CN111019003A - Waste fabric nanocellulose and preparation method thereof - Google Patents
Waste fabric nanocellulose and preparation method thereof Download PDFInfo
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- CN111019003A CN111019003A CN201911308956.7A CN201911308956A CN111019003A CN 111019003 A CN111019003 A CN 111019003A CN 201911308956 A CN201911308956 A CN 201911308956A CN 111019003 A CN111019003 A CN 111019003A
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- waste
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- nanocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
Abstract
The invention discloses a waste fabric nano-cellulose and a preparation method thereof. The invention relates to a method for preparing carboxymethyl nano-cellulose by a two-step method of chemical pretreatment and mechanical treatment after simply treating recycled waste cotton fabrics. The specific method is that the collected waste cotton fabrics are disinfected and crushed, and if the waste cotton fabrics are not white, the waste cotton fabrics need to be bleached; and carrying out carboxymethyl modification treatment on the crushed cotton fabric fibers, and carrying out high-pressure homogenization or shearing emulsification to obtain the CMNC. The obtained CMNC is that the cellulose nano-fiber has higher thermal stability than nano-cellulose obtained by other materials, and has higher carboxyl content than CNFs obtained by TEMPO catalytic oxidation. And with the improvement of the substitution degree of the carboxymethyl insoluble in water, the obtained CNF has better dispersibility in water and can be used for emulsion dispersion, biological composite materials, transparent films and the like. Meanwhile, the CMNC has the advantages of abundant and cheap synthetic raw materials, low preparation cost, green and environment-friendly preparation process and the like, and widens the recycling channel of waste cotton fabrics.
Description
Technical Field
The invention relates to the field of high-valued utilization of waste fabric environmental protection recovery, in particular to a (carboxymethyl) nano-cellulose of a waste fabric and a preparation method thereof.
Background
In recent years, the global population is rapidly increased, and the demands of various textiles are rapidly increased along with the rapid development of global economy; the rapid upgrade of the fashion industry also accelerates the upgrade of textiles, thereby causing a great deal of waste textiles and resources. Under the conditions of global warming and optimistic global environmental conditions, the effective utilization of the waste clothes, particularly the high-value utilization of the waste clothes, has great significance on the sustainable development of resources and energy.
Nanocellulose, because of its many advantages such as being renewable, biocompatible, excellent mechanical properties, is utilized in many areas of life, in particular as product packaging, paper and cardboard, food product factories, health and hygiene products, paints, cosmetics, etc.
Furthermore, nanocellulose-based materials will play an important role in the future nano-area. However, the large-scale preparation of the nano-cellulose by using waste fabrics as raw materials is rarely involved at present.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides waste fabric nanocellulose (CMNC or NCMC for short) and a preparation method thereof. The method has the advantages of simple and safe process, low cost, large-scale production and green and environment-friendly process; the preparation process of the invention prepares the carboxymethyl nanocellulose with different degrees of substitution by taking the waste fabric as a raw material. The method integrates the advantages of the preparation process of derivatization modification and size degradation of the waste fabric, obtains the nanocellulose with different carboxyl contents by a two-step method of modification pretreatment and simple mechanical treatment of the high-quality waste cotton cellulose, and provides a new method for high-valued conversion and utilization of the waste fabric.
The invention is realized by the following technical scheme:
a method for preparing carboxymethyl nanocellulose from waste cotton fabric comprises the steps of bleaching, disinfecting and crushing collected waste cotton fabric to obtain cotton fabric fibers; weighing quantitative cotton fabric fibers, adding a sodium hydroxide solution for activation swelling treatment, and adding an etherification reagent chloroacetic acid or sodium chloroacetate for etherification reaction; cooling, centrifuging, washing with deionized water for 3-5 times, removing supernatant, retaining the water-insoluble carboxymethyl cellulose with low substitution degree in the lower layer, and dialyzing for 1-2 days; then diluting to about 0.5%, circulating for 1-10 times by a homogenizer, or shearing by using a shearing emulsifier to obtain the carboxymethyl nano-cellulose.
The molar ratio of the sodium hydroxide to the chloroacetic acid or the sodium chloroacetate is 1.5-2: 1.
The addition amount of the chloroacetic acid or the sodium chloroacetate is 2 to 10 percent of the total solution amount.
The temperature of the etherification reaction is 45-75 ℃.
The etherification reaction time is 1-6 h.
The waste cotton fabrics are cut into blocks before being crushed.
Carboxymethyl nanocellulose of waste cotton fabrics is prepared by the method.
The invention relates to a method for preparing carboxymethyl nano-cellulose by a two-step method of chemical pretreatment and mechanical treatment after simply treating recycled waste cotton fabrics. Disinfecting and crushing the collected waste cotton fabrics, and if the waste cotton fabrics are not white, bleaching the waste cotton fabrics; and carrying out carboxymethyl modification treatment on the crushed cotton fabric fibers, and carrying out high-pressure homogenization or shearing emulsification to obtain the CMNC. The obtained CMNC is Cellulose Nanofiber (CNFs), has higher thermal stability than nanocellulose obtained from other materials, and has higher carboxyl content than CNFs obtained by TEMPO catalytic oxidation. And with the improvement of the substitution degree of the carboxymethyl insoluble in water, the obtained CNF has better dispersibility in water and can be used for emulsion dispersion, biological composite materials, transparent films and the like.
Compared with the prior art, the invention has the following advantages and effects:
(1) the preparation technology of the nano-cellulose integrates the advantages of the preparation process of derivatization modification and size degradation of the waste fabric, obtains the nano-cellulose with different carboxyl contents by a two-step method of modification pretreatment and mechanical treatment of the high-quality waste cotton cellulose, and provides a new method for high-valued conversion and utilization of the waste fabric;
(2) the cellulose used in the invention is waste cotton fabric, belongs to renewable waste in the textile industry, has the advantages of high purity, long length, better mechanical property and the like, and belongs to the reutilization of waste;
(3) the preparation process of the nano-cellulose is simple, convenient and feasible, convenient to operate and easy to industrialize; meanwhile, the CMNC has the advantages of abundant and cheap synthetic raw materials, low preparation cost, green and environment-friendly preparation process and the like, and widens the recycling channel of waste cotton fabrics.
(4) The nano-cellulose contains carboxymethyl groups, has high thermal stability and viscosity, and can be used as a thickener for food and cosmetics, a framework of an ion exchange membrane and a framework of a biological composite material.
Detailed Description
Hereinafter, the preparation process of carboxymethyl nanocellulose from the waste fabric according to the present invention will be described in further detail by way of examples, but the embodiments of the present invention are not limited thereto.
Bleaching, sterilizing, cutting into small pieces and pulverizing the collected waste cotton fabrics. Weighing a certain amount of cotton fabric fibers, adding a sodium hydroxide solution for activation swelling treatment, then adding an etherification reagent chloroacetic acid or sodium chloroacetate, and reacting at 45-75 ℃ for 1-6 h. Cooling, centrifuging, washing with deionized water for 3 times, removing supernatant, retaining the lower water-insoluble carboxymethyl cellulose with low substitution degree, and dialyzing for 2 days. Diluting the dialyzed carboxymethyl cellulose with low substitution degree to about 0.5%, and circulating for several times by a homogenizer, or shearing for a certain time by using a shearing emulsifier to obtain the carboxymethyl nano cellulose. Wherein the molar ratio of the chloroacetic acid (sodium) to the alkalizing agent sodium hydroxide is 1.5-2: 1.
Example 1:
accurately weighing 5g of crushed waste cotton fiber, adding 300g of 5% sodium hydroxide solution, stirring for 1h, washing with ethanol, filtering, putting into a three-necked flask, adding 6g of chloroacetic acid ethanol solution, heating to 45 ℃, slowly adding 3.8g of NaOH aqueous solution, stirring for reacting for 3h, and cooling to room temperature; and centrifugally washing with deionized water for three times, reserving the lower layer, dialyzing for 2 days, and homogenizing for 5 times by using a high-pressure homogenizer to obtain the carboxymethyl nano cellulose CMNC.
Example 2: accurately weighing 5g of crushed waste cotton fiber, adding 1.8g of NaOH solution (10g of water and 90mL of absolute ethyl alcohol), stirring for 1h at 30 ℃, adding 2.0g of chloroacetic acid, stirring for 2h at 75 ℃, and cooling to room temperature; and centrifugally washing with deionized water for three times, reserving the lower layer, dialyzing for 2 days, and shearing 10Min by using a shearing emulsifier to obtain the nano carboxymethyl cellulose NCMC.
Example 3: accurately weighing 5g of crushed waste cotton fiber, adding 1.8g of NaOH solution (10g of water and 90mL of absolute ethyl alcohol), stirring for 1h at 30 ℃, adding 2.0g of chloroacetic acid, stirring for 3h at 60 ℃, and cooling to room temperature; and centrifugally washing with deionized water for three times, reserving the lower layer, dialyzing for 2 days, and circulating for 5 times by using a high-pressure homogenizer to obtain the nano-carboxymethyl cellulose NCMC.
Example 4: accurately weighing 5g of crushed waste cotton fiber, adding 300g of 5% sodium hydroxide solution, stirring for 1h, washing with ethanol, filtering, putting into a three-necked flask, adding 15g of chloroacetic acid ethanol solution, heating to 45 ℃, slowly adding 9.5g of NaOH aqueous solution, stirring for reacting for 3h, and cooling to room temperature; and centrifugally washing with deionized water for three times, reserving the lower layer, dialyzing for 2 days, and homogenizing for 5 times by using a high-pressure homogenizer to obtain the carboxymethyl nano cellulose CMNC.
As mentioned above, the carboxymethyl nanocellulose is prepared by simply treating the recovered waste cotton fabric and then performing a two-step method of chemical pretreatment and mechanical treatment, so that a novel method which is simpler and more convenient in technical means is provided for high-value conversion and utilization of the waste cotton fabric, and the application value is outstanding.
As mentioned above, the preparation method of the invention sterilizes and crushes the collected waste cotton fabrics, if the waste cotton fabrics are not white, the color bleaching is needed; and carrying out carboxymethyl modification treatment on the crushed cotton fabric fibers, and carrying out high-pressure homogenization or shearing emulsification to obtain the CMNC. The obtained CMNC is Cellulose Nanofiber (CNFs), has higher thermal stability than nanocellulose obtained from other materials, and has higher carboxyl content than CNFs obtained by TEMPO catalytic oxidation. And with the improvement of the substitution degree of the carboxymethyl insoluble in water, the obtained CNF has better dispersibility in water and can be used for emulsion dispersion, biological composite materials, transparent films and the like.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (7)
1. A method for preparing carboxymethyl nano-cellulose from waste fabrics is characterized by comprising the following steps: bleaching, disinfecting and crushing the collected waste cotton fabrics to obtain cotton fabric fibers; weighing quantitative cotton fabric fibers, adding a sodium hydroxide solution for activation swelling treatment, and adding an etherification reagent chloroacetic acid or sodium chloroacetate for etherification reaction; cooling, centrifuging, washing with deionized water for 3-5 times, removing supernatant, retaining the water-insoluble carboxymethyl cellulose with low substitution degree in the lower layer, and dialyzing for 1-2 days; then diluting to about 0.5%, circulating for 1-10 times by a homogenizer, or shearing by using a shearing emulsifier to obtain the carboxymethyl nano-cellulose.
2. The method for preparing carboxymethyl nanocellulose from the waste fabric according to claim 1, wherein: the molar ratio of the sodium hydroxide to the chloroacetic acid or the sodium chloroacetate is 1.5-2: 1.
3. The method for preparing carboxymethyl nanocellulose from the waste fabric according to claim 2, wherein: the addition amount of the chloroacetic acid or the sodium chloroacetate is 2 to 10 percent of the total solution amount.
4. The method for preparing carboxymethyl nanocellulose from the waste fabric according to claim 3, wherein: the temperature of the etherification reaction is 45-75 ℃.
5. The method for preparing carboxymethyl nanocellulose from the waste fabric according to claim 2, wherein: the etherification reaction time is 1-6 h.
6. The method for preparing carboxymethyl nanocellulose from the waste fabric according to claim 2, wherein: the waste cotton fabrics are cut into blocks before being crushed.
7. Carboxymethyl nanocellulose of waste cotton fabric, characterized by being prepared by the method of any one of claims 1 to 6.
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| CN201911308956.7A CN111019003A (en) | 2019-12-18 | 2019-12-18 | Waste fabric nanocellulose and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861429A (en) * | 2021-10-27 | 2021-12-31 | 江南大学 | Modified polyvinylamine surface-modified fiber material and preparation method thereof |
| CN114409811A (en) * | 2021-12-21 | 2022-04-29 | 浙江金昌特种纸股份有限公司 | Nano cellulose capable of being stably dispersed in high-salt environment and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643357A (en) * | 2012-04-28 | 2012-08-22 | 长安大学 | Method for preparing sodium carboxymethylcellulose by abandoned cotton fabrics |
| CN104761648A (en) * | 2015-04-15 | 2015-07-08 | 桂林理工大学 | Method for preparing nanocellulose at low energy consumption |
| CN107602709A (en) * | 2017-10-25 | 2018-01-19 | 北京理工大学 | A kind of carboxymethyl nano cellulose material cleans preparation method |
| CN109970872A (en) * | 2017-12-28 | 2019-07-05 | 上海凯矜新材料科技有限公司 | Prepare cellulose nano-fibrous method |
-
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- 2019-12-18 CN CN201911308956.7A patent/CN111019003A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643357A (en) * | 2012-04-28 | 2012-08-22 | 长安大学 | Method for preparing sodium carboxymethylcellulose by abandoned cotton fabrics |
| CN104761648A (en) * | 2015-04-15 | 2015-07-08 | 桂林理工大学 | Method for preparing nanocellulose at low energy consumption |
| CN107602709A (en) * | 2017-10-25 | 2018-01-19 | 北京理工大学 | A kind of carboxymethyl nano cellulose material cleans preparation method |
| CN109970872A (en) * | 2017-12-28 | 2019-07-05 | 上海凯矜新材料科技有限公司 | Prepare cellulose nano-fibrous method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861429A (en) * | 2021-10-27 | 2021-12-31 | 江南大学 | Modified polyvinylamine surface-modified fiber material and preparation method thereof |
| CN113861429B (en) * | 2021-10-27 | 2022-05-10 | 江南大学 | Modified polyvinylamine surface modified fiber material and preparation method thereof |
| CN114409811A (en) * | 2021-12-21 | 2022-04-29 | 浙江金昌特种纸股份有限公司 | Nano cellulose capable of being stably dispersed in high-salt environment and preparation method thereof |
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