CN104130425B - A kind of preparation method of material of regenerated cellulose - Google Patents
A kind of preparation method of material of regenerated cellulose Download PDFInfo
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- CN104130425B CN104130425B CN201310158819.6A CN201310158819A CN104130425B CN 104130425 B CN104130425 B CN 104130425B CN 201310158819 A CN201310158819 A CN 201310158819A CN 104130425 B CN104130425 B CN 104130425B
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Abstract
The invention discloses a kind of preparation method of material of regenerated cellulose of material of regenerated cellulose preparing technical field.The solvent used is carboxylic acid type ionic liquid or its cosolvent with the polar organic solvent composition without Labile protons.Carboxylic acid type ionic liquid is preferably the methylimidazole acetate of 1 ethyl 3, the methylimidazole acetate of 1 propyl group 3 or the methylimidazole acetate of 1 butyl 3；One or more of the secondary solvent in DMF, DMAc, DMI, DMSO, pyridine, acetone, dichloromethane and dichloroethanes；Coagulator is preferably alcohol organic solvent.The selection of optimization is：It is 5: 5 that carboxylic acid type ionic liquid, which is selected from the methylimidazole acetate of 1 ethyl 3 or the methylimidazole acetate of 1 butyl 3, secondary solvent DMF, and the mass ratio of the two, and coagulator selects ethanol.The present invention can be obviously improved the mechanical property of regenerated cellulosics, reduce environmental pollution.
Description
Technical field
The invention belongs to material of regenerated cellulose preparing technical field, more particularly to one kind can improve material of regenerated cellulose
The preparation method of mechanical property, especially toughness.
Background technology
Cellulose is that the natural polymer most wide, reserves are maximum is distributed in nature, and annual plant passes through photosynthesis energy
Hundred billion tons of cellulose is produced, it can be said that cellulose is a kind of inexhaustible renewable resource.Cellulose
Also there is fully biodegradable, good biocompatibility, good mechanical performance is easily modified to wait many advantages, has been widely used
In industrial production and people's daily life.The characteristics of cellulose is due to self assemble state structure, i.e. intramolecular, intermolecular deposit
In substantial amounts of hydrogen bond, while there is higher crystallinity again, therefore native cellulose can not melt, it is also difficult to it is molten to be dissolved in general
Agent, this brings great inconvenience to the processed and applied of cellulose.
Industrialized viscose process regenerated cellulose, occupies leading position, so far always in regenerated cellulose industry
Existing more than 100 years history.By regenerated cellulose film (glassine paper), long filament and the short silk of viscose process production in national economy
With important application.But due to, largely using compounds such as alkali, sulfuric acid and carbon disulfide, easily being produced big in process
Toxic gases such as the hydrogen sulfide of amount, carbon disulfide and contaminated wastewater is serious, development prospect is restricted, existing at present gradually to be washed in a pan
The gesture eliminated.4- methyhnorpholine-N-oxides (NMMO) system also has industrialized production, and its regenerated cellulose produced is named as
Lyocell fiber, but this method solvent is expensive, and recovery technology is harsh.In addition with lithium chloride/dimethyl acetamide
(LiCl/DMAc) the cellulose solvent system such as system, urea alkali systems, but the characteristics of due to dissolution system itself, industrialized production
It is difficult.Therefore find suitable solvent, and by cellulose it is economic and environment-friendly to dissolve processing be always the target that people pursue.And most
In recent years, ionic liquid is used for the dissolving of cellulose and processing has aroused widespread concern.Using ionic liquid as medium
Prepare material of regenerated cellulose, there is the advantage such as environmentally friendly, with short production cycle, convenient solvent reclaiming, be it is a kind of have very much it is latent
The cellulose new method for processing of power.
Ionic liquid is the direct solvent of cellulose, and direct solvent method production material of regenerated cellulose generally comprises：Shaping,
The key steps such as solidification, washing and drying.And the basic structure of regenerated cellulose is formed in coagulation step, often to regenerated fiber
Cellulosic material performance plays conclusive effect.The process of solidification is extremely complex, phase between solvent, cellulose, non-solvent coagulator
Interaction, generate gel structure.The gel structure that different curing conditions obtains may be different, cause regenerated cellulose after drying
The structures such as the crystallinity of material, density are different, and then cause the change of material property.By setting solvent, dissolution conditions,
Coagulator, curing condition and drying condition etc. are possible to obtain the material of regenerated cellulose of function admirable.
The mechanical property of material of regenerated cellulose is relevant with dicyandiamide solution and technology of preparing relation, but generally has fracture
The shortcomings that elongation is relatively low, i.e. lacking toughness.The shortcomings that to overcome poor toughness, glassine paper industry (it is fine to produce regeneration with viscose process
Tie up plain film) in, it is common to use elasticizer plasticizing product, otherwise film is crisp, easily splits, it is difficult to meets actual operation requirements.Plasticizer is
The small molecule being easy to run off, this is inappropriate for the application field for requiring long service.In addition, also result in film using plasticizer
Tensile strength reduce (Zhangwei Jin, Jianqiang Wang et al.Journal ofApplied rapidly
Polymer Science.2012,125,704-709), because plasticizer reduces the adhesion between macromolecular chain.Use
A route that is elastomer blended and improving regenerated cellulose toughness, that is, add elastomer polymer and cellulose blending, but
The raising of elongation at break is accompanied by, the intensity and modulus of regenerated cellulose film is significantly reduced (Xiaomin Zhang, Jin
Zhu et al.Macromolecular Research.2012, vol.20, No.7, pp703-708).
The content of the invention
It is an object of the invention to provide a kind of preparation method of material of regenerated cellulose, the preparation method can improve regeneration
The mechanical property of cellulosic material, especially toughness.
A kind of preparation method of material of regenerated cellulose, including by raw cellulose successively by dissolving, deaeration, shaping,
Material of regenerated cellulose is made after solidification, washing, drying and other steps.
It is characterized in that：
The solvent used in described dissolving step is carboxylic acid type ionic liquid or carboxylic acid type ionic liquid and secondary solvent
The cosolvent of composition, wherein, described secondary solvent is the polar organic solvent without Labile protons；Described carboxylic acid type ion
For the cation of liquid preferably based on imidazole ring, the carboxylate radicals such as acetic acid ion, propionate, butyric acid ion can be selected in anion
Ion；It is highly preferred that described carboxylic acid type ionic liquid is 1- ethyl-3-methylimidazoles acetate, 1- propyl group -3- methylimidazoles
Acetate or 1- butyl -3- methylimidazole acetate；Described secondary solvent be preferably substituent amide-type, sulfone class, ketone and
Halogenated hydrocarbon etc., addition for the cosolvent gross mass 0-70% (in use with do not cause cellulose separate out for the upper limit),
It may be selected from the one or more in DMF, DMAc, DMI, DMSO, pyridine, acetone, dichloromethane and dichloroethanes；
The coagulator used in described coagulation step is the organic solvent containing Labile protons, including alcohols, thio-alcohol,
Ammonia and carboxylic acids etc.；Preferably alcohol organic solvent, as may be selected in methanol, ethanol and isopropanol it is a kind of be used alone or
It is a variety of to be used in mixed way；More preferably ethanol or ethanol/water, ethanol/acetone solution (wherein ethanol using ethanol as main component
Mass content be at least 80%)；
The selection of optimization is：Carboxylic acid type ionic liquid is selected from 1- ethyl-3-methylimidazoles acetate or 1- butyl -3- first
Base imidazoles acetate, secondary solvent DMF, and carboxylic acid type ionic liquid and DMF mass ratio are 5: 5, while coagulator selects
Use ethanol.
The preparation method of material of regenerated cellulose provided by the invention can be obviously improved the mechanical property of regenerated cellulosics
Energy, especially toughness, can significantly improve material of regenerated cellulose elongation at break；Using regenerated fiber provided by the invention
The preparation method of cellulosic material, it can obtain under conditions of plasticizer is not added, the elongation at break of regenerated cellulosics
Significantly improve, more than 40% can be reached, and tensile strength is still very high.
Embodiment
The mechanical property of regenerated cellulose contacts with its close structure.The poor toughness of regenerated cellulose is mainly its strand
Section locomitivity it is low cause, i.e., under external force cellulosic molecule have little time relaxation fall internal stress and be broken.Therefore
It is to improve the key of regenerated cellulose toughness to improve cellulosic molecule locomitivity.The locomitivity and cellulose of cellulosic molecule
Crystallinity, density and hydrogen bond quantity of formation have much relations：Density is big, intermolecular to pile up close, cellulosic molecule space
Reduce；Crystallinity is big, and hydrogen bond density is big, and cellulosic molecule is fettered by surrounding molecular and reduces locomitivity.Therefore, knot is changed
Brilliant degree, density or hydrogen bond quantity, the mechanical property of regenerated cellulose can be regulated and controled in theory.For regenerated cellulose,
Its structure is mainly influenceed by dissolving and curing condition.Fortunately, regeneration prepared under different dissolvings or curing condition
The crystallinity and density of cellulose have very big difference, and this is just to control regenerated cellulose by changing dissolving or curing condition
Structure and then its mechanical property that changes provides the foundation and fact basis.The present invention is by examining a variety of dissolvings and curing condition
Examine, filtered out the solvent and coagulator for preparing the regenerated cellulose with optimal mechanical property.
Below with the methylimidazole acetate ionic liquid (EmimAc) of 1- ethyls -3/methylimidazole vinegar of DMF and 1- butyl -3
Exemplified by hydrochlorate ionic liquid (BmimAc)/DMF systems, technical scheme is described further.
The cellulose used in following examples is commercially available Cotton Pulp, is crushed before use, molten in order to mix
Solution.Ionic liquid is commercially available the methylimidazole acetate ionic liquid (EmimAc) of 1- ethyls -3 and the methylimidazole vinegar of 1- butyl -3
Hydrochlorate (BmimAc) ionic liquid, DMF, DMAC and DMSO are AR.
In order to compare the impact effect of coagulator, under the conditions of each embodiment, obtained cellulose solution respectively with ethanol and
Two kinds of coagulator solidifications of deionization, i.e., each embodiment include the preparation of two kinds of samples.
The cellulosic raw material used in following embodiments may be selected from any cellulosic material, such as Cotton Pulp and wood pulp
The dregs of rice.
Embodiment 1：
2g Cotton Pulps and 23gEmimAc are added in 50mL three-necked flasks, heats in 80 DEG C of oil baths, is stirred using machinery
Mix, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h, stops stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 70MPa, extension at break
Rate is about 14%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, film fragility is big, in drying process easily
Split, it is difficult to the film for meeting extension test condition is made.
Embodiment 2：
2g Cotton Pulps and 23gEmimAc/DMF (11.5gEmimAc, 11.5gDMF) cosolvent are added into 50mL three-necked flasks
In, heated in 80 DEG C of oil baths, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h,
Stop stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 93MPa, extension at break
Rate is about 34%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
60MPa, elongation at break are about 5%.
Embodiment 3：
2g Cotton Pulps and 23gEmimAc/DMF (9.2gEmimAc, 13.8gDMF) cosolvent are added into 50mL three-necked flasks
In, heated in 80 DEG C of oil baths, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h,
Stop stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 98MPa, extension at break
Rate is about 23%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
87MPa, elongation at break are about 5%.
Embodiment 4：
2g Cotton Pulps and 23gBmimAc are added in 50mL three-necked flasks, heats in 80 DEG C of oil baths, is stirred using machinery
Mix, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h, stops stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 80MPa, extension at break
Rate is about 16%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film drying process is easily broken
Split, it is difficult to be met the sample of extension test condition.
Embodiment 5：
2g Cotton Pulps and 23gBmimAc/DMF (11.5gBmimAc, 11.5gDMF) cosolvent are added into 50mL three-necked flasks
In, heated in 80 DEG C of oil baths, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h,
Stop stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 97MPa, extension at break
Rate is about 47%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
70MPa, elongation at break are about 6.5%.
Embodiment 6：
2g Cotton Pulps and 23gBmimAc/DMF (9.2gBmimAc, 13.8gDMF) cosolvent are added into 50mL three-necked flasks
In, heated in 80 DEG C of oil baths, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h,
Stop stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 103MPa, and fracture is stretched
Long rate is about 30%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
95MPa, elongation at break are about 6%.
Embodiment 7：
2g Cotton Pulps and 23gBmimAc/DMF (6.9gBmimAc, 16.1gDMF) cosolvent are added into 50mL three-necked flasks
In, heated in 80 DEG C of oil baths, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h,
Stop stirring, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution with along a direction, spread over it
Turn into uniform cellulose solution film on glass plate.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 102MPa, and fracture is stretched
Long rate is about 22%.
If above-mentioned coagulator is changed into deionized water, it is film-made by the same manner, gained film tensile strength is about 109MPa,
Elongation at break is about 14%.
The Comprehensive Correlation data of above-described embodiment 1~7 are enumerated in table 1：
The tensile property of the regenerated cellulose film of table 1
In table, EmimAc is the methylimidazole acetate of 1- ethyls -3；BmimAc is the methylimidazole acetate of 1- butyl -3.
As shown in table 1, by taking cellulose/BmimAc solution as an example, if selection deionized water is as coagulator, gained cellulose
Hydrogel is the opaque shape of milky and easy fragmentation, and gained material of regenerated cellulose fragility is larger after drying, easy fragmentation, it is difficult to
Obtain complete membrane；If the organic solvents such as alcohols are selected as coagulator, gained gelatinous transparent, through drying gained thin film mechanics
Can preferably, tensile strength 80MPa, elongation at break is up to 16% or so.Add from table 1 it can also be seen that in ionic liquid
Enter DMF composition cosolvent, can further improve the toughness of material of regenerated cellulose, can finally reach the plasticising of viscose process preparation
The elongation at break of glassine paper afterwards.
During using ethanol as coagulator, the dosage of secondary solvent is not the higher the better, but optimal with mass ratio 5: 5.To go
When ionized water is coagulator, the dosage of secondary solvent is the higher the better, but the dosage of secondary solvent reaches the 70% of solvent total amount
When, although the film toughness of gained increases, effect is still not so good as with the film of alcohol solidification, due to the limitation of solvability,
The dosage of secondary solvent can not further be improved.Under the conditions of various secondary solvent ratios, the institute using deionized water as coagulator
Obtain the good toughness that RCF regenerated cellulose film is all not so good as the RCF regenerated cellulose film obtained by ethanol as coagulator under similarity condition.
Contrasted with this, if selecting non-carboxylic acid type ionic liquid, such as 1- butyl -3- methylimidazole chloride ion liquids
(BmimCl), 1- pi-allyls -3- methylimidazoles chloride ion liquid (AmimCl), then cosolvent and coagulator are selected in any case,
The elongation at break of gained RCF regenerated cellulose film is all than relatively low, 8% or so.So the present invention uses carboxylic acid type ion
Liquid (or being used together with secondary solvent) dissolves cellulose, and using organic solvents such as alcohols as coagulator, the two has
Match selection relation.
It is due to phase of the carboxyl anion with coagulator of carboxylic acid type ionic liquid it is considered that above-mentioned this matching relationship
Interaction decides the structure of regenerated cellulose, and then influences its mechanical property.For the difference in regenerated cellulose structure, I
Selected part sample density measure has been carried out to it, concrete outcome is shown in Table 2.
The density of the regenerated cellulose film of table 2
As shown in table 2, we understand using deionized water as coagulator obtained by RCF regenerated cellulose film density as
1.52g/cm3Left and right, and the density of gained RCF regenerated cellulose film is 1.47g/cm using ethanol as coagulator3Left and right.Deionization
Water does the density that density of film obtained by coagulator does film obtained by coagulator far above ethanol, and this shows that the regeneration that the two is obtained is fine
Tie up plain film and difference in structure be present.The reason for difference in this structure is perhaps its performance difference.It is presumed that use second
The RCF regenerated cellulose film density of alcohol solidification gained is smaller, and its molecules align is more loose so that its intramolecular and intermolecular hydrogen
The quantity of key is reduced, while free volume increases, and the locomitivity of its strand improves, and strand can be transported under external force
Dynamic to reset, material can be produced compared with large deformation.
In summary, carboxylic acid type ionic liquid (including carboxylic acid type ionic liquid and carboxylic acid type ionic liquid with without active
The cosolvent of the polar organic solvent composition of proton) after dissolving cellulose, its solution and coagulator have selection matching relationship：With
The material of regenerated cellulose performance that the organic solvents such as alcohols do prepared by coagulator is better than obtained by deionized water does coagulator
Material of regenerated cellulose.Carboxylic acid type ionic liquid and DMF, DMAc, DMI, DMSO, pyridine, acetone, dichloromethane and dichloroethanes
The cosolvent formed Deng the polar organic solvent without Labile protons can also dissolve cellulose, can make cellulose using cosolvent
Solution viscosity reduces, it is often more important that can further improve the mechanical property of regenerated cellulose.
When the cation of carboxylic acid type ionic liquid of the present invention is imidazole type, best results, because of its stability
It is higher；Anion can be acetate, propionate, butyric acid root etc..Because of the methylimidazole acetate ionic liquid of 1- ethyls -3
(EmimAc) and the methylimidazole acetate ionic liquid (BmimAc) of 1- butyl -3 can commercially, at present both from
Sub- liquid is optimal selection.
The secondary solvent that the present invention uses is the polar solvent without Labile protons, such as DMF, DMAc, DMSO, pyridine, third
Ketone, dichloromethane and dichloroethanes are medium, because the solvent containing Labile protons will cause cellulose to separate out, it is impossible to molten as aiding in
Agent uses, and non-polar solven is immiscible with ionic liquid.The addition of secondary solvent with do not cause cellulose separate out for the upper limit.
Coagulator of the present invention, it is that alcohols, thio-alcohol, Ammonia and carboxylic acids etc. are organic molten containing Labile protons
Agent, wherein it is preferred that the alcohol organic solvent containing Labile protons, such as the one or more in methanol, ethanol, isopropanol.From using valency
The combined factors such as lattice, toxicity consider that ethanol is optimal selection.
In a word, using carboxylic acid type ionic liquid as solvent, it is coagulator with appropriate organic solvent, such as alcohol, can prepares
The material of regenerated cellulose of high tenacity.Secondary solvent using the polar organic solvent without Labile protons as ionic liquid can
Further enhance this effect.
Embodiment 8：
2g Cotton Pulps and EmimAc/DMAc (11.5gEmimAc, 11.5gDMAc) are added in 50mL three-necked flasks, 80
Heated in DEG C oil bath, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h, stops stirring
Mix, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 100MPa, and fracture is stretched
Long rate is about 36%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
70MPa, elongation at break are about 6.8%.
Embodiment 9：
2g Cotton Pulps and EmimAc/DMSO (11.5gEmimAc, 11.5gDMSO) are added in 50mL three-necked flasks, 80
Heated in DEG C oil bath, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h, stops stirring
Mix, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 106MPa, and fracture is stretched
Long rate is about 29%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
66MPa, elongation at break are about 5.6%.
Embodiment 10：
2g Cotton Pulps and BmimAc/DMAc (11.5gBmimAc, 11.5gDMAc) are added in 50mL three-necked flasks, 80
Heated in DEG C oil bath, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h, stops stirring
Mix, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 98MPa, extension at break
Rate is about 34%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
64MPa, elongation at break are about 6.2%.
Embodiment 11：
2g Cotton Pulps and BmimAc/DMSO (11.5gBmimAc, 11.5gDMSO) are added in 50mL three-necked flasks, 80
Heated in DEG C oil bath, using mechanical agitation, cellulose is completely dissolved to obtain as clear as crystal cellulose solution after stirring 2h, stops stirring
Mix, bubble in solution is removed completely.
Take a small amount of solution to be poured on pre-prepd glass plate, scrape cellulose solution in one direction with plastic film mulch device, make
It is sprawled turns into uniform cellulose solution film on a glass.
A tank is taken, is put into enough ethanol.The glass plate for spreading cellulose solution is put into the tank, cellulose
Come off after film solidification from glass plate.
Drying process uses glass plate and vacuum drying oven.Between clean cellulose membrane is clipped in layer glass plate, it is put into true
Dried in empty baking oven, until being completely dried to obtain RCF regenerated cellulose film.The film sample made is cut into 1x5cm batten,
Tensile strength and elongation at break are tested on universal tensile testing machine.Gained film tensile strength is about 96MPa, extension at break
Rate is about 37%.
If above-mentioned ethanol is changed into deionized water, the constant film of other operating conditions, gained film tensile strength is about
63MPa, elongation at break are about 5.8%.
Claims (4)
1. it is a kind of improve material of regenerated cellulose toughness preparation method, including by raw cellulose successively by dissolving, deaeration,
Material of regenerated cellulose is made after shaping, solidification, washing, drying steps；Characterized in that, used in described dissolving step
Solvent is the cosolvent of carboxylic acid type ionic liquid and secondary solvent composition, wherein, described secondary solvent is without Labile protons
Polar organic solvent；The coagulator used in described coagulation step is the organic solvent containing Labile protons；Described is solidifying
It is used alone or a variety of is used in mixed way Gu agent is a kind of in methanol, ethanol and isopropanol；
The cation of described carboxylic acid type ionic liquid is based on imidazole ring；
The anion of described carboxylic acid type ionic liquid is selected from acetic acid ion, propionate or butyric acid ion；
Described secondary solvent is selected from substituent amide-type, sulfone class, ketone and halogenated hydrocarbon, and addition is the total matter of the cosolvent
The 0-70% of amount, in use with do not cause cellulose separate out for the upper limit.
2. the preparation method according to claim 1 for improving material of regenerated cellulose toughness, it is characterised in that described carboxylic
Acid type ion liquid is 1- ethyl-3-methylimidazoles acetate, 1- propyl group -3- methylimidazoles acetate or 1- butyl -3- methyl
Imidazoles acetate.
3. the preparation method according to claim 1 for improving material of regenerated cellulose toughness, it is characterised in that described is auxiliary
One or more of the cosolvent in DMF, DMAc, DMI, DMSO, pyridine, acetone, dichloromethane and dichloroethanes.
4. the preparation method according to claim 1 for improving material of regenerated cellulose toughness, it is characterised in that described carboxylic
Acid type ion liquid is selected from 1- ethyl-3-methylimidazoles acetate or 1- butyl -3- methylimidazole acetate, secondary solvent are
DMF, and the carboxylic acid type ionic liquid and DMF mass ratio are 5:5, while the coagulator selects ethanol.
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| CN104437629B (en) * | 2014-12-12 | 2017-05-10 | 江苏科技大学 | Method for preparing simulated cellulose enzyme from mixed acid |
| CN107573401B (en) * | 2016-07-05 | 2021-07-13 | 中国科学院过程工程研究所 | Method for preparing high polymer by dissolving fermentation bacterium residues in ionic liquid solvent system |
| CN106702802B (en) * | 2016-12-30 | 2018-09-04 | 中国科学院过程工程研究所 | A kind of method that ionic liquid-sulfamic acid binary system extracts high pure cellulose from stalk |
| CN109206670B (en) * | 2017-07-03 | 2020-04-24 | 中国科学院化学研究所 | Composition of polysaccharide derivative containing phenolic hydroxyl and preparation method and application thereof |
| CN108727623B (en) * | 2018-06-14 | 2021-03-19 | 北京林业大学 | Preparation method of cellulose-based antibacterial food packaging film |
| CN111620365A (en) * | 2019-02-28 | 2020-09-04 | 中国科学院化学研究所 | High-concentration silver halide solution, preparation method thereof and regeneration method of silver halide |
| CN111621062B (en) * | 2019-02-28 | 2022-03-01 | 中国科学院化学研究所 | Polysaccharide/silver halide composite material and preparation method and application thereof |
| CN110330569A (en) * | 2019-08-22 | 2019-10-15 | 齐鲁工业大学 | A kind of preparation method of high substituted degree oxycellulose |
| CN113248752A (en) * | 2021-04-15 | 2021-08-13 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of bacterial cellulose dissolution regeneration film |
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