CN109880135A - The preparation method of cellulose membrane material under a kind of novel dissolution system - Google Patents
The preparation method of cellulose membrane material under a kind of novel dissolution system Download PDFInfo
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- CN109880135A CN109880135A CN201910090265.8A CN201910090265A CN109880135A CN 109880135 A CN109880135 A CN 109880135A CN 201910090265 A CN201910090265 A CN 201910090265A CN 109880135 A CN109880135 A CN 109880135A
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Abstract
The invention discloses a kind of preparation methods of cellulose membrane material under novel dissolution system, include the following steps: (1) using cellulose as raw material, cellulose, organic base and organic solvent are mixed, mixture is obtained, the CO of 0.1-15MPa pressure is passed through into mixture2, reacted 0.1-24 hours at 30-100 DEG C, form the cellulose solution of homogeneous phase；(2) by cellulose solution by being poured on smooth supporting layer, then slowly strike off solution with scraper after evacuation and centrifugal degassing；(3) supporting layer with cellulose solution is put into rapidly in the regeneration bath of lower aliphatic alcohols of water, the acid-base salt solution of water or C1-C3, regenerated from washing obtains fiber film material after dry.The present invention has dissolution system economy, high-efficient, strong operability, convenient for purifying and recycle；The feature that the fiber film material of preparation has a wide range of application, production cost is low, transparent and mechanical property is good.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose membrane, cellulose membrane material under especially a kind of novel dissolution system
Preparation method.
Background technique
With the progress of human society, the demand of the energy is increasingly increased, the energy master to depend on for existence and development
To derive from petroleum-based sources.In view of the non-renewable of petroleum resources, find the new energy replace conventional petroleum resource at
For the hot spot of research, it is all fixation to solar energy that lignocellulosic has resource the same simultaneously, is had widely distributed and with can
Reproducibility and sustainability, as the potential main energy sources for replacing petroleum-based sources.Wherein cellulose is lignocellulosic
Chief component has many advantages, such as preferable chemical and thermal stability, biocompatibility, biodegradable, nontoxic.CO2It is
The main reason for influencing Global Greenhouse Effect, although CO2Have for greenhouse effects and seriously affect, but itself can be used as
Important C1 resource is utilized, therefore about CO2Capture fixation have become a hot topic of research.Cellulose is due to intermolecular and molecule
Interior hydrogen bond action keeps it insoluble in common organic solvents, is unable to melt-processed, so that it is restricted in homogeneous modification,
Recently with CO2/ DBU/DMSO be dissolution system dissolve cellulose proposition (Xie, Haibo, Yu, XueYang,
Yunlongetal.Greenchemistry,2014,16(5):2422-2427；Zhang,QinghuaOztekin,
Etal.ChemSusChem, 2013,6 (4): 593-596), dissolution for cellulose and modified from high efficiency, sustainability
Bring breakthrough progress.
Important application form of the cellulose membrane material as cellulosic material, in biologic applications, new energy battery membranes, gas
Seperation film, chiral separation and food packaging applications are widely applied.Cellulose regenerated membrane material mainly passes through viscose process and organic molten
The preparation of agent method of reproduction.But the factors such as backbone structure of cellulose high molecular weight itself, high-crystallinity, rigidity, do not dissolve in it
Common solvent, to limit corresponding processability.With the proposition of the dissolution system of each new cellulose, difference regeneration
The technique of cellulose membrane is suggested, especially glyoxaline ion liquid cellulose dissolution processing more it is common (VitzJ,
ErdmengerT,HaenschC,etal.Greenchemistry,2009,11(3):417-424.).However, ionic liquid valence
Lattice are higher, prepare and purify process complexity and are highly energy-consuming process, in addition, the toxicity of ionic liquid is not recognized completely also
Know, therefore it does not have economy, sustainability in the dissolution production of cellulose.
Chinese patent 201210374955.4 protects a kind of based on CO2The cellulose dissolution processes of switching mode solvent,
It is mainly characterized by utilizing CO that is cheap, being easy preparation2Switch property ionic compound or CO2Switch property ionic compound with it is organic
The mixed solvent system of solvent composition realizes non-derivative dissolution and the CO of cellulose2Derivatization dissolution.Based on renewable resource
Utilization and the angle that utilizes of greenhouse gases set out, realize cellulose dissolution in a mild condition, obtain homogeneous cellulose solution,
Breakthrough progress is brought for the processing and modification of subsequent fiber element.
The invention patent is to be based on cellulose in the presence of an organic base, with CO2It is reversible that reaction generates cellulose base carbonate
Ion liquid compound realizes the dissolution of cellulose.There are different crystal properties, mechanics in different regenerated solvent regeneration preparations
The regenerated cellulose film of intensity, optical property.Realize the recycling of regenerated solvent and organic solvent.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of cellulose membrane material under novel dissolution system.The present invention
With dissolution system economy, high-efficient, strong operability, convenient for purifying and recycle；The fiber film material application model of preparation
Enclose the feature wide, production cost is low, transparent and mechanical property is good.
Technical solution of the present invention: the preparation method of cellulose membrane material under a kind of novel dissolution system, including walk as follows
It is rapid:
(1) using cellulose as raw material, cellulose, organic base and organic solvent is mixed, mixture is obtained, led into mixture
Enter the CO of 0.1-15MPa pressure2, reacted 0.1-24 hours at 30-100 DEG C, form homogeneous cellulose solution；
(2) it by cellulose solution by being poured on smooth supporting layer after evacuation and centrifugal degassing, then is slowly struck off with scraper molten
Liquid；
(3) supporting layer with cellulose solution is put into rapidly the lower aliphatic of water, the acid-base salt solution of water or C1-C3
In the regeneration bath of alcohol, regenerated from washing obtains fiber film material after dry.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, the cellulose are microcrystalline cellulose or α-
Cellulose and from cotton pulp Hectometer, wood pulp Hectometer, bamboo slurry Hectometer, agricultural crop straw or crop seeds leather shell resulting separation plant
The mixture of one or both of fibres element or more, structure are as follows:
Wherein polymerization scope is 50 < n < 1000.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, in mixture described in step (1), fiber
The mass concentration of element is 0.1-20wt%, the mass concentration of organic base is 0.5-50wt%, and surplus is organic solvent.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, the organic base are one in following structures
Kind or two kinds or more of mixture:
Wherein:
A series, R1 is the alkyl that carbon atom number is 1-6, and R2, R3 and R4 are independent methyl；
B series, n=1 or n=2；M=1-6；R is independent hydrogen, methyl or ethyl；R1 is independent hydrogen or carbon atom number
For the alkyl of 1-6；R2, R3, R4 and R5 are independent hydrogen, methyl or ethyl.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, the organic solvent be dimethyl sub-maple,
N- methylpyrrolidone, tetramethylurea, tetraethyl urea, N, N- dimethyl-imidazolinone, N,N-dimethylformamide, N, N- diethyl
Yl acetamide, pyrrolidones, 2- piperazine ketone, epsilon-caprolactams, N, N- dimethyl propylene alkenyl urea, sulfolane or pentadiene sulfone
One or both of or more mixture.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, the supporting layer are glass plate, stainless
Steel board or engineering plastics.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, after solution described in step (2) strikes off,
With a thickness of 5-1000 μm.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, step (2) the cellulose solution middle-jiao yang, function of the spleen and stomach
Ion has the following structure feature:
Wherein:
A series, R1The alkyl for being 1-6 for carbon atom number, R2、R3And R4It is independent methyl；
B series, n=1 or n=2；M=1-6；R is independent hydrogen, methyl or ethyl；R1It is independent hydrogen or carbon atom number
For the alkyl of 1-6；R2、R3、R4And R5It is independent hydrogen, methyl or ethyl；
Cellulose anion has the following structure:
Wherein 50 ﹤ n ﹤ 1000.
The preparation method of cellulose membrane material under novel dissolution system above-mentioned, the acid-base salt solution of step (3) described water
Concentration be 1-20wt%, regeneration gained gel detergent 1-48h；Drying temperature is 20-100 DEG C, dry 1-72h.
Beneficial effects of the present invention
1, under novel dissolution system, cellulose organic base effect under with CO2Reaction generate cellulose base it is reversible from
Sub- liquid compound realizes the dissolution of cellulose.Dissolution system economy, high-efficient, strong operability are convenient for purifying and circulation benefit
With.
2, the dissolution system can obtain unformed cellulose in certain regenerated solvent, compared to other systems,
Prepare it is specific have unformed cellulose membrane have more advantage, expanded the application range of same system fiber film material.
3, cellulose membrane is prepared using various celluloses as raw material, wherein further including from agriculture and forestry organic waste material resource acquisition
Cellulose be raw material.Raw material sources are extensive, and substantially reduce the production cost of cellulose membrane, realize biomass resource
High-efficiency Sustainable utilize.
4, the present invention can prepare the cellulose membrane of good transparency and higher mechanical property, and preparation process is simple, can grasp
The property made is strong.
Detailed description of the invention
Fig. 1 is the invention patent flow chart of steps；
Fig. 2 is different regenerated cellulose film XRD；
Fig. 3 is different regenerated cellulose film stress-strain diagrams；
Fig. 4 is different regenerated cellulose film transmitances；
Fig. 5 is different regenerated cellulose film AFM；
Fig. 6 is different regenerated cellulose film SEM.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1:
Weigh different types of cellulose 5wt% (0.65g), 11 carbon -7- of organic base 1,8- diazabicylo [5.4.0]
Alkene (DBU) 1.83g and dimethyl sulfoxide (DMSO) 10g (the ratio between DBU and the molal quantity of glucose unit in cellulose are 3:1),
It is added to autoclave together to tighten, is passed through the CO of 0.5MPa2, it is stirred to react under 50 1 hour, it is molten obtains homogeneous cellulose
Liquid is scraped solution on Die and mould plate using coating device after the processing of cellulose solution evacuation and centrifugal degassing, and film tool plate is put into ethyl alcohol
Middle regeneration is impregnated for 24 hours with ethyl alcohol, is dried in vacuo at 60 DEG C.Mechanics Performance Testing, phase are carried out to dry regenerated cellulose film
The experimental result answered is as shown in table 1:
The mechanical property of 1 variety classes cellulose membrane of table
This example demonstrates the invention patent for the cellulose of separate sources and the cellulose of different molecular weight
Universality range.
Embodiment 2:
Weigh alpha-cellulose 5wt% (0.65g), organic base (in organic base and cellulose the molal quantity of glucose unit it
Than being added to autoclave together and tightening, be passed through the CO of 0.5MPa for 3:1) and dimethyl sulfoxide (DMSO) 10g2, under 50
It is stirred to react 1 hour, obtains homogeneous cellulose solution, it, will be molten using coating device after the processing of cellulose solution evacuation and centrifugal degassing
Liquid is scraped on Die and mould plate, and film tool plate is put into ethyl alcohol and is regenerated, is impregnated for 24 hours with ethyl alcohol, is dried in vacuo at 60 DEG C.To dry
Regenerated cellulose film carries out Mechanics Performance Testing, and corresponding experimental result is as shown in table 2:
The mechanical property of cellulose membrane under the different organic base dissolution systems of table 2
Universality this example demonstrates the invention patent for different organic bases as the component part of dissolution system
Range.
Embodiment 3:
Weigh different quality cellulose, 11 carbon -7- alkene (DBU) of organic base 1,8- diazabicylo [5.4.0] wherein
(the ratio between DBU and the molal quantity of glucose unit in cellulose are 3:1) and dimethyl sulfoxide (DMSO) 10g, are added to height together
Pressure reaction kettle is tightened, and the CO of 0.5MPa is passed through2, it is stirred to react under 50 1 hour, obtains homogeneous cellulose solution, by cellulose
After the processing of solution evacuation and centrifugal degassing, solution is scraped on Die and mould plate using coating device, film tool plate is put into ethyl alcohol and is regenerated, second is used
Alcohol impregnates for 24 hours, is dried in vacuo at 60 DEG C.Mechanics Performance Testing, corresponding experiment knot are carried out to dry regenerated cellulose film
Fruit is as shown in table 3:
The mechanical property of the cellulose membrane of 3 various concentration cellulose solution of table preparation
This example demonstrates the invention patent for the universality range of various concentration cellulose solution.
Embodiment 4:
Weigh different types of cellulose 5wt% (0.65g), 11 carbon -7- of organic base 1,8- diazabicylo [5.4.0]
Alkene (DBU) 1.83g and dimethyl sulfoxide (DMSO) 10g (the ratio between DBU and the molal quantity of glucose unit in cellulose are 3:1),
It is added to autoclave together to tighten, is passed through the CO of 0.5MPa2, it is stirred to react under 50 1 hour, it is molten obtains homogeneous cellulose
Liquid is scraped solution on Die and mould plate using coating device after the processing of cellulose solution evacuation and centrifugal degassing, and film tool plate is put into ethyl alcohol
Middle regeneration is impregnated for 24 hours with different regenerated solvents, is dried in vacuo at 60 DEG C.Mechanical property is carried out to dry regenerated cellulose film
It can test, corresponding experimental result is as shown in table 4:
The mechanical property of the cellulose membrane of 4 various concentration cellulose solution of table preparation
This example demonstrates the invention patent for the universality range of different regenerated solvents.
Claims (9)
1. the preparation method of cellulose membrane material under a kind of novel dissolution system, which comprises the steps of:
(1) using cellulose as raw material, cellulose, organic base and organic solvent is mixed, mixture is obtained, is passed through into mixture
The CO of 0.1-15MPa pressure2, reacted 0.1-24 hours at 30-100 DEG C, form homogeneous cellulose solution；
(2) by cellulose solution by being poured on smooth supporting layer, then slowly strike off solution with scraper after evacuation and centrifugal degassing；
(3) supporting layer with cellulose solution is put into rapidly the lower aliphatic alcohols of water, the acid-base salt solution of water or C1-C3
In regeneration bath, regenerated from washing obtains fiber film material after dry.
2. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: described
Cellulose is microcrystalline cellulose or alpha-cellulose and starches Hectometer, agricultural crop straw or farming species from cotton pulp Hectometer, wood pulp Hectometer, bamboo
The mixture of one or both of plant cellulose of resulting separation or more, structure are as follows in sub- leather shell:
Wherein polymerization scope is 50 < n < 1000.
3. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: step
(1) in the mixture described in, the mass concentration of cellulose is 0.1-20wt%, the mass concentration of organic base is 0.5-50wt%,
Surplus is organic solvent.
4. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: described
Organic base is the mixture of one or both of following structures or more:
A:
B:
Wherein:
A series, R1 is the alkyl that carbon atom number is 1-6, and R2, R3 and R4 are independent methyl；
B series, n=1 or n=2；M=1-6；R is independent hydrogen, methyl or ethyl；R1 is independent hydrogen or carbon atom number is 1-
6 alkyl；R2, R3, R4 and R5 are independent hydrogen, methyl or ethyl.
5. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: described
Organic solvent is dimethyl sub-maple, N- methylpyrrolidone, tetramethylurea, tetraethyl urea, N, N- dimethyl-imidazolinone, N, N-
Dimethylformamide, N, N- diethyl acetamide, pyrrolidones, 2- piperazine ketone, epsilon-caprolactams, N, N- dimethyl propylene alkenyl
The mixture of one or both of urea, sulfolane or pentadiene sulfone or more.
6. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: described
Supporting layer, be glass plate, stainless steel materials or engineering plastics.
7. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: step
(2) after the solution described in strikes off, with a thickness of 5-1000 μm.
8. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: step
(2) cation has the following structure feature in the cellulose solution:
A:
B:
Wherein:
A series, R1The alkyl for being 1-6 for carbon atom number, R2、R3And R4It is independent methyl；
B series, n=1 or n=2；M=1-6；R is independent hydrogen, methyl or ethyl；R1It is independent hydrogen or carbon atom number is 1-6
Alkyl；R2、R3、R4And R5It is independent hydrogen, methyl or ethyl；
Cellulose anion has the following structure:
Wherein 50 ﹤ n ﹤ 1000.
9. the preparation method of cellulose membrane material under novel dissolution system according to claim 1, it is characterised in that: step
(3) concentration of the acid-base salt solution of the water is 1-20wt%, regeneration gained gel detergent 1-48h；Drying temperature is 20-100
DEG C, dry 1-72h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229354A (en) * | 2019-06-24 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of method and system dissolving cellulose |
| CN110283349A (en) * | 2019-06-27 | 2019-09-27 | 贵州大学 | A kind of preparation method of lignosulfonates cellulose composite membrane |
| CN111519269A (en) * | 2020-06-30 | 2020-08-11 | 山东金正新科农业发展有限公司 | Method for preparing regenerated cellulose fiber by double-component coagulating bath |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103694482A (en) * | 2012-09-27 | 2014-04-02 | 中国科学院大连化学物理研究所 | Cellulose solution, cellulose dissolution method and regenerated cellulose |
| CN104610557A (en) * | 2013-11-01 | 2015-05-13 | 中国科学院化学研究所 | Regenerated cellulose membrane, functional membrane, and preparation method of regenerated cellulose membrane and functional membrane |
| WO2016193542A1 (en) * | 2015-05-29 | 2016-12-08 | Teknologian Tutkimuskeskus Vtt Oy | Molar mass controlled cellulose |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694482A (en) * | 2012-09-27 | 2014-04-02 | 中国科学院大连化学物理研究所 | Cellulose solution, cellulose dissolution method and regenerated cellulose |
| CN104610557A (en) * | 2013-11-01 | 2015-05-13 | 中国科学院化学研究所 | Regenerated cellulose membrane, functional membrane, and preparation method of regenerated cellulose membrane and functional membrane |
| WO2016193542A1 (en) * | 2015-05-29 | 2016-12-08 | Teknologian Tutkimuskeskus Vtt Oy | Molar mass controlled cellulose |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229354A (en) * | 2019-06-24 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of method and system dissolving cellulose |
| CN110229354B (en) * | 2019-06-24 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | Method and system for dissolving cellulose |
| CN110283349A (en) * | 2019-06-27 | 2019-09-27 | 贵州大学 | A kind of preparation method of lignosulfonates cellulose composite membrane |
| CN111519269A (en) * | 2020-06-30 | 2020-08-11 | 山东金正新科农业发展有限公司 | Method for preparing regenerated cellulose fiber by double-component coagulating bath |
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Application publication date: 20190614 |