CN104130425A - Preparation method of regenerated cellulose material - Google Patents
Preparation method of regenerated cellulose material Download PDFInfo
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- CN104130425A CN104130425A CN201310158819.6A CN201310158819A CN104130425A CN 104130425 A CN104130425 A CN 104130425A CN 201310158819 A CN201310158819 A CN 201310158819A CN 104130425 A CN104130425 A CN 104130425A
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Abstract
The invention belongs to the technical field of preparation of a regenerated cellulose material and discloses a preparation method of the regenerated cellulose material. A employed solvent is a carboxylic acid type ionic liquid or is a co-solvent which is composed of the carboxylic acid type ionic liquid and an active-proton-free polar organic solvent, wherein the carboxylic acid type ionic liquid is preferably selected from 1-ethyl-3-methylimidazole acetate, 1-propyl-3-methylimidazole acetate or 1-butyl-3- methylimidazole acetate; an auxiliary solvent is selected from one or more of DMF, DMAc, DMI, DMSO, pyrrodine, acetone, dichloromethane and dichloroethane; and a solidifying agent is preferably selected from alcohol organic solvents. The carboxylic acid type ionic liquid is most preferably selected from the 1-ethyl-3-methylimidazole acetate and the 1-butyl-3-methylimidazole acetate; the auxiliary solvent is most preferably DMF; and the solidifying agent is preferably ethanol; wherein a mass ration of the carboxylic acid type ionic liquid to the auxiliary solvent is 5:5. By means of the preparation method, mechanical performances of a regenerated cellulose product can be significantly improved and environmental pollution can be reduced.
Description
Technical field
The invention belongs to material of regenerated cellulose preparing technical field, particularly one can improve material of regenerated cellulose mechanical property, especially the preparation method of toughness.
Background technology
Mierocrystalline cellulose is that occurring in nature distributes the most extensively, the maximum natural polymer of reserves, and annual plant can produce the Mierocrystalline cellulose of hundred billion tons by photosynthesis, therefore can say that Mierocrystalline cellulose is a kind of inexhaustible renewable resources.Mierocrystalline cellulose also has fully biodegradable, good biocompatibility, and good mechanical performance, is easy to the many advantages such as modification, has been widely used in industrial production and people's daily life.Mierocrystalline cellulose is due to the feature of self aggregated structure, be in molecule, intermolecularly all have a large amount of hydrogen bonds, have again higher degree of crystallinity simultaneously, therefore natural cellulose can not melting, also be difficult to be dissolved in general solvent, this has brought great inconvenience to cellulosic processed and applied.
Industrialized viscose process regenerated cellulose occupies dominant position in regenerated cellulose industry always, so far the history of existing more than 100 year.Regenerated cellulose film (glassine paper), long filament and the short silk produced by viscose process have important application in national economy.But due to a large amount of compounds such as alkali, sulfuric acid and dithiocarbonic anhydride that use in the course of processing, easily produce a large amount of toxic gas such as hydrogen sulfide, dithiocarbonic anhydride and contaminated wastewater serious, development prospect is restricted, at present the existing gesture being eliminated gradually.4-methylmorpholine-N-oxide compound (NMMO) system is existing suitability for industrialized production also, the regenerated cellulose called after Lyocell fiber of its production, but the method solvent is expensive, recovery technology harshness.In addition also have lithium chloride/N,N-DIMETHYLACETAMIDE (LiCl/DMAc) system, the cellosolve systems such as urea alkali systems, but due to dissolution system self, suitability for industrialized production difficulty.Therefore find suitable solvent, and by the economic environmental protection of Mierocrystalline cellulose to dissolve processing be the target that people pursue always.And recent years, ionic liquid arouses widespread concern for cellulosic dissolving and processing.Preparing material of regenerated cellulose taking ionic liquid as medium, have the advantages such as environmentally friendly, with short production cycle, convenient solvent reclaiming, is the very potential Mierocrystalline cellulose new method for processing of one.
Ionic liquid is cellulosic direct solvent, and direct solvent method is produced material of regenerated cellulose and generally comprised: key steps such as being shaped, solidifying, washing and be dry.And in coagulation step, form the basic structure of regenerated cellulose, often material of regenerated cellulose performance is played to conclusive effect.The process of solidifying is very complicated, between solvent, Mierocrystalline cellulose, non-solvent peptizer, interacts, and generates gel structure.The gel structure that different curing conditions obtains may be different, cause the structure such as degree of crystallinity, density of dry rear material of regenerated cellulose different, and then cause the variation of material property.Likely obtain the material of regenerated cellulose of excellent property by setting solvent, dissolution conditions, peptizer, curing condition and drying conditions etc.
The mechanical property of material of regenerated cellulose is relevant with solvent system and technology of preparing relation, but has generally the shortcoming that elongation at break is lower, i.e. lacking toughness.For overcoming the shortcoming of poor toughness, glassine paper industry (with viscose process produce regenerated cellulose film) in, generally use elasticizer plasticizing product, otherwise film crisp, easily split, be difficult to meet actual operation requirements.Softening agent is the small molecules easily running off, and this is inappropriate for the Application Areas that requires long service.In addition, use softening agent also to cause the tensile strength of film to reduce rapidly (Zhangwei Jin, Jianqiang Wang et al.Journal ofApplied Polymer Science.2012,125,704-709), this is because softening agent has reduced the bonding force between macromolecular chain.Using elastomer blended is also a route that improves regenerated cellulose toughness, add elastomer polymer and cellulose blending, but be accompanied by the raising of elongation at break, the strength and modulus of regenerated cellulose film also significantly reduces (Xiaomin Zhang, Jin Zhu et al.Macromolecular Research.2012, vol.20, No.7, pp703-708).
Summary of the invention
The object of this invention is to provide a kind of preparation method of material of regenerated cellulose, this preparation method can improve the mechanical property of material of regenerated cellulose, especially toughness.
A preparation method for material of regenerated cellulose, comprises raw cellulose successively through dissolving, deaeration, is shaped, solidifies, makes material of regenerated cellulose after washing, drying and other steps.
It is characterized in that:
The solvent using in described dissolving step is the cosolvent of carboxylic acid type ionic liquid or carboxylic acid type ionic liquid and secondary solvent composition, and wherein, described secondary solvent is the polar organic solvent that does not contain Labile protons; The positively charged ion of described carboxylic acid type ionic liquid is preferably taking imidazole ring as basis, and negatively charged ion can be selected the carboxylic acid ions such as acetic acid ion, propionic acid ion, butyric acid ion; More preferably, described carboxylic acid type ionic liquid is 1-ethyl-3-methylimidazole acetate, 1-propyl group-3-Methylimidazole acetate or 1-butyl-3-Methylimidazole acetate; Described secondary solvent is preferably substituting group amides, sulfone class, ketone and halogenated hydrocarbon etc., addition is the 0-70% (in use not cause Mierocrystalline cellulose to be separated out as the upper limit) of described cosolvent total mass, can be selected from one or more in DMF, DMAc, DMI, DMSO, pyridine, acetone, methylene dichloride and ethylene dichloride;
The peptizer using in described coagulation step is the organic solvent that contains Labile protons, comprises alcohols, thio-alcohol, Ammonia and carboxylic-acid etc.; Be preferably alcohol organic solvent, as selected the one in methyl alcohol, ethanol and Virahol to use separately or multiple mixing use; Be more preferably ethanol or the ethanol/water taking ethanol as main component, ethanol/acetone solution (wherein the mass content of ethanol is at least 80%);
Optimized being chosen as: carboxylic acid type ionic liquid is selected from 1-ethyl-3-methylimidazole acetate or 1-butyl-3-Methylimidazole acetate, and secondary solvent is DMF, and the mass ratio of carboxylic acid type ionic liquid and DMF is 5: 5, peptizer is selected ethanol simultaneously.
The preparation method of material of regenerated cellulose provided by the invention can obviously improve mechanical property, the especially toughness of regenerated fibre cellulose product, can make material of regenerated cellulose elongation at break significantly improve; Adopt the preparation method of material of regenerated cellulose provided by the invention, can not add under the condition of softening agent, the elongation at break of regenerated fibre cellulose product is significantly improved, high energy reaches more than 40%, and tensile strength is still very high.
Embodiment
The mechanical property of regenerated cellulose and its close structure contact.To be mainly that the motor capacity of its molecule segment is low cause the poor toughness of regenerated cellulose, and cellulosic molecule has little time to relax internal stress and ruptures under external force.Therefore improving cellulosic molecule motor capacity is the key that improves regenerated cellulose toughness.The motor capacity of cellulosic molecule and cellulose crystallity, density and hydrogen bond quantity of formation have much relations: density is large, intermolecular piling up closely, and cellulosic molecule space reduces; Degree of crystallinity is large, and hydrogen bond density is large, and cellulosic molecule is reduced motor capacity by molecule constraint around.Therefore, change degree of crystallinity, density or hydrogen bond quantity, can regulate and control in theory the mechanical property of regenerated cellulose.For regenerated cellulose, its structure is mainly subject to the impact of dissolving and curing condition.Fortunately, difference dissolve or curing condition under degree of crystallinity and the density of prepared regenerated cellulose have very big-difference, this is just for dissolving by change or the structure of curing condition control regenerated cellulose and then change its mechanical property and provide the foundation and fact basis.The present invention, by the investigation to multiple dissolving and curing condition, has filtered out solvent and the peptizer of preparing the regenerated cellulose with best mechanical property.
Taking 1-ethyl-3 Methylimidazole acetate ionic liquids (EmimAc)/DMF and 1-butyl-3 Methylimidazole acetate ionic liquids (BmimAc)/DMF system as example, technical scheme of the present invention is described further below.
The Mierocrystalline cellulose using in following examples is commercially available Cotton Pulp, pulverizes, so that mixed dissolution before using.Ionic liquid is commercially available 1-ethyl-3 Methylimidazole acetate ionic liquids (EmimAc) and 1-butyl-3 Methylimidazole acetate (BmimAc) ionic liquid, and DMF, DMAC and DMSO are analytical reagent.
In order to compare the impact effect of peptizer, under each embodiment condition, the cellulose solution making solidifies with ethanol and two kinds of peptizer of deionization respectively, the preparation that each embodiment comprises two kinds of samples.
The cellulosic raw material using in following embodiment can be selected from any cellulosic material, such as Cotton Pulp and wood pulps.
Embodiment 1:
2g Cotton Pulp and 23gEmimAc are added in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stops stirring, and bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 70MPa, and elongation at break is about 14%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, film fragility is large, in drying process, easily splits, and is difficult to make the film that meets Elongation test condition.
Embodiment 2:
By 2g Cotton Pulp and 23gEmimAc/DMF (11.5gEmimAc, 11.5gDMF) cosolvent adds in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stop stirring, bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 93MPa, and elongation at break is about 34%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 60MPa, and elongation at break is about 5%.
Embodiment 3:
By 2g Cotton Pulp and 23gEmimAc/DMF (9.2gEmimAc, 13.8gDMF) cosolvent adds in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stop stirring, bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 98MPa, and elongation at break is about 23%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 87MPa, and elongation at break is about 5%.
Embodiment 4:
2g Cotton Pulp and 23gBmimAc are added in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stops stirring, and bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 80MPa, and elongation at break is about 16%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film drying process is easily broken, and is difficult to be met the sample of Elongation test condition.
Embodiment 5:
By 2g Cotton Pulp and 23gBmimAc/DMF (11.5gBmimAc, 11.5gDMF) cosolvent adds in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stop stirring, bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 97MPa, and elongation at break is about 47%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 70MPa, and elongation at break is about 6.5%.
Embodiment 6:
By 2g Cotton Pulp and 23gBmimAc/DMF (9.2gBmimAc, 13.8gDMF) cosolvent adds in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stop stirring, bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 103MPa, and elongation at break is about 30%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 95MPa, and elongation at break is about 6%.
Embodiment 7:
By 2g Cotton Pulp and 23gBmimAc/DMF (6.9gBmimAc, 16.1gDMF) cosolvent adds in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stop stirring, bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, uses along a direction and scrapes cellulose solution, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 102MPa, and elongation at break is about 22%.
If above-mentioned peptizer is changed to deionized water, by the same manner masking, gained film stretching intensity is about 109MPa, and elongation at break is about 14%.
In table 1, list the Comprehensive Correlation data of above-described embodiment 1～7:
The tensile property of table 1 regenerated cellulose film
In table, EmimAc is 1-ethyl-3 Methylimidazole acetate; BmimAc is 1-butyl-3 Methylimidazole acetate.
As shown in table 1, taking Mierocrystalline cellulose/BmimAc solution as example, if select deionized water as peptizer, gained cellulose aquagel is the opaque shape of oyster white and easily cracked, gained material of regenerated cellulose fragility is larger after drying, easily cracked, is difficult to obtain complete film; If select the organic solvents such as alcohols as peptizer, gained gel is transparent, and drying gained thin film mechanical performance is better, and tensile strength is 80MPa, and elongation at break reaches 16% left and right.From table 1, it can also be seen that, in ionic liquid, add DMF composition cosolvent, can further improve the toughness of material of regenerated cellulose, finally can reach the elongation at break of the glassine paper after plasticising prepared by viscose process.
During taking ethanol as peptizer, the consumption of secondary solvent is not more high better, but with 5: 5 the bests of mass ratio.During taking deionized water as peptizer, the consumption of secondary solvent is more high better, but the consumption of secondary solvent reach solvent total amount 70% time, although the film toughness of gained increases, but effect is still not as the film with alcohol solidification, due to the restriction of dissolving power, cannot further improve the consumption of secondary solvent.Under various secondary solvent ratio conditions, be all not so good as under similarity condition the good toughness as peptizer gained RCF regenerated cellulose film with ethanol using deionized water as peptizer gained RCF regenerated cellulose film.
Contrast therewith, if select non-carboxylic acid type ionic liquid, as 1-butyl-3-Methylimidazole chlorion liquid (BmimCl), 1-allyl group-3-Methylimidazole chlorion liquid (AmimCl), select in any case cosolvent and peptizer, the elongation at break of gained RCF regenerated cellulose film is all lower, all in 8% left and right.So the present invention adopts carboxylic acid type ionic liquid (or together using with secondary solvent) dissolving cellulos, use the organic solvents such as alcohols as peptizer, the two has match selection relation.
We think above-mentioned this matching relationship, are determining the structure of regenerated cellulose due to the carboxyl anion of carboxylic acid type ionic liquid and the interaction of peptizer, and then affect its mechanical property.For the structural difference of regenerated cellulose, we have carried out density measurement to it by selected part sample, and concrete outcome is in table 2.
The density of table 2 regenerated cellulose film
As shown in table 2, our known density taking deionized water as peptizer gained RCF regenerated cellulose film is as 1.52g/cm
3left and right, and density taking ethanol as peptizer gained RCF regenerated cellulose film is as 1.47g/cm
3left and right.Deionized water does peptizer gained density of film does the density of peptizer gained film far above ethanol, this shows that the two RCF regenerated cellulose film obtaining structurally exists difference.This structural difference is perhaps the reason of its performance difference.We infer, less by the RCF regenerated cellulose film density of alcohol solidification gained, its molecular arrangement is comparatively loose, make in its molecule and the minimizing of the quantity of intermolecular hydrogen bonding, free volume increases simultaneously, the motor capacity of its molecular chain improves, the molecular chain rearrangement of can moving under external force, and material can produce compared with large deformation.
In sum, after carboxylic acid type ionic liquid (comprise carboxylic acid type ionic liquid and carboxylic acid type ionic liquid with the cosolvent containing the polar organic solvent composition of Labile protons) dissolving cellulos, its solution and peptizer have selection matching relationship: do the material of regenerated cellulose that the prepared material of regenerated cellulose performance of peptizer is better than making of deionized water peptizer gained with organic solvents such as alcohols.Carboxylic acid type ionic liquid and DMF, DMAc, DMI, DMSO, pyridine, acetone, methylene dichloride and ethylene dichloride etc. also can dissolving cellulos containing the cosolvent of the polar organic solvent composition of Labile protons, use cosolvent can make cellulose solution reduced viscosity, the more important thing is the mechanical property that can further improve regenerated cellulose.
In the time that the positively charged ion of carboxylic acid type ionic liquid of the present invention is imidazole type, best results, because of its stability higher; Negatively charged ion can be acetate moiety, propionate, butyric acid root etc.Can buy from the market because of 1-ethyl-3 Methylimidazole acetate ionic liquids (EmimAc) and 1-butyl-3 Methylimidazole acetate ionic liquid (BmimAc), these two kinds of ionic liquids are optimal selection at present.
The secondary solvent that the present invention adopts is the polar solvent that does not contain Labile protons, as medium in DMF, DMAc, DMSO, pyridine, acetone, methylene dichloride and ethylene dichloride, because the solvent containing Labile protons will cause Mierocrystalline cellulose to be separated out, can not use as secondary solvent, and non-polar solvent and ionic liquid do not dissolve each other.The addition of secondary solvent is not to cause Mierocrystalline cellulose to be separated out as the upper limit.
Peptizer of the present invention, is the organic solvent that contains Labile protons such as alcohols, thio-alcohol, Ammonia and carboxylic-acid, wherein preferably containing the alcohol organic solvent of Labile protons, as one or more in methyl alcohol, ethanol, Virahol.From using the combined factors such as price, toxicity to consider, ethanol is optimal selection.
In a word, taking carboxylic acid type ionic liquid as solvent, with suitable organic solvent, if alcohol is peptizer, can prepare the material of regenerated cellulose of high tenacity.Can further strengthen this effect using the polar organic solvent that does not contain Labile protons as the secondary solvent of ionic liquid.
Embodiment 8:
2g Cotton Pulp and EmimAc/DMAc (11.5gEmimAc, 11.5gDMAc) are added in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stops stirring, and bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 100MPa, and elongation at break is about 36%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 70MPa, and elongation at break is about 6.8%.
Embodiment 9:
2g Cotton Pulp and EmimAc/DMSO (11.5gEmimAc, 11.5gDMSO) are added in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stops stirring, and bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 106MPa, and elongation at break is about 29%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 66MPa, and elongation at break is about 5.6%.
Embodiment 10:
2g Cotton Pulp and BmimAc/DMAc (11.5gBmimAc, 11.5gDMAc) are added in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stops stirring, and bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 98MPa, and elongation at break is about 34%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 64MPa, and elongation at break is about 6.2%.
Embodiment 11:
2g Cotton Pulp and BmimAc/DMSO (11.5gBmimAc, 11.5gDMSO) are added in 50mL there-necked flask, in 80 DEG C of oil baths, heat, adopt mechanical stirring, after stirring 2h, Mierocrystalline cellulose dissolves to obtain as clear as crystal cellulose solution completely, stops stirring, and bubble in solution is removed completely.
The solution that takes a morsel is poured on pre-prepd sheet glass, scrapes cellulose solution with plastic film mulch device along a direction, and it is spread over becomes uniform cellulose solution film on sheet glass.
Get a tank, put into enough ethanol.The sheet glass that is spreading cellulose solution is put into this tank, after cellulose membrane solidifies, come off from sheet glass.
Drying operation is used sheet glass and vacuum drying oven.Clean cellulose membrane is clipped between layer glass plate, puts into vacuum drying oven dry, until complete drying obtains RCF regenerated cellulose film.The film sample making is cut into the batten of 1x5cm, test tensile strength and elongation at break on universal tensile testing machine.Gained film stretching intensity is about 96MPa, and elongation at break is about 37%.
If above-mentioned ethanol is changed to deionized water, the constant masking of other operational conditions, gained film stretching intensity is about 63MPa, and elongation at break is about 5.8%.
Claims (10)
1. a preparation method for material of regenerated cellulose, comprises raw cellulose successively through dissolving, deaeration, is shaped, solidifies, makes material of regenerated cellulose after washing, drying step; It is characterized in that, the solvent using in described dissolving step is the cosolvent of carboxylic acid type ionic liquid or carboxylic acid type ionic liquid and secondary solvent composition, and wherein, described secondary solvent is the polar organic solvent that does not contain Labile protons; The peptizer using in described coagulation step is the organic solvent that contains Labile protons.
2. the preparation method of material of regenerated cellulose according to claim 1, is characterized in that, the positively charged ion of described carboxylic acid type ionic liquid is taking imidazole ring as basis.
3. the preparation method of material of regenerated cellulose according to claim 1 and 2, is characterized in that, the negatively charged ion of described carboxylic acid type ionic liquid is selected from acetic acid ion, propionic acid ion or butyric acid ion.
4. the preparation method of material of regenerated cellulose according to claim 1, is characterized in that, described carboxylic acid type ionic liquid is 1-ethyl-3-methylimidazole acetate, 1-propyl group-3-Methylimidazole acetate or 1-butyl-3-Methylimidazole acetate.
5. the preparation method of material of regenerated cellulose according to claim 1, it is characterized in that, described secondary solvent is selected from substituting group amides, sulfone class, ketone and halogenated hydrocarbon, and addition is the 0-70% of described cosolvent total mass, in use not cause Mierocrystalline cellulose to be separated out as the upper limit.
6. the preparation method of material of regenerated cellulose according to claim 1, is characterized in that, described secondary solvent is selected from one or more in DMF, DMAc, DMI, DMSO, pyridine, acetone, methylene dichloride and ethylene dichloride.
7. the preparation method of material of regenerated cellulose according to claim 1, is characterized in that, described peptizer is alcohols, thio-alcohol, Ammonia and carboxylic-acid.
8. the preparation method of material of regenerated cellulose according to claim 1, is characterized in that, described peptizer is that the one in methyl alcohol, ethanol and Virahol is used separately or multiple mixing is used.
9. the preparation method of material of regenerated cellulose according to claim 1, is characterized in that, described peptizer is ethanol/water or the ethanol/acetone solution taking ethanol as main component, and wherein the mass content of ethanol is at least 80%.
10. the preparation method of material of regenerated cellulose according to claim 1, it is characterized in that, described carboxylic acid type ionic liquid is selected from 1-ethyl-3-methylimidazole acetate or 1-butyl-3-Methylimidazole acetate, secondary solvent is DMF, and the mass ratio of carboxylic acid type ionic liquid and DMF is 5: 5, peptizer is selected ethanol simultaneously.
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| CN109206670A (en) * | 2017-07-03 | 2019-01-15 | 中国科学院化学研究所 | A kind of composition of polysaccharide derivates of phenolic hydroxy group and its preparation method and application |
| CN108727623A (en) * | 2018-06-14 | 2018-11-02 | 北京林业大学 | A kind of preparation method of the antibacterial food package film of cellulose base |
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