CN107177040A - A kind of cellulose solution and its dissolving method and application - Google Patents

A kind of cellulose solution and its dissolving method and application Download PDF

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CN107177040A
CN107177040A CN201710414026.4A CN201710414026A CN107177040A CN 107177040 A CN107177040 A CN 107177040A CN 201710414026 A CN201710414026 A CN 201710414026A CN 107177040 A CN107177040 A CN 107177040A
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cellulose
solution
hydroxide
ammonium hydroxide
cellulose solution
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CN107177040B (en
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吕昂
王洋
张俐娜
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Wuhan University WHU
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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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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Abstract

The invention discloses a kind of cellulose solution and its dissolving method and application.Cellulose is scattered in the alkyl phosphonium hydroxide aqueous ammonium that concentration is 0.5 ~ 2.5 M, stood at 10 ~ 30 DEG C to dispersion liquid fully charge, continued to freeze 0 ~ 12 h, then thaw at room temperature, that is, obtain the cellulose solution of transparent and homogeneous；Described alkyl ammonium hydroxide is the one or more in TMAH, triethyl methyl ammonium hydroxide, tetraethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide.The present invention is applied to molecular weight 7.0 × 104~3.0×105Native cellulose, simple to operate, solvability is strong, and cellulose solution stability is strong, environmentally safe, and dissolving is physical process, is not chemically reacted；Dicyandiamide solution is one-component solvent, and obtained cellulose solution can regenerate by coagulating bath of water to cellulose, and the alkyl ammonium hydroxide in waste liquid is easily recycled and recycled, with application prospect widely.

Description

A kind of cellulose solution and its dissolving method and application
Technical field
The present invention relates to a kind of cellulose solution and its dissolving method and application, belong to natural polymer subdomains.
Background technology
Into 21st century, the raw material and environment-friendly material and sustainable development of regenerative resource and resource are given full play to one's skill Art turns into the important directions of science and technology research and development.Plant cellulose is renewable resource most abundant on the earth, belongs to environment-friendly material Material, makes full use of cellulose not only can be with environmental protection, and can save limited petroleum resources, however, chemistry work at present Cellulose is far from reaching the stage made full use of in industry, be primarily due to cellulose dissolution process in existing process it is numerous and diverse, into This height and there is pollution.As viscose process has environmental pollution, expensive and solution is reclaimed；Other organic or inorganic solvents are such as Dimethyl sulfoxide-nitrogen oxides (U.S.patent 3236669,1966), ZnCl2The aqueous solution (U.S.Patent 5290349, 1994), LiCl/DMAc (U.S.Patent4302252,1981) etc. due to course of dissolution is numerous and diverse and price problem and be difficult to industry Change；N- methyl morpholine oxide-N- oxides (NMMO) (U.S.patent 2179181,1939；Brit.1144048,1967； U.S.patent4246221,1981) due to the reason such as its is expensive, spinning temperature is higher, industrialized production is made slow progress. Japan Report NaOH aqueous dissolutions cellulose (JapanPatent 1777283,1983；U.S.Patent4634470), but The wood pulp cellulose (degree of polymerization is less than 250) crossed through Steam explosion treatment, and obtained filament low intensity must be used. In addition with alkali/urea aqueous solvent (00114486.3；03128386.1；200310111447.8； 200310111567.8), but combination solvent is belonged to, the molecular weight for dissolving cellulose is not high, and solution is easier to gel, and recovery process It is complicated.
The content of the invention
In order to overcome, cellulose dissolution process present in prior art is numerous and diverse, cost is high and has pollution, dissolve cellulose The deficiency such as molecular weight not high, condition is harsh, cellulose solution stability difference, utilize alkyl phosphonium hydroxide the invention provides one kind The method that ammonium dissolves cellulose, this method can quickly and easily dissolve the cellulose of HMW, and condition is easily controllable, and Stability of solution is good, environmentally safe, and easily reclaims and recycle.
To achieve the above object, the present invention provides following technical scheme：
A kind of dissolving method of cellulose, comprises the following steps：Cellulose is scattered in the alkyl that concentration is 0.5~2.5M In ammonium hydroxide aqueous solution, stood at -10~-30 DEG C to dispersion liquid fully charge, continue to freeze 0~12h, then in room temperature It is lower to thaw, that is, obtain the cellulose solution of transparent and homogeneous；Described alkyl ammonium hydroxide is TMAH, triethyl group first One kind in base ammonium hydroxide, tetraethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide.
Described cellulose is that molecular weight is less than 3.0 × 105Native cellulose.
In described cellulose solution, content of cellulose is 0.2~15wt%.
A kind of cellulose solution, is obtained by the dissolving method of above-mentioned cellulose.
Application of the above-mentioned cellulose solution in regenerated cellulose field of membrane preparation.
Alkyl ammonium hydroxide of the present invention promotes the mechanism of cellulose dissolution as follows：TMAH, triethyl methyl Ammonium hydroxide, tetraethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, the quaternary ammonium cations of benzyltriethylammonium hydroxide have Hydroxide ion is to cellulose under enhanced hydrophobicity successively, the similar cationic surface active agent of its structure, cryogenic conditions While intramolecular and intermolecular hydrogen bonding are split, alkyl quaternary ammonium ion is due to the characteristic of its hydrophobic effect and surfactant It can be had an effect with cellulose chain hydrophobic part, so as to be gathered on the interface of cellulose chain and water, promote cellulose chain It is scattered, the aggregation again of cellulose chain is also prevented, so that the solubility and stability of cellulose are improved, and quaternary ammonium alkyl Ion hydrophobicity is stronger, and the solubility of cellulose is higher, and stability is stronger.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) present invention to cellulose without pre-processing, but it is water-soluble that cellulose directly is put into alkyl ammonium hydroxide Freeze-thaw is carried out in liquid to be completely dissolved, and easy to operate, solvability is strong, can dissolve molecular weight 3.0 × 105With Under cellulose, cellulose dissolution degree is higher, in the final solution of preparation the concentration range of alkyl ammonium hydroxide be 0.5~ 2.5M, and the stability of cellulose solution is strong.
(2) present invention is using alkyl phosphonium hydroxide aqueous ammonium as the dicyandiamide solution of cellulose, environmentally safe, cellulose Dissolving and regeneration in alkyl phosphonium hydroxide aqueous ammonium are all physical processes, are not chemically reacted, waste liquid is easily reclaimed and followed Ring is used.
(3) dicyandiamide solution of the present invention is one-component solvent, and prepared cellulose solution can be coagulator using water to fiber Element is regenerated and prepared by material, and liquid waste processing reclaims easy, is conducive to industrialized production.
Brief description of the drawings
Fig. 1 is the comparison diagram before and after freeze-thaw after cellulose is mixed with alkyl phosphonium hydroxide aqueous ammonium；Wherein, Fig. 1 (a) tetramethylammonium hydroxide aqueous solution is represented, Fig. 1 (b) represents triethyl methyl ammonium hydroxide aqueous solution, and Fig. 1 (c) represents tetrem Base ammonium hydroxide, Fig. 1 (d) represents the benzyltrimethylammonium hydroxide aqueous solution, and Fig. 1 (e) represents benzyltriethylammonium hydroxide water Solution；
Fig. 2~10 be different dissolution systems prepare cellulose solution under the conditions of temperature varied cyclical storage modulus and loss mould The change of amount and recovery capacity figure：
Fig. 2 represents the 7.0 × 10 of 2wt%4Molecular weight cotton linter is dissolved in the sodium hydroxide solution that concentration is 1.88M；
Fig. 3 represents the 7.0 × 10 of 2wt%4Molecular weight cotton linter is dissolved in the lithium hydroxide solution that concentration is 1.88M；
Fig. 4 represents the 7.0 × 10 of 5wt%4Molecular weight cotton linter is dissolved in sodium hydroxide/urine that concentration is 7wt%/12wt% Plain solution；
Fig. 5 represents the 7.0 × 10 of 5wt%4Molecular weight cotton linter be dissolved in concentration be 4.6wt%/15wt% lithium hydroxide/ Urea liquid；
Fig. 6 represents the 7.0 × 10 of 5wt%4It is molten that molecular weight cotton linter is dissolved in the TMAH that concentration is 1.88M Liquid；
Fig. 7 represents the 7.0 × 10 of 5wt%4Molecular weight cotton linter is dissolved in the triethyl methyl ammonium hydroxide that concentration is 1.88M Solution；
Fig. 8 represents the 7.0 × 10 of 5wt%4Molecular weight cotton linter is dissolved in the tetraethyl ammonium hydroxide that concentration is 1.88M Et4NOH solution；
Fig. 9 represents the 7.0 × 10 of 5wt%4Molecular weight cotton linter is dissolved in the benzyltrimethylammonium hydroxide that concentration is 1.88M Solution；
Figure 10 represents the 7.0 × 10 of 5wt%4Molecular weight cotton linter is dissolved in the benzyl triethyl ammonium hydroxide that concentration is 1.88M Ammonium salt solution.
Embodiment
Technical scheme is described further below in conjunction with specific example：
Embodiment 1
Take cotton linter pulp (viscosity-average molecular weight Mη=0.7 × 105) 5 grams, put into 95 grams of 1.88M TMAH water In solution, it is put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed After 4h transparent cellulose solution is can obtain in (25 DEG C) defrostings of room temperature.The content of cellulose is in obtained cellulose solution 5wt%, TMAH concentration is about 1.88M, and remaining is water.
Embodiment 2
Take cotton linter pulp (Mη=0.7 × 105) 6 grams, put into 94 grams of 1.88M triethyl methyl ammonium hydroxide aqueous solutions, Be put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge be cooled in -22 DEG C, place 4h after (25 DEG C) of room temperature, which is thawed, can obtain transparent cellulose solution.The content of cellulose is 6wt% in obtained cellulose solution, Triethyl methyl ammonium hydroxide concentration is about 1.88M, and remaining is water.
Embodiment 3
Take cotton linter pulp (Mη=0.7 × 105) 8 grams, put into 92 grams of 1.88M tetraethyl ammonium hydroxide aqueous solution, in room It is put into after warm (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h in room temperature It is that can obtain transparent cellulose solution that (25 DEG C), which thaw,.Content of cellulose is 8wt%, tetraethyl in obtained cellulose solution Ammonium hydroxide concentration is about 1.88M, and remaining is water.
Embodiment 4
Take cotton linter pulp (Mη=0.7 × 105) 10 grams, put into 90 grams of 1.88M benzyltrimethylammonium hydroxide aqueous solution In, it is put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h Transparent cellulose solution is can obtain in (25 DEG C) defrostings of room temperature.Content of cellulose is in obtained cellulose solution 10wt%, benzyltrimethylammonium hydroxide concentration is about 1.88M, and remaining is water.
Embodiment 5
Take cotton linter pulp (Mη=0.7 × 105) 12 grams, put into 88 grams of 1.88M benzyltriethylammonium hydroxide aqueous solution In, it is put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h Transparent cellulose solution is can obtain in (25 DEG C) defrostings of room temperature.Content of cellulose is in obtained cellulose solution 12wt%, benzyltriethylammonium hydroxide concentration is about 1.88M, and remaining is water.
Embodiment 6
Take medical absorbent cotton (Mη=2.1 × 105) 8 grams, put into 92 grams of 1.88M benzyltriethylammonium hydroxide aqueous solution In, it is put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h Transparent cellulose solution is can obtain in (25 DEG C) defrostings of room temperature.Content of cellulose is 8wt% in obtained cellulose solution, Benzyltriethylammonium hydroxide concentration is about 1.88M, and remaining is water.
Embodiment 7
Take cotton linter pulp (Mη=0.7 × 105) 3 grams, put into 97 grams of 0.5M benzyltriethylammonium hydroxide aqueous solution, Be put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge be cooled in -22 DEG C, place 4h after (25 DEG C) of room temperature, which is thawed, can obtain transparent cellulose solution.Content of cellulose is 3wt%, benzyl in obtained cellulose solution Base triethylammonium hydroxide concentration is about 0.5M, and remaining is water.
Embodiment 8
Take cotton linter pulp (Mη=0.7 × 105) 5 grams, put into 95 grams of 1.88M tetramethylammonium hydroxide aqueous solutions, in room It is put into after warm (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h in room temperature It is that can obtain transparent cellulose solution that (25 DEG C), which thaw,.The content of cellulose is 5wt%, tetramethyl in obtained cellulose solution Base ammonium hydroxide concentration is about 1.88M, and remaining is water.
By obtained cellulose solution evacuation and centrifugal degassing under room temperature (25 DEG C), casting film-forming, is then placed on a glass Soak after 5min and take out in ionized water, continuation is rinsed well with deionized water, and regenerated cellulose film is can be prepared by after drying.
Embodiment 9
Take cotton linter pulp (Mη=0.7 × 105) 5 grams, put into 95 grams of 1.88M triethyl methyl ammonium hydroxide aqueous solutions, Be put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge be cooled in -22 DEG C, place 4h after (25 DEG C) of room temperature, which is thawed, can obtain transparent cellulose solution.The content of cellulose is 5wt% in obtained cellulose solution, Triethyl methyl ammonium hydroxide concentration is about 1.88M, and remaining is water.
By obtained cellulose solution evacuation and centrifugal degassing under room temperature (25 DEG C), casting film-forming, is then placed on a glass Soak after 5min and take out in ionized water, continuation is rinsed well with deionized water, and regenerated cellulose film is can be prepared by after drying.
Embodiment 10
Take cotton linter pulp (Mη=0.7 × 105) 5 grams, put into 95 grams of 1.88M tetraethyl ammonium hydroxide aqueous solution, in room It is put into after warm (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h in room temperature It is that can obtain transparent cellulose solution that (25 DEG C), which thaw,.Content of cellulose is 5wt%, tetraethyl in obtained cellulose solution Ammonium hydroxide concentration is about 1.88M, and remaining is water.
By obtained cellulose solution evacuation and centrifugal degassing under room temperature (25 DEG C), casting film-forming, is then placed on a glass Soak after 5min and take out in ionized water, continuation is rinsed well with deionized water, and regenerated cellulose film is can be prepared by after drying.
Embodiment 11
Take cotton linter pulp (Mη=0.7 × 105) 5 grams, put into 95 grams of 1.88M benzyltrimethylammonium hydroxide aqueous solution, Be put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge be cooled in -22 DEG C, place 4h after (25 DEG C) of room temperature, which is thawed, can obtain transparent cellulose solution.Content of cellulose is 5wt%, benzyl in obtained cellulose solution Base trimethylammonium hydroxide concentration is about 1.88M, and remaining is water.
By obtained cellulose solution evacuation and centrifugal degassing under room temperature (25 DEG C), casting film-forming, is then placed on a glass Soak after 5min and take out in ionized water, continuation is rinsed well with deionized water, and regenerated cellulose film is can be prepared by after drying.
Embodiment 12
Take cotton linter pulp (Mη=0.7 × 105) 5 grams, put into 95 grams of 1.88M benzyltriethylammonium hydroxide aqueous solution, Be put into after room temperature (25 DEG C) shaken well in freezer compartment of refrigerator and mixture fully charge be cooled in -22 DEG C, place 4h after (25 DEG C) of room temperature, which is thawed, can obtain transparent cellulose solution.Content of cellulose is 5wt%, benzyl in obtained cellulose solution Base triethylammonium hydroxide concentration is about 1.88M, and remaining is water.
By obtained cellulose solution evacuation and centrifugal degassing under room temperature (25 DEG C), casting film-forming, is then placed on a glass Soak after 5min and take out in ionized water, continuation is rinsed well with deionized water, and regenerated cellulose film is can be prepared by after drying.
Embodiment 13：The influence of various concentrations and variety classes alkyl phosphonium hydroxide ammonium salt solution to cellulose cotton short flannel solubility
Compound concentration is respectively 0.5M, 1.0M, 1.5M, 1.88M tetramethylammonium hydroxide aqueous solution, triethyl group first first Base ammonium hydroxide aqueous solution, the tetraethyl ammonium hydroxide aqueous solution, the benzyltrimethylammonium hydroxide aqueous solution, benzyl triethyl ammonium hydrogen-oxygen Change aqueous ammonium；Take cotton linter pulp (Mη=7.0 × 104), put into the above-mentioned aqueous solution, after room temperature (25 DEG C) shaken well It is put into freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, places i.e. available in (25 DEG C) defrostings of room temperature after 4h Transparent cellulose solution.Cellulose dissolution degree result is listed in table 1 in obtained cellulose solution.
7.0 × 10 in the various concentrations of table 1 and variety classes alkyl phosphonium hydroxide ammonium salt solution4Molecular weight cellulose cotton linter is molten Xie Du (wt%)
Embodiment 14：Influence of the variety classes alkyl phosphonium hydroxide ammonium salt solution to cellulose cotton short flannel solubility
It is water-soluble for 1.88M tetramethylammonium hydroxide aqueous solution, triethyl methyl ammonium hydroxide that compound concentration is distinguished first Liquid, the tetraethyl ammonium hydroxide aqueous solution, the benzyltrimethylammonium hydroxide aqueous solution, the benzyltriethylammonium hydroxide aqueous solution；Take Cotton linter pulp (Mη=7.0 × 104、1.0×105、2.1×105), put into the above-mentioned aqueous solution, it is equal in (25 DEG C) vibrations of room temperature It is put into after even in freezer compartment of refrigerator and mixture fully charge is cooled in -22 DEG C, is placed after 4h in (25 DEG C) defrostings of room temperature Obtain transparent cellulose solution.Cellulose dissolution degree result is listed in table 2 in obtained cellulose solution.
The concentration of table 2 is different molecular weight cellulose cotton short flannel solubility in 1.88M variety classes alkyl phosphonium hydroxide ammonium salt solutions (wt%)
Embodiment 15：Influence of the dissolution system to carbon atom chemical shift
It is water-soluble for 1.88M tetramethylammonium hydroxide aqueous solution, triethyl methyl ammonium hydroxide that compound concentration is distinguished first Liquid, the tetraethyl ammonium hydroxide aqueous solution, the benzyltrimethylammonium hydroxide aqueous solution, the benzyltriethylammonium hydroxide aqueous solution, hydrogen Sodium hydroxide solution, sodium hydroxide/urea liquid and lithium hydroxide/urea liquid；Take cotton linter pulp (Mη=7.0 × 104), input Into the above-mentioned aqueous solution.Physical dissolution proves by carbon-13 nmr spectra, as shown in table 3, the cellulose solution prepared by the present invention In, each carbon atom chemical shift and carbon atom chemical shift in sodium hydroxide, sodium hydroxide/urea, lithium hydroxide/urea system Unanimously (Cai, J.；Zhang, L.Macromolecular Bioscience 2005,5,539.), illustrate cellulose in alkyl It is consistent in dissolving and regeneration and sodium hydroxide, sodium hydroxide/urea, lithium hydroxide/urea system in ammonium hydroxide aqueous solution, All it is physical process, does not chemically react.
The carbon atom chemistry of 3 alkyl ammonium hydroxides of table-cellulose solution and the cellulose solution of other physical dissolution systems Displacement (ppm)
Embodiment 16
First with different dissolution systems to 7.0 × 104Molecular weight cotton linter is dissolved, and is obtained content of cellulose and is 2wt% or 5wt% cellulose solution, to above-mentioned cellulose solution under the conditions of temperature varied cyclical storage modulus and loss modulus Change and recovery capacity are tested, and as a result as shown in Fig. 2~Figure 10, storage modulus then represents molten with loss modulus curve intersection Gel occurs for liquid.
Above-described embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect Detailed description, should be understood that the foregoing is only the present invention instantiation, be not intended to limit the invention, Within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., should be included in the present invention's Within protection domain.

Claims (5)

1. a kind of dissolving method of cellulose, it is characterised in that comprise the following steps：By cellulose be scattered in concentration for 0.5 ~ In 2.5 mol/L alkyl phosphonium hydroxide aqueous ammonium, stood at -10 ~ -30 DEG C to dispersion liquid fully charge, continue to freeze 0 ~ 12 h, then thaw at room temperature, that is, obtain the cellulose solution of transparent and homogeneous；Described alkyl ammonium hydroxide is tetramethyl Ammonium hydroxide, triethyl methyl ammonium hydroxide, tetraethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl triethyl ammonium hydrogen-oxygen Change one kind in ammonium.
2. the dissolving method of cellulose according to claim 1, it is characterised in that：Described cellulose is less than for molecular weight 3.0×105Native cellulose.
3. the dissolving method of cellulose according to claim 1, it is characterised in that：In described cellulose solution, fiber Cellulose content is 0.2 ~ 15 wt%.
4. a kind of cellulose solution, it is characterised in that：Prepared as the dissolving method of the cellulose described in claim any one of 1-3 Obtain.
5. application of the cellulose solution in regenerated cellulose field of membrane preparation described in claim 4.
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Cited By (11)

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CN108276591A (en) * 2018-03-01 2018-07-13 南京林业大学 A kind of cellulose solution and preparation method thereof
CN108468204A (en) * 2018-03-08 2018-08-31 深圳市彩铜时代科技有限公司 The preparation method of antibacterial inorganic metal salt cellulose fibre
CN108822343A (en) * 2018-04-25 2018-11-16 武汉水木弘新材料有限公司 A kind of preparation method of phase transformation material of regenerated cellulose
WO2019180321A1 (en) 2018-03-20 2019-09-26 Helsingin Yliopisto Method of processing cellulosic materials
CN111909393A (en) * 2020-07-07 2020-11-10 湖北工业大学 Cellulose solution and method for dissolving cellulose
CN112876693A (en) * 2021-02-10 2021-06-01 湖北工业大学 Lignocellulose solution and lignocellulose dissolving method
CN113564731A (en) * 2021-06-17 2021-10-29 武汉纺织大学 Method for recycling waste denim laser ash and recycled material
CN113861446A (en) * 2021-10-13 2021-12-31 东华理工大学 Cellulose solvent, cellulose dissolving method and cellulose solution
CN115304803A (en) * 2022-07-29 2022-11-08 华南农业大学 High-transparency high-haze regenerated cellulose-based composite film and preparation method and application thereof
CN115656071A (en) * 2022-11-14 2023-01-31 青岛科技大学 Preparation method of hydroxypropyl cellulose solution and determination method of cellulase activity
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CN104710627A (en) * 2015-03-02 2015-06-17 西南交通大学 Process method for improving dissolving property of cellulose in tetrabutyl ammonium hydroxide aqueous solution

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WO2013085053A1 (en) * 2011-12-09 2013-06-13 株式会社ダイセル Method for producing aqueous cellulose solution and method for producing cellulose derivative
CN104710627A (en) * 2015-03-02 2015-06-17 西南交通大学 Process method for improving dissolving property of cellulose in tetrabutyl ammonium hydroxide aqueous solution

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* Cited by examiner, † Cited by third party
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CN108276591A (en) * 2018-03-01 2018-07-13 南京林业大学 A kind of cellulose solution and preparation method thereof
CN108276591B (en) * 2018-03-01 2021-05-11 南京林业大学 Cellulose solution and preparation method thereof
CN108468204A (en) * 2018-03-08 2018-08-31 深圳市彩铜时代科技有限公司 The preparation method of antibacterial inorganic metal salt cellulose fibre
WO2019180321A1 (en) 2018-03-20 2019-09-26 Helsingin Yliopisto Method of processing cellulosic materials
CN108822343A (en) * 2018-04-25 2018-11-16 武汉水木弘新材料有限公司 A kind of preparation method of phase transformation material of regenerated cellulose
CN111909393A (en) * 2020-07-07 2020-11-10 湖北工业大学 Cellulose solution and method for dissolving cellulose
CN112876693A (en) * 2021-02-10 2021-06-01 湖北工业大学 Lignocellulose solution and lignocellulose dissolving method
CN112876693B (en) * 2021-02-10 2022-10-21 湖北工业大学 Lignocellulose solution and lignocellulose dissolving method
CN113564731A (en) * 2021-06-17 2021-10-29 武汉纺织大学 Method for recycling waste denim laser ash and recycled material
CN113861446A (en) * 2021-10-13 2021-12-31 东华理工大学 Cellulose solvent, cellulose dissolving method and cellulose solution
CN115304803A (en) * 2022-07-29 2022-11-08 华南农业大学 High-transparency high-haze regenerated cellulose-based composite film and preparation method and application thereof
CN115656071A (en) * 2022-11-14 2023-01-31 青岛科技大学 Preparation method of hydroxypropyl cellulose solution and determination method of cellulase activity
CN116512373A (en) * 2023-05-05 2023-08-01 武汉大学 Cellulose substrate material and preparation method thereof

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