CN106220869B - A kind of preparation method of polysaccharide dispersion liquid - Google Patents
A kind of preparation method of polysaccharide dispersion liquid Download PDFInfo
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- CN106220869B CN106220869B CN201610592201.4A CN201610592201A CN106220869B CN 106220869 B CN106220869 B CN 106220869B CN 201610592201 A CN201610592201 A CN 201610592201A CN 106220869 B CN106220869 B CN 106220869B
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- polysaccharide
- licl
- dmac
- cellulose
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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
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
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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
- C08J2301/04—Oxycellulose; Hydrocellulose
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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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
A kind of preparation method of polysaccharide dispersion liquid, is related to polysaccharide.The following steps are included: 1) polysaccharide is dried after exchange of solvent；2) using DMAc as solvent, prepare LiCl mass concentration be 2%~6% DMAc/LiCl solution, add step 1) it is activated, drying after polysaccharide, up to polysaccharide Heterodisperse liquid, LiCl is added, makes its total mass concentration 3%~20% to get polysaccharide dispersion liquid.Avoid the degradation that cellulose and chitin can be effectively prevent using hot conditions and solvent volatilization, the energy conservation of low-temperature atmosphere-pressure condition and saving equipment manufacturing cost.LiCl is added in two steps, and agglomeration rendezvous problem when saving the dissolution time of a part of LiCl, and completely solving especially compounding high concentration cellulose solution in course of dissolution substantially reduces dissolution time.
Description
Technical field
The present invention relates to polysaccharide, more particularly to a kind of preparation method of polysaccharide dispersion liquid.
Background technique
The polysaccharide such as lignocellulosic have the characteristics that abundant raw material is easy to get, is degradable, is renewable, price is low, environmental-friendly.
As renewable resource, the higher value application of lignocellulosic and chitin can be in light industry, material, the energy, chemical industry, food
Etc. industries bring huge economic benefit.Since there are a large amount of intramolecular and intermolecular hydrogen bondings in structure, it is difficult normal
Advise reagent dissolution.However under homogeneous dissolved state, the reaction of hydroxyl and derivatization reagent on the polysaccharide chains such as lignocellulosic
It will become more efficiently and uniform.Therefore, the research for the dissolution system of the polysaccharide such as lignocellulosic is always research work
The focus of person.
DMAc/LiCl dicyandiamide solution is the good solvent for dissolving the polysaccharide such as cellulose, can get homogeneous and transparent cellulose
" true solution ", good to the adaptability of the polysaccharide such as separate sources and characteristic cellulose, dissolved solution is more stable, therefore the solvent
System is widely used.It is considered as be only second to ionic liquid strong during dissolution, processing, characterization or homogeneous derivatization
Big dicyandiamide solution, and as one kind there are commonly solvent, DMAc is much more cheap than ionic liquid.
Currently, the research of DMAc/LiCl dicyandiamide solution has achieved some experiences and achievement.It is influenced in the dicyandiamide solution more
Sugar dissolves there are two the most key factors: raw material activation step and LiCl concentration.Activation process before dissolution be in order to open or
These hydrogen bond structures of the polysaccharide such as cellulose are weakened, and macromolecular chain state in which is made to become relatively freely loose, are conducive to
New hydrogen bond network structure is established during dicyandiamide solution penetrates into, to achieve the effect that be completely dispersed and dissolve.
By taking cellulose as an example, in system dissolution, there are two types of cellulose activation process is usual, one is low temperature (5~
Exchange of solvent is carried out with the combination of water, methanol, acetone and DMAc etc. under the conditions of 60 DEG C, similarly hereinafter)；Another kind be high temperature (130~
150 DEG C) DMAc activation.The corresponding course of dissolution of two class activation methods is dissolution in low temperature and high-temperature digestion respectively.High-temperature activation
Advantage is that course of dissolution step is few, and LiCl dosage is relatively fewer, but temperature used is close to the boiling point of DMAc, many results of study
Show that this process can make cellulose degradation, while a degree of discoloration can occur for solution, with activation time extension and temperature
Degree improves, and these problems can become more serious, although can be eliminated or alleviate by being passed through nitrogen, hot conditions
Virtually improve cost and to equipment requirement.Dissolution in low temperature was activated due to that need to pass through the exchange of solvent of two or more reagents
Journey, step is relatively cumbersome, but completely avoids the degradation of cellulose.It is that cellulose is added in high-temperature activation and its course of dissolution
The DMAc activation of heat, adds 3%~20% LiCl, completes being completely dissolved for cellulose after lasting stirring；And low-temperature solvent
The LiCl addition manner of exchange utilization is usually the DMAc/LiCl solution of concentration needed for first preparing in 1h finally, is then added again
Enter activated cellulose, stirring to being completely dissolved, low temperature dissolution method can make cellulose in entire course of dissolution almost without
Degradation occurs.
LiCl Concentrations on Dissolution influential effect is very big in solution, and in the case where the certain cellulose concentration of solution requires, LiCl is dense
It spends low, is not achieved the effect of dissolution, concentration is high to be easy to happen supersaturation instead again influences the dissolution of cellulose.Research shows that
DMAc/LiCl system is by DMAc and Li+Ions binding plays peptizaiton to cellulose after forming complex cation, simultaneously
Cellulose participates in Li again+The dispersion of ion, this be dissolution motive force, LiCl concentration when low entire dicyandiamide solution to cellulose
Active force is weaker.In other words, the adjusting of LiCl concentration can control the dissolved state of cellulose.Such as prepare certain density fiber
Plain solution, LiCl content need to be higher than some concentration, and otherwise solution will be not enough to reach the state being completely dissolved.
Cellulose after low-temperature activation has two in dissolution: (1) low temperature under among DMAcs it is completely dissolved 6~
The LiCl of 9wt% needs certain time (in 1h), the time needed for virtually increasing course of dissolution again, although heating can contract
This short part-time, but DMAc solution is easy flavescence color；(2) the cellulose particles intergranular after activating has certain bonding, either
DMAc/LiCl solvent is added in cellulose, or cellulose is added in the solvent, original easily bonding slower due to dispersing
Cellulose have the bulk of more cohesion and be suspended in the clear solution of surrounding, especially dissolution is extracted from lignocellulosic
Cellulose out or when dissolving larger amount of cellulose, since disperse system viscosity becomes larger, mixing effect is gradually deteriorated, this
Problem shows particularly evident, and bulks of these cohesions are difficult quickly to be dissolved at this moment, to be completely dissolved, dissolve first is that extending
Time, second is that reinforcing the mechanical stirring with intensity at high speed, LiCl/DMA can just slowly infiltrated through, and agglomeration is internal to be realized gradually
Dissolution, this causes very big difficulty to the use of cellulose.The present invention can solve this technical problem, make polysaccharide to be dissolved
Dissolution in low temperature in DMAc/LiCl system becomes very easy.It is abundant first using the DMAc of the LiCl Han 2~6wt% concentration
Polysaccharide after dispersion activation, the LiCl of the concentration are dissolved in the used time in DMAc and want much shorter, it is only necessary to less than 10min, add
LiCl makes 3~20wt% of its total concentration, and with the dissolution of LiCl, the glycocalix tentatively dispersed is further evenly dispersed,
To achieve the purpose that the polysaccharide sufficiently dissolves, the time of a part of dissolution lithium chloride has also been saved in this way, maximum can have been played
The solvability of lithium chloride.
It is worth noting that though the DMAc solution of 2~6wt%LiCl cannot be completely dissolved cellulose, fiber is known as
Good peptizaiton, cellulose are scattered in entire solution with relatively small particle and form Heterodisperse system, at this time mixed liquor
Viscosity is low, is easy to stir, and adds after LiCl makes 3~20wt% of its total concentration, LiCl is easily dispersed, therefore is being stirred at low speed
Under with LiCl dissolution, further dispersion becomes the homogeneous phase solution of clear to cellulose quickly.
In addition, being different from high-temperature activation process, if directly the cellulose be added at low temperature pure without LiCl
In DMAc solution, dispersion effect is poor, and solid liquid phase layering is obvious, is then added at one time LiCl, this mode is after the long period
Resulting to remain difficult to obtain completely homogeneous cellulose dispersion liquid, solute effect is poor.And other polysaccharide are in the dicyandiamide solution
Dissolution also encounter problem like above.
Summary of the invention
It is an object of the invention to ask to solve technology present in polysaccharide course of dissolution in above-mentioned DMAc/LiCl system
Topic, provides a kind of preparation method of polysaccharide dispersion liquid.
The present invention the following steps are included:
1) polysaccharide is dried after exchange of solvent；
2) using DMAc as solvent, the DMAc/LiCl solution that LiCl mass concentration is 2%~6% is prepared, step 1) is added
It is activated, drying after polysaccharide to get polysaccharide Heterodisperse liquid, add LiCl, make its total mass concentration 3%~
20% to get polysaccharide dispersion liquid.
In step 1), the polysaccharide includes but is not limited to cellulose；The cellulose include but is not limited to gossypin,
One of flaxen fiber element, microcrystalline cellulose, lignocellulosic etc.；The lignocellulosic can be selected from wheat stalk, Chinese silvergrass straw
One of stalk, corn stover, bamboo fibre etc. extract obtained cellulose；The temperature of the exchange of solvent can be 5~60 DEG C；
The solvent that solvent for use exchange uses can be selected from methanol and DMAc or water, acetone and DMAc；The temperature of the drying can for 40~
70 DEG C, the time of drying can be 1~8h.
In step 2), the proportion of the polysaccharide and DMAc/LiCl solution can be 1 ︰ (10~50), wherein polysaccharide is with matter
Amount calculates, and DMAc/LiCl solution is in terms of volume；The mass percentage concentration of gained polysaccharide dispersion liquid is 2%~15%.
The present invention first uses the polysaccharide such as low-temperature solvent exchange step activated cellulose or chitin in conventional method, then
Using the method for two steps addition LiCl, i.e., first using DMAc as solvent, prepare the DMAc/ that LiCl mass percentage concentration is 2%~6%
LiCl solution, the polysaccharide after activation is added carry out preliminary dispersion to first obtain its Heterodisperse system (LiCl in this step
Concentration is lower than the concentration, and the polysaccharide such as cellulose are easy precipitating, the effect tentatively dispersed is not achieved), then plus it is remaining required
LiCl (so that LiCl total concentration is 3%~20%), quickly obtains homogeneous and transparent this kind of polysaccharide in LiCl course of dissolution
Homogeneous dispersed phase.In entire course of dissolution, it is easy thoroughly to overcome polysaccharide in course of dissolution (especially highly concentrated solution preparation)
The defect of reunion agglomeration, not only carries out at low temperature but also only needs lower stirring rate and intensity, and solution rate is fast, low energy consumption, because
This has very big advantage in terms of efficiency and economy.
The present invention have it is following the utility model has the advantages that
1) the invention avoids hot conditions are used, it can be effectively prevent the degradation and solvent volatilization of cellulose and chitin,
The energy conservation of low-temperature atmosphere-pressure condition and saving equipment manufacturing cost.
2) present invention adds LiCl in two steps, and since polysaccharide carries out after tentatively dispersing, LiCl, which is added, makes its total concentration 3%
~20%, LiCl is dissolved while cellulose and chitin dissolve, therefore save the dissolution time of a part of LiCl, and it is complete
Agglomeration rendezvous problem when solving especially compounding high concentration cellulose solution entirely in course of dissolution, when substantially reducing dissolution
Between.
Specific embodiment
Below by way of specific embodiment, further the present invention will be described in detail and explanation.
Embodiment 1
10.5g microcrystalline cellulose is first passed through four methanol and a DMAc exchange of solvent, each 30min, mistake by step 1.
60 DEG C of drying 2h in clean, dry anhydrous beaker are contained in after filter；
Step 2. prepares the DMAc/LiCl solution that 200ml concentration is 4wt%, and LiCl can be dissolved in DMAc quickly, by step 1
The microcrystalline cellulose of middle activation is added in the solution system, and cellulose obtains evenly dispersed, formation cellulose Heterodisperse
System；
Remaining LiCl, which is added, in step 3. makes its total concentration 8wt%, lasting to stir, and obtains after 30min homogeneous and transparent
Cellulose homogeneous-phase disperse system, wherein the mass volume ratio of cellulose and DMAc/LiCl solution is 1 ︰ 20, unit g/mL.
To cellulose dissolution since being added residue LiCl, dissolution time is only 20min.
Embodiment 2
First the filter paper by 10.5g through pulverization process is by four methanol and a DMAc exchange of solvent for step 1., every time
30min is contained in 60 DEG C of drying 2h in clean, dry anhydrous beaker after filtering；
Step 2. prepares the DMAc/LiCl solution that 200ml LiCl concentration is 5wt%, and LiCl can be dissolved in DMAc quickly, will
The microcrystalline cellulose activated in step 1 is added in the solution system, and cellulose obtains evenly dispersed；
Remaining LiCl, which is added, in step 3. makes its total concentration 8wt%, lasting to stir, and it is molten to obtain homogeneous and transparent cellulose
Liquid, no any agglomerate are formed.Wherein the mass volume ratio of cellulose and DMAc/LiCl solution is 1 ︰ 20, unit g/mL.
To cellulose dissolution since being added residue LiCl, dissolution time is only 30min.
Embodiment 3
Step 1. takes 5.25g smashed from the cellulose extracted in Chinese silvergrass in clean container, by four methanol and
DMAc exchange of solvent, each 30min are contained in 60 DEG C of drying 2h in clean, dry anhydrous beaker after filtering；
Step 2. prepares the DMAc/LiCl solution that 100ml LiCl concentration is 4wt%, and LiCl can be dissolved in DMAc quickly, will
The microcrystalline cellulose activated in step 1 is added in the solution system, and cellulose obtains evenly dispersed；
Remaining LiCl, which is added, in step 3. makes its total concentration 8wt%, lasting to stir, and obtains faint yellow homogeneous and transparent fibre
Plain solution is tieed up, no any agglomerate is formed.Wherein the mass volume ratio of cellulose and DMAc/LiCl solution is 1 ︰ 20, unit g/
mL。
To cellulose dissolution since being added residue LiCl, dissolution time is only 20min.
Embodiment 4
Step 1. takes 10.5g smashed from the cellulose extracted in bamboo scraps in clean container, by four methanol and
DMAc exchange of solvent, each 30min are contained in 60 DEG C of drying 2h in clean, dry anhydrous beaker after filtering；
Step 2. prepares the DMAc/LiCl solution that 200ml LiCl concentration is 4wt%, and LiCl can be dissolved in DMAc quickly, will
The microcrystalline cellulose activated in step 1 is added in the solution system, and cellulose obtains evenly dispersed；
Remaining LiCl is added in step 3., lasting to stir, and faint yellow homogeneous and transparent cellulose solution is obtained, without any group
Block is formed.Wherein the mass volume ratio of cellulose and DMAc/LiCl solution is 1 ︰ 20, unit g/mL.
To cellulose dissolution since being added residue LiCl, dissolution time is only 25min.
Embodiment 5
Step 1. takes the smashed chitin of 10.5g in clean container, handles through exchange of solvent, is contained in after filtering dry
Only, in dry anhydrous beaker；
Step 2. prepares the DMAc/LiCl solution that 200ml LiCl concentration is 4wt%, and LiCl can be dissolved in DMAc quickly, will
The chitin activated in step 1 is added in the solution system, and chitin obtains evenly dispersed formation Heterodisperse liquid；
Remaining LiCl, which is added, in step 3. makes its total concentration 8wt%, lasting to stir, and obtains faint yellow homogeneous and transparent first
Shell element solution, no any agglomerate are formed.Wherein the mass volume ratio of chitin and DMAc/LiCl solution is 1 ︰ 20, unit g/
mL。
To cellulose dissolution since being added residue LiCl, dissolution time is only 25min.
The invention can avoid agglomeration problems during preparing the DMAc/LiCl polysaccharide disperse system of high concentration.The present invention
Related this easy, quick high concentration polysaccharide disperses liquid and preparation method thereof, has the advantages that energy saving, time saving, has biggish
Practical application value.
Claims (7)
1. a kind of preparation method of polysaccharide dispersion liquid, it is characterised in that the following steps are included:
1) polysaccharide is dried after exchange of solvent；
2) using DMAc as solvent, the DMAc/LiCl solution that LiCl mass concentration is 2%~6% is prepared, adds step 1) through work
Polysaccharide after changing, drying adds LiCl, makes its total mass concentration 3%~20%, i.e., to get polysaccharide Heterodisperse liquid
Much sugar dispersion liquids；The proportion of the polysaccharide and DMAc/LiCl solution is 1 ︰ (10~50), wherein polysaccharide is calculated by mass,
DMAc/LiCl solution is in terms of volume.
2. a kind of preparation method of polysaccharide dispersion liquid as described in claim 1, it is characterised in that in step 1), the polysaccharide packet
Include cellulose.
3. a kind of preparation method of polysaccharide dispersion liquid as claimed in claim 2, it is characterised in that the cellulose includes cotton fiber
One of element, flaxen fiber element, microcrystalline cellulose, lignocellulosic.
4. a kind of preparation method of polysaccharide dispersion liquid as claimed in claim 3, it is characterised in that the lignocellulosic is selected from small
One of Wheat Straw, Chinese silvergrass stalk, corn stover, bamboo fibre extract obtained cellulose.
5. a kind of preparation method of polysaccharide dispersion liquid as described in claim 1, it is characterised in that in step 1), the solvent is handed over
The temperature changed is 5~60 DEG C.
6. a kind of preparation method of polysaccharide dispersion liquid as described in claim 1, it is characterised in that in step 1), solvent for use is handed over
The solvent for changing use is selected from methanol and DMAc or water, acetone and DMAc.
7. a kind of preparation method of polysaccharide dispersion liquid as described in claim 1, it is characterised in that in step 1), the drying
Temperature is 40~70 DEG C, and the time of drying is 1~8h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181762A (en) * | 1995-02-21 | 1998-05-13 | 塞尔卡特股份有限公司 | Cellulose particles, method for producing them and their use |
| CN101508786A (en) * | 2009-03-20 | 2009-08-19 | 武汉科技学院 | Method for dissolution of bacteria cellulose |
| CN103788383A (en) * | 2014-01-27 | 2014-05-14 | 上海工程技术大学 | Method for dissolving natural cellulose |
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2016
- 2016-07-26 CN CN201610592201.4A patent/CN106220869B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181762A (en) * | 1995-02-21 | 1998-05-13 | 塞尔卡特股份有限公司 | Cellulose particles, method for producing them and their use |
| CN101508786A (en) * | 2009-03-20 | 2009-08-19 | 武汉科技学院 | Method for dissolution of bacteria cellulose |
| CN103788383A (en) * | 2014-01-27 | 2014-05-14 | 上海工程技术大学 | Method for dissolving natural cellulose |
Non-Patent Citations (1)
| Title |
|---|
| 棉纤维在LiCl/DMAc极性溶液中的溶解性能研究;陈一等;《纤维素科学与技术》;20090915;第17卷(第3期);第12-18页 |
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