CN103012822A - Method for preparing regenerated cellulose membrane using cellulose carbamate - Google Patents
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Abstract
The invention discloses a method for preparing a regenerated cellulose membrane using cellulose carbamate. The method comprises the steps of: dispersing the cellulose carbamate in 6-10wt% sodium hydroxide/0.1-3wt% zinc chloride aqueous solution, freezing the resulting solution under a low temperature condition to below -10 DEG C, taking the frozen solution out to unfreeze under a condition not higher than 50 DEG C, thereby obtaining a cellulose carbamate solution with high stability, defoaming the cellulose carbamate solution, casting and wiping the membrane, and carrying out direct coagulating and formation in a coagulating bath to prepare the regenerated cellulose membrane with low residual nitrogen. The membrane has good mechanical property and light transmittance; by adopting the method, saponification and regeneration processes in alkaline solutions, such as NaOH solution, can be eliminated, the production process is nontoxic and pollution-free; a process for producing a cellophane by means of viscose, which causes heavy pollution, can be replaced; and the method has obvious application prospect.
Description
Invention field
The present invention relates to a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate, belong to the natural polymer field, also belong to chemistry, agricultural and field of environment engineering.
Technical background
Mierocrystalline cellulose is the renewable resources that extensively exists on the earth.Over more than 100 year, people have carried out systematic research to its structure, chemistry and physical properties, especially in recent years, day by day minimizing along with prospective oil, cellulosic research and development application has been reached unprecedented height, except Mierocrystalline cellulose in the large industry of textile and paper two with original form as raw material, its derivative is widely used in suitability for industrialized production as raw material equally, wherein the viscose fiber by the cellulose xanthate preparation occupies critical role in the regenerated fiber of textile industry.But this technique exists serious environmental issue in spinning process.
As a kind of substitute of adhering process, over nearly 20 years, people more pay close attention to cellulose carbamate (CC) technique, have formed a kind of novel and economic CC synthetic route at present.Compare with adhering process, this technique is except to eco-friendly, and the processing of CC and spinning process and adhering process are very close, can utilize existing viscose glue production unit to implement on the carbamate technological principle.The report that many relevant cellulose carbamate dissolvings and preparation cellulose carbamate or regenerated fibre cellulose product have wherein been arranged both at home and abroad, patent WO 03099871(2003), DE 10127189(2003), CN 100516326C(2007) and US 2005/0234229A1(2005) in the method that discloses be the synthetic cellulose carbamate dissolution in low temperature that obtains in the sodium hydroxide solvent, and in the precipitation bath that contains acid or salt solidification forming with the preparation cellulose carbamate fibre, film or sponge, and can continue containing 0.5%NaOH and 12wt%Na
2SO
4Middle regeneration obtains corresponding regenerated fibre cellulose product.But prepare thus the cellulose carbamate solution less stable.Patent US 2008/0023874A1(2008) method that discloses then is to obtain spinning solution take N-methyl-N-oxide compound morpholine (NMMO) as solvent, solidification forming prepares cellulose carbamate fibre again in the NMMO aqueous solution 10% after aftertreatment extruding through spinning nozzle under 85 ~ 95 ℃ of conditions, continues then that regeneration prepares regenerated cellulose fibre in 0.5% the NaOH aqueous solution.The middle proposition of patent US2009259032 (A1) (2009) is then solidified in the butyl methyl imidazoles aqueous solution take ionic liquid as the dissolution with solvents cellulose carbamate and is prepared the cellulose carbamate film in addition, wherein cellulose carbamate content is 20 ~ 50wt% in the solution, nitrogen content is 0.1 ~ 7%, the tensile strength that obtains the cellulose carbamate film is 75 ~ 350MPa, elongation at break is 8 ~ 30%, Young's modulus is 5000 ~ 20000MPa, but NMMO solvent and ionic liquid are subjected to dissolution conditions harsh, being difficult for recovery waits the restriction of unfavourable condition to be unfavorable for industrializing implementation.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of solution-stabilized and lower-cost method that is directly prepared regenerated cellulose film by cellulose carbamate is provided.
The present invention for the technical scheme that provides is provided is: a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate, be specially: cellulose carbamate is dissolved in the aqueous solution of the sodium hydroxide that contains 6 ~ 10wt%, 0.1 ~ 3wt% zinc oxide, be refrigerated to below-10 ℃, taking-up is thawed not being higher than under 50 ℃ the condition, obtain cellulose carbamate solution, then with solution deaeration, curtain coating knifing, and in precipitation bath solidification forming, water is rinsed well and is namely obtained regenerated cellulose film.
As a kind of preferred, the aqueous solution of described dissolving cellulos carbamate is for containing the aqueous solution of 7 ~ 8wt% sodium hydroxide and 0.6 ~ 1.8wt% zinc oxide.
Cellulose carbamate content in the described cellulose carbamate solution is 4 ~ 8wt%.
Described precipitation bath is 1 ~ 15wt%H
2SO
4The aqueous solution, the aqueous solution of 1 ~ 15wt%HCl, the aqueous solution of 1 ~ 10mol/L HAC, 1 ~ 15wt%H
3PO
4The aqueous solution, 1 ~ 20wt%H
2SO
4/ 5 ~ 20wt%Na
2SO
4The aqueous solution or 1 ~ 20wt%H
2SO
4/ 5 ~ 20wt% (NH
4)
2SO
4The aqueous solution in a kind of.As a kind of preferred, described precipitation bath is 3 ~ 10wt%H
2SO
4The aqueous solution, 3 ~ 10wt%HCl aqueous solution, 2 ~ 5mol/L HAC aqueous solution, 3 ~ 10wt%H
3PO
4The aqueous solution, 3 ~ 15wt%H
2SO
4/ 5 ~ 20wt%Na
2SO
4The aqueous solution or 3 ~ 15wt%H
2SO
4/ 5 ~ 20wt% (NH
4)
2SO
4A kind of in the aqueous solution.
Described coagulation bath temperature is 5 ~ 80 ℃, and the process of setting spent time is 1 ~ 30min.
Cellulose carbamate can be applied for a patent from this laboratory (application number: 200910062951.0, publication number: microwave synthesis method known CN101597336A) prepares, namely at first Mierocrystalline cellulose is immersed in and makes it fully adsorb urea in the aqueous solution of urea, then squeeze out unnecessary aqueous solution of urea; Drying obtains the uniform mixture of Mierocrystalline cellulose/urea; Then obtain the cellulose carbamate product by washing, drying at last through microwave heating Mierocrystalline cellulose/urea solid mixture.Because the inventive method only relates to the dissolving of cellulose carbamate, so naturally be applicable to the cellulose carbamate of other method preparation.
Sodium hydrate content is lower in the cellulose carbamate spinning solution that the present invention prepares, reduced the consumption to acid solutions such as sulfuric acid in the sour precipitation bath, and the zinc sulfate that generates in the process of setting or other corresponding zinc salt can be used as peptizer and use, and be economical convenient.
The regenerated cellulose film that the present invention prepares has good transmittance and mechanical property, its tensile strength is 59 ~ 112MPa, dried elongation at break is 7 ~ 13%, Young's modulus is 4769 ~ 7890MPa, transmittance is 80 ~ 90%, residual nitrogen amount low (＜0.3%), the process that can remove desired saponification in the basic solutions such as NaOH in other open technique, regeneration from.
The inventive method is take a kind of new solvent compositions as solvent, dissolving obtains the cellulose carbamate solution of low alkali number, high stability, and curtain coating knifing after the deaeration, directly solidification forming just prepares and has good transmittance and mechanical property regenerated cellulose film.Present method cost is low, and is simple to operation, is easy to suitability for industrialized production.This method is expected to replace the with serious pollution technique that present viscose process is produced glassine paper, brings thus economic benefit and social benefit, has very high industrial applications and is worth.
Compared with the prior art, advantage of the present invention and useful benefit are:
1) the used a kind of new solvent compositions of the inventive method and dissolving method thereof the solubleness that can significantly improve cellulose carbamate and the stability of gained solution, left standstill under the normal temperature condition 12 ~ 240 hours and gel not, cost is low, solute effect is good, help the raising of regenerated cellulose film transmittance and mechanical property, be conducive to suitability for industrialized production.
2) in the general method, when the nitrogen content of cellulose carbamate was 2 ~ 3%, cellulose carbamate could dissolve preferably.Use present method to dissolving used Mierocrystalline cellulose element carbamate nitrogen content without explicitly calling for.Particularly when nitrogen content lower (0.5 ~ 1.2%), still can dissolve the cellulose carbamate solution that obtains 4.0 ~ 8.0wt%, so only need solidification forming in acid coagulating bath just prepares the regenerated cellulose film of residual nitrogen amount low (＜0.3%), removed the process of basic solution saponification such as using sodium hydroxide (NaOH) in other technique, regeneration from, cost.
3) its alkalinity is lower by (6.0 ~ 8.0wt%) in the cellulose carbamate solution that obtains of dissolving, can obviously reduce the consumption of the acid solution such as sulfuric acid in the sour precipitation bath, and the zinc sulfate that generates in the process of setting or other corresponding zinc salt can be used as peptizer and use, and be economical convenient.
Embodiment
Below in conjunction with concrete example technical scheme of the present invention and application are described further, rather than limit the invention.
Embodiment 1
Getting 15 gram nitrogen contents is 1.218% cellulose carbamate sample (viscosity-average molecular weight 8.8 * 10
4) be dissolved in the aqueous solution of 275 gram 7.0wt%NaOH/1.6wt%ZnO, put into refrigerator and cooled and freeze to-10 ℃, freezingly from refrigerator, to take out after complete, 50 ℃ of envrionment conditionss are thawed, and stir to obtain the 5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 25 ℃ 1wt%
2SO
4Take out after solidifying 5min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 59MPa, and elongation at break is 9%, and Young's modulus is 4769MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 2
Getting 15 gram nitrogen contents is 1.218% cellulose carbamate (viscosity-average molecular weight 8.8 * 10
4) be dissolved in the aqueous solution of 275 gram 7.0wt%NaOH/1.6wt%ZnO, put into refrigerator and cooled and freeze to-12 ℃, freezingly from refrigerator, to take out after complete, 25 ℃ of envrionment conditionss are thawed, and stir just to obtain the 5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 5 ℃ 5wt%
2SO
4Take out after solidifying 5min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 86MPa, and elongation at break is 9%, and Young's modulus is 7077MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 3
Getting 13 gram nitrogen contents is 1.262% cellulose carbamate (viscosity-average molecular weight 5.6 * 10
4) be dissolved in the 187 gram 7.5wt%NaOH/1.6wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, freezingly from refrigerator, to take out after complete, 35 ℃ of envrionment conditionss are thawed, and stir just to obtain the 6.5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 25 ℃ 3wt%
2SO
4Take out after solidifying 30min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 112MPa, and elongation at break is 11%, and Young's modulus is 7079MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 4
Getting 21 gram nitrogen contents is 1.262% cellulose carbamate (viscosity-average molecular weight 5.6 * 10
4) be dissolved in the 279 gram 8.5wt%NaOH/1.2wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-18 ℃, freezingly from refrigerator, to take out after complete, 42 ℃ of envrionment conditionss are thawed, and stir just to obtain the 7.0wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems takes out after the HCl aqueous solution of then putting into 15 ℃ 1wt% solidifies 3min, and water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 110MPa, and elongation at break is 12%, and Young's modulus is 6565MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 5
Getting 18 gram nitrogen contents is 1.952% cellulose carbamate (viscosity-average molecular weight 10.2 * 10
4) be dissolved in the 282 gram 7.0wt%NaOH/0.8wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, freezingly from refrigerator, to take out after complete, 48 ℃ of envrionment conditionss are thawed, and stir just to obtain the 6wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems takes out after the HCl aqueous solution of then putting into 10 ℃ 15wt% solidifies 10min, and water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 72MPa, and elongation at break is 10%, and Young's modulus is 5716MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 6
Getting 11 gram nitrogen contents is 1.089% cellulose carbamate (viscosity-average molecular weight 10.7 * 10
4) be dissolved in the 289 gram 8.0wt%NaOH/1.8wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-11 ℃, freezingly from refrigerator, take out after complete, thaw, stir under 50 ℃ of conditions and just obtain the 5.5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems takes out after the HAC aqueous solution of then putting into 30 ℃ 1mol/L solidifies 15min, and water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 93MPa, and elongation at break is 13%, and Young's modulus is 6174MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 7
Getting 13 gram nitrogen contents is 1.732% cellulose carbamate (viscosity-average molecular weight 5.8 * 10
4) be dissolved in the 287 gram 9.0wt%NaOH/2.5wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-24 ℃, freezingly from refrigerator, to take out after complete, 50 ℃ of envrionment conditionss are thawed, and stir just to obtain the 6.5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems takes out after the HAC aqueous solution of then putting into 25 ℃ 10mol/L solidifies 5min, and water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 82MPa, and elongation at break is 8%, and Young's modulus is 5997MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 8
Getting 15 gram nitrogen contents is 1.163% cellulose carbamate (viscosity-average molecular weight 5.8 * 10
4) be dissolved in the 185 gram 6.5wt%NaOH/0.5wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, freezingly from refrigerator, take out after complete, thaw, stir under 45 ℃ of envrionment conditionss and just obtain the 7.5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 80 ℃ 1wt%
2SO
4/ 5wt%Na
2SO
4Take out after solidifying 10min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 72MPa, and elongation at break is 9%, and Young's modulus is 5716MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 9
Getting 15 gram nitrogen contents is 1.009% cellulose carbamate (viscosity-average molecular weight 7.8 * 10
4) be dissolved in the 285 gram 6.0wt%NaOH/0.1wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-15 ℃, freezingly from refrigerator, take out after complete, thaw, stir under 30 ℃ of envrionment conditionss and just obtain the 5.0wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 50 ℃ 20wt%
2SO
4/ 20wt%Na
2SO
4Take out after solidifying 5min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 90MPa, and elongation at break is 8%, and Young's modulus is 7013MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 10
Getting 24 gram nitrogen contents is 1.2% cellulose carbamate (viscosity-average molecular weight 5.5 * 10
4) be dissolved in the 276 gram 10.0wt%NaOH/3.0wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-14 ℃, freezingly from refrigerator, to take out after complete, 40 ℃ of envrionment conditionss are thawed, and stir just to obtain the 8.0wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 25 ℃ 1wt%
2SO
4/ 5wt% (NH
4)
2SO
4Take out after solidifying 5min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 97MPa, and elongation at break is 9%, and Young's modulus is 6743MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 11
Getting 12 gram nitrogen contents is 0.50% cellulose carbamate (viscosity-average molecular weight 10.7 * 10
4) be dissolved in the 288 gram 8.0wt%NaOH/2.0wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, freezingly from refrigerator, to take out after complete, 35 ℃ of envrionment conditionss are thawed, and stir just to obtain the 4.0wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 30 ℃ 20wt%
2SO
4/ 20wt% (NH
4)
2SO
4Take out after solidifying 5min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 91MPa, and elongation at break is 9%, and Young's modulus is 6581MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 12
Getting 20 gram nitrogen contents is 1.218% cellulose carbamate sample (viscosity-average molecular weight 8.8 * 10
4) be dissolved in the aqueous solution of 380 gram 7.0wt%NaOH/1.6wt%ZnO, put into refrigerator and cooled and freeze to-10 ℃, freezingly from refrigerator, to take out after complete, 50 ℃ of envrionment conditionss are thawed, and stir to obtain the 5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 25 ℃ 1wt%
3PO
4Take out after solidifying 3min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 100MPa, and elongation at break is 8%, and Young's modulus is 6937MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 13
Getting 15 gram nitrogen contents is 1.218% cellulose carbamate sample (viscosity-average molecular weight 9.8 * 10
4) be dissolved in the aqueous solution of 275 gram 7.0wt%NaOH/1.6wt%ZnO, put into refrigerator and cooled and freeze to-10 ℃, freezingly from refrigerator, to take out after complete, 50 ℃ of envrionment conditionss are thawed, and stir to obtain the 5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 25 ℃ 15wt%
3PO
4Take out after solidifying 5min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 106MPa, and elongation at break is 7%, and Young's modulus is 7890MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Embodiment 14
Getting 15 gram nitrogen contents is that 1.728% cellulose carbamate (viscosity-average molecular weight 8.0 * 104) is dissolved in the aqueous solution of 275 gram 7.5wt%NaOH/1.6wt%ZnO, putting into refrigerator and cooled freezes to-12 ℃, freezingly from refrigerator, take out after complete, 25 ℃ of envrionment conditionss are thawed, and stir just to obtain the 5wt% cellulose carbamate solution.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed, obtain transparent cellulose carbamate solution.Then glass-tube curtain coating knifing on sheet glass that copper wire (diameter 0.5mm) is arranged with two ends systems puts into the H of 5 ℃ 15wt%
2SO
4Take out after solidifying 1min in the aqueous solution, water is rinsed well.Be attached at last naturally to dry on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.Recording the tensile strength of regenerated cellulose film under dry state by electronic tension tester is 72MPa, and elongation at break is 3%, and Young's modulus is 7707MPa.Its transmittance is 80%, and it is that 0(detects error ± 0.3 that the ammonia nitrogen detector detects residual nitrogen amount).
Claims (6)
1. method that is directly prepared regenerated cellulose film by cellulose carbamate, it is characterized in that: cellulose carbamate is dissolved in the aqueous solution of the sodium hydroxide that contains 6 ~ 10 wt%, 0.1 ~ 3 wt% zinc oxide, be refrigerated to below-10 ℃, taking-up is thawed not being higher than under 50 ℃ the condition, obtain cellulose carbamate solution, then with solution deaeration, curtain coating knifing, and in precipitation bath solidification forming, water is rinsed well and is namely obtained regenerated cellulose film.
2. a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate according to claim 1 is characterized in that: the aqueous solution of described dissolving cellulos carbamate is for containing the aqueous solution of 7 ~ 8 wt% sodium hydroxide and 0.6 ~ 1.8 wt% zinc oxide; Cellulose carbamate content in the described cellulose carbamate solution is 4 ~ 8 wt%.
3. a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate according to claim 1 and 2, it is characterized in that: described precipitation bath is 1 ~ 15 wt% H
2SO
4The aqueous solution, the aqueous solution of 1 ~ 15 wt% HCl, the aqueous solution of 1 ~ 10 mol/L HAC, 1 ~ 15 wt% H
3PO
4The aqueous solution, 1 ~ 20 wt% H
2SO
4/ 5 ~ 20 wt% Na
2SO
4The aqueous solution or 1 ~ 20 wt%H
2SO
4/ 5 ~ 20 wt% (NH
4)
2SO
4The aqueous solution in a kind of.
4. a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate according to claim 3, it is characterized in that: described precipitation bath is 3 ~ 10 wt% H
2SO
4The aqueous solution, 3 ~ 10 wt% HCl aqueous solution, 2 ~ 5mol/L HAC aqueous solution, 3 ~ 10wt% H
3PO
4The aqueous solution, 3 ~ 15 wt% H
2SO
4/ 5 ~ 20 wt% Na
2SO
4The aqueous solution or 3 ~ 15 wt%H
2SO
4/ 5 ~ 20 wt% (NH
4)
2SO
4A kind of in the aqueous solution.
5. a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate according to claim 1 and 2, it is characterized in that: described coagulation bath temperature is 5 ~ 80 ℃, the process of setting spent time is 1 ~ 30 min.
6. a kind of method that is directly prepared regenerated cellulose film by cellulose carbamate according to claim 3, it is characterized in that: described coagulation bath temperature is 5 ~ 80 ℃, the process of setting spent time is 1 ~ 30 min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319737A (en) * | 2013-06-21 | 2013-09-25 | 武汉大学 | Preparation method of cellulose/zinc oxide nanoparticle composite material |
| CN104941683A (en) * | 2015-06-09 | 2015-09-30 | 南京林业大学 | Micro-nano ZnO/composite cellulose strip material and preparation method thereof |
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| CN101104957A (en) * | 2007-08-20 | 2008-01-16 | 中国科学院新疆理化技术研究所 | Process for preparing cellulose carbamate fibre |
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| CN101104957A (en) * | 2007-08-20 | 2008-01-16 | 中国科学院新疆理化技术研究所 | Process for preparing cellulose carbamate fibre |
| CN102432894A (en) * | 2011-10-17 | 2012-05-02 | 武汉大学 | Cellulose carbamate dissolved combined solvent and using method thereof |
| CN102691125A (en) * | 2012-06-19 | 2012-09-26 | 武汉大学 | Method for preparing regenerated cellulose fibers with cellulose carbamate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103319737A (en) * | 2013-06-21 | 2013-09-25 | 武汉大学 | Preparation method of cellulose/zinc oxide nanoparticle composite material |
| CN104941683A (en) * | 2015-06-09 | 2015-09-30 | 南京林业大学 | Micro-nano ZnO/composite cellulose strip material and preparation method thereof |
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