high water absorption rate.
The invention selects low-temperature forming, is beneficial to Na2SO4The formation of crystalline compounds, whereas under natural conditions the formation of cellulose sponges is slow. Na added in the invention2SO4The activity of hydrogen ions can be inhibited by utilizing the same ion effect of the cellulose and sulfuric acid so as to prevent the cellulose from being excessively degraded.
The cellulose sponge prepared by the invention has the elongation at break of more than 2.0 percent, the tensile strength of 0.2MPa and the tearing strength of 0.17 KN.m.
the aqueous solution system of NaOH/thiourea has strong dissolving capacity, and the dissolving capacity is gradually enhanced along with the reduction of temperature; and the tensile strength and the tearing strength of the finished cellulose sponge product can be improved by increasing the concentration of the cellulose.
The invention adopts Na2SO4As a pore-forming agent of the cellulose sponge, the cellulose sponge prepared by the pore-forming agent has an open pore structure.
Detailed Description
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
Example 1
1) Cellulose pretreatment: crushing the wood pulp board into particles with the particle size of less than 50 microns, then putting the particles into an aqueous solution of sodium hydroxide for soaking at room temperature for 2 hours, filtering, washing a filter cake with water, and then removing water to obtain pretreated cellulose;
2) Preparation of cellulose solution: dissolving sodium hydroxide and thiourea in water to obtain a sodium hydroxide/thiourea solution (100 mL: 2g of sodium hydroxide: 2g of thiourea), then putting the pretreated cellulose into the sodium hydroxide/thiourea solution (the weight percentage of the cellulose is 6 percent), freezing the cellulose for 2 hours at the temperature of-5 ℃, and then unfreezing the cellulose at room temperature to obtain a unfrozen cellulose solution;
3) preparation of cellulose sponge: adding 40g of pore-forming agent sodium sulfate (the particle size is less than 5 microns) into 100g of unfrozen cellulose solution, stirring to obtain mixed slurry, and pouring the mixed slurry into a mold for low-temperature molding for 72 hours; and (3) after low-temperature forming, placing the obtained product into a coagulating bath of sulfuric acid and sodium sulfate for high-temperature impregnation at 70 ℃ for 1h (the mass percentage of the sulfuric acid in the coagulating bath is 12%, and the concentration of the sodium sulfate is 220 g/L), and filtering, washing and drying the obtained product after impregnation to obtain the cellulose sponge.
Example 2
1) Cellulose pretreatment: crushing the wood pulp board into particles with the particle size of less than 50 microns, then putting the particles into an aqueous solution of sodium hydroxide for soaking at room temperature for 2 hours, filtering, washing a filter cake with water, and then removing water to obtain pretreated cellulose;
2) Preparation of cellulose solution: dissolving sodium hydroxide and thiourea in water to obtain a sodium hydroxide/thiourea solution (100 mL: 2g of sodium hydroxide: 2g of thiourea), then putting the pretreated cellulose into the sodium hydroxide/thiourea solution (the weight percentage of the cellulose is 10 wt%), freezing for 2 hours at-5 ℃, and then unfreezing at room temperature to obtain a unfrozen cellulose solution;
3) Preparation of cellulose sponge: adding pore-forming agent sodium sulfate (the particle size is less than 5 microns) into the unfrozen cellulose solution, stirring to obtain mixed slurry, and pouring the mixed slurry into a mould to perform low-temperature forming for 72 hours; after low-temperature forming, placing the mixture into a coagulating bath of sulfuric acid and sodium sulfate for high-temperature impregnation at 70 ℃ for 1h (the mass percentage of the sulfuric acid in the coagulating bath is 10 wt%, and the concentration of the sodium sulfate is 220 g/L), and filtering, washing and drying the impregnated product to obtain the cellulose sponge.
The cellulose sponges prepared in examples 1 and 2 were tested for mechanical properties and the results are shown in table 1:
Determination of tensile Strength: determination of tensile strength and elongation at break according to IS01798-1983 for soft cellular polymer materials;
determination of tear Strength: the tear properties of the flexible foams were determined according to GBl 0808-89.
TABLE 1
| elongation at break/% | Tensile strength/MPa | Tear Strength/KN.m | |
| Example 1 | 2.2 | 0.23 | 0.18 |
| Example 2 | 2.1 | 0.24 | 0.17 |
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (5)
1. A preparation method of an environment-friendly cellulose sponge material is characterized by comprising the following steps: the preparation steps are as follows:
1) Pretreatment of cellulose
Crushing the wood pulp board into particles with the particle size of less than 50 microns, then putting the particles into an aqueous solution of sodium hydroxide for soaking at room temperature for 2 hours, filtering, washing a filter cake with water, and then removing water to obtain pretreated cellulose;
2) Preparation of cellulose solution
Dissolving sodium hydroxide and thiourea in water to obtain a sodium hydroxide/thiourea solution, then putting the pretreated cellulose into the sodium hydroxide/thiourea solution, freezing at-5 ℃ for 2 hours, and then unfreezing at room temperature to obtain a cellulose solution;
3) Preparation of cellulose sponge material
Adding a pore-forming agent sodium sulfate into the cellulose solution, stirring to obtain mixed slurry, and pouring the mixed slurry into a mold for low-temperature molding for 72 hours; and (3) after low-temperature forming, putting the obtained product into a coagulating bath of sulfuric acid and sodium sulfate for soaking at 70 ℃ for 1h, and filtering, washing and drying the obtained product after soaking to obtain the cellulose sponge material.
2. The method for preparing the environment-friendly cellulose sponge material as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the mass percentage concentration of the cellulose in the cellulose solution is 6%.
3. The method for preparing the environment-friendly cellulose sponge material as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the amount of the pore-forming agent sodium sulfate is 40% of the weight of the cellulose solution.
4. The method for preparing the environment-friendly cellulose sponge material as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the mass percentage of the sulfuric acid in the coagulating bath is 12%, and the concentration of the sodium sulfate is 220 g/L.
5. the method for preparing the environment-friendly cellulose sponge material as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the particle size of the pore-forming agent sodium sulfate is less than 5 microns.
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| CN201810579716.XA CN110577663A (en) | 2018-06-07 | 2018-06-07 | Preparation method of environment-friendly cellulose sponge material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029135A (en) * | 2020-09-07 | 2020-12-04 | 江苏恒富新材料科技有限公司 | Preparation method of wood fiber sponge |
| CN112625296A (en) * | 2020-11-30 | 2021-04-09 | 宁波尼可海绵科技有限公司 | Production process and device of degradable sponge product |
| CN114262462A (en) * | 2021-12-22 | 2022-04-01 | 江苏恒富新材料科技有限公司 | Preparation method and performance research of cellulose modified and super absorbent sponge |
Citations (4)
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|---|---|---|---|---|
| EP1269951A1 (en) * | 2001-01-12 | 2003-01-02 | Hogy Medical Co., Ltd. | Absorbable protective coatings for wound with the use of cellulose sponge and process for producing the same |
| CN101100518A (en) * | 2007-06-22 | 2008-01-09 | 武汉大学 | Method for dissolving cellulose |
| 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 |
| CN102634069A (en) * | 2012-04-25 | 2012-08-15 | 桂林理工大学 | Method for preparing hemostatic sponge by use of sisal cellulose oxide |
-
2018
- 2018-06-07 CN CN201810579716.XA patent/CN110577663A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1269951A1 (en) * | 2001-01-12 | 2003-01-02 | Hogy Medical Co., Ltd. | Absorbable protective coatings for wound with the use of cellulose sponge and process for producing the same |
| CN101100518A (en) * | 2007-06-22 | 2008-01-09 | 武汉大学 | Method for dissolving cellulose |
| 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 |
| CN102634069A (en) * | 2012-04-25 | 2012-08-15 | 桂林理工大学 | Method for preparing hemostatic sponge by use of sisal cellulose oxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029135A (en) * | 2020-09-07 | 2020-12-04 | 江苏恒富新材料科技有限公司 | Preparation method of wood fiber sponge |
| CN112625296A (en) * | 2020-11-30 | 2021-04-09 | 宁波尼可海绵科技有限公司 | Production process and device of degradable sponge product |
| CN114262462A (en) * | 2021-12-22 | 2022-04-01 | 江苏恒富新材料科技有限公司 | Preparation method and performance research of cellulose modified and super absorbent sponge |
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Application publication date: 20191217 |