CN104045839A - Dissolution method of cellulose subjected to anhydride microwave modification - Google Patents
Dissolution method of cellulose subjected to anhydride microwave modification Download PDFInfo
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- CN104045839A CN104045839A CN201410309653.8A CN201410309653A CN104045839A CN 104045839 A CN104045839 A CN 104045839A CN 201410309653 A CN201410309653 A CN 201410309653A CN 104045839 A CN104045839 A CN 104045839A
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Abstract
The invention provides a dissolution method of cellulose subjected to anhydride microwave modification. The dissolution method is characterized by specifically comprising the steps of step 1, carrying out vacuum drying on cellulose and anhydride small molecules; step 2, uniformly mixing the raw materials comprising cellulose, an ionic liquid and anhydride small molecules at a ratio of (10-20%) : (50-70%): (20-40%); step 3, heating and reacting the mixture obtained in the step 2 under microwave irradiation at a predetermined time, washing the product and drying to obtain anhydride-modified cellulose; and step 4, adding the anhydride-modified cellulose obtained in the step 3 into a complex solvent comprising sodium hydroxide, urea, thiourea and water, unformly mixing, feeding into a twin-screw extruder, and extruding at -12-6 DEG C to obtain the anhydride-modified cellulose solution. By virtue of the processing modification process disclosed by the invention, the cellulose solution which is easily dissolved, environmental friendly and clean can be obtained.
Description
Technical field
The present invention has introduced cellulosic a kind of novel dissolving method after modification, relates in particular to after the overcritical modification of Mierocrystalline cellulose under the condition of low temperature high-shear dissolving spinning fast.
Background technology
Mierocrystalline cellulose is one of renewable resources the most widely that occurring in nature exists, consumption along with the energy, tellurian petroleum resources worsening shortages, environmental pollution is serious, the mankind are badly in need of finding the large green energy resource of new reserves, and Mierocrystalline cellulose is as reproducible natural resource, utilize Mierocrystalline cellulose to replace oil to obtain the industrial chemicals of Sustainable development, will be a kind of feasible and have a technological line of broad prospect of application.
Mierocrystalline cellulose is a kind of renewable resources of cheapness, according to scientist, estimates, the Mierocrystalline cellulose obtaining by photosynthesis every year surpasses 1,000 hundred million tons, surpasses present oil reserves, Mierocrystalline cellulose wide material sources.Meanwhile, cellulosic renewable, requirement that degradability meets contemporary recycling economy and environmental protection.
The mankind to cellulosic utilization origin very early, copper ammonia fibre and viscose fiber have had the history of more than 100 year, but traditional technology technique is tediously long, produce complicated, power consumption and process cost all higher, and cause serious environmental pollution, further developing of viscose fiber is affected.20th century, organic solvent (the comprising NMMO etc.) spining technology of the eighties also had certain effect, yet because continuous production technology, spinning technique, equipment and solvent recovering system, the high in cost of production problem of its true solution is all difficult to be resolved, had a strong impact on its development.So be badly in need of finding a kind of low cost, high-level efficiency, environmental protection, easy industrialized novel cellulose dissolution solvent system.
In recent years, cellulose dissolution is carried out in low-temperature alkaline/urea combination solution to the regenerated cellulose fibre that spinning obtains and caused domestic and international expert's great attention.Low-temperature alkaline urea cellulosic fibre, at the existing pilot scale line of China's report, is still subject to the restriction of equipment, technique, and the course of processing is complicated, and production energy consumption is very large, apart from through engineering approaches, industrialization, still has certain gap.
Summary of the invention
The object of the present invention is to provide the method for a kind of Mierocrystalline cellulose dissolution in low temperature after acid anhydrides microwave modification, in order to improve the dissolved efficiency of Mierocrystalline cellulose in low-temperature alkaline/thiocarbamide/urea soln, first we adopt various acid anhydrides to carry out microwave chemical modification to Mierocrystalline cellulose, for realizing the molten through engineering approaches, industrialization spun of cellulosic low temperature, produces significant.
In order to achieve the above object, the invention provides the dissolving method of a kind of Mierocrystalline cellulose after acid anhydrides microwave modification, it is characterized in that, concrete steps comprise:
Step 1: by Mierocrystalline cellulose and the vacuum-drying of acid anhydrides small molecules;
Step 2: the raw material that comprises Mierocrystalline cellulose, ionic liquid and acid anhydrides small molecules is mixed by the proportioning of 10-20%: 50-70%: 20-40%;
Step 3: the mixture of step 2 gained after reacting by heating certain hour, is obtained to anhydride modified Mierocrystalline cellulose after product is washed, is dried under microwave irradiation;
Step 4: the anhydride modified Mierocrystalline cellulose of step 3 gained is joined in the double solvents that comprises sodium hydroxide, urea, thiocarbamide and water, mix rear feeding twin screw extruder, extrude at-12-6 ℃, obtain anhydride modified cellulose solution.
Preferably, the microwave irradiation power in described step 3 is 500w-1000w, and Heating temperature is 80 ℃-120 ℃, and the reaction times is 0.5-3h.
Preferably, the anhydride modified cellulosic acid anhydride-grafted rate in described step 3 is at 10-50%.
Preferably, the Mierocrystalline cellulose in described step 1 is common cotton fiber, and the polymerization degree is at 300-600.
Preferably, the ionic liquid in described step 2 is at least one in 1-butyl-3-Methylimidazole villaumite ([BMIM] Cl) and 1-ethyl-3-methylimidazole acetate ([EMIM] Ac).
Preferably, the acid anhydrides small molecules in described step 1 is at least one in acetic anhydride, maleic anhydride and Tetra hydro Phthalic anhydride.
Preferably, the double solvents in described step 4 is comprised of sodium hydroxide 5-10wt%, urea 5-15wt%, thiocarbamide 5-15wt% and deionized water 70-80wt%.
Preferably, the concentration of the anhydride modified Mierocrystalline cellulose in described step 4 in low temperature double solvents is 15-20%.
Preferably, in described step 4, the screw speed of twin screw extruder is 200-400rpm, twin screw length-to-diameter ratio is 1: 35-1: 55, cross-head pressure is 3-5MPa, and vacuum pump pressure is 0.8-1MPa, and each section of temperature is: first paragraph :-12～-6 ℃, second segment :-8～-2 ℃, the 3rd section :-4～2 ℃, the 4th section: 0～5 ℃, head: 0～5 ℃.
The present invention will based on ionic liquid be Mierocrystalline cellulose after solvent acid anhydrides microwave modification, add certain proportion alkali solvent system, by homogenizer, be mixed into after suspension, low temperature Screw Extrusion again, under the processing condition of setting, under the effect of low temperature high-shear, plasticising reduces chain segment unit reactive force along molecular chain Overlay, hydrogen bond force weakens, and under the poly-effect of the group such as sodium hydroxide and thiocarbamide, thereby obtains being applicable to the cellulose solution of spinning.In extrusion, realize conveying, mixing, dissolving, deaeration, filtration of material etc. simultaneously, finally can form stable, even, transparent modified fibre cellulose solution, do not produce gelatin phenomenon.
Compared with prior art, the invention has the beneficial effects as follows:
Adopt processing modified technique of the present invention to obtain and be easy to dissolving, green clean cellulose solution.Acid anhydrides small molecules has destroyed in cellulosic molecule and intermolecular hydrogen bond to cellulosic modification effectively, in dissolution process, urea and thiocarbamide formation external envelope compound have further stoped cellulosic molecule self aggregation, make cellulose solution more stable, in the cellulose solution of gained, content of cellulose is high, be applicable to spinning, expand Mierocrystalline cellulose Application Areas.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.In following embodiment, Mierocrystalline cellulose used is that the polymerization degree is at the common cotton fiber of 300-600.In embodiment, twin screw extruder used can be realized low temperature and extrudes, its can have with disclosed in cn103290503A be the identical syndeton of continuous low-temperature dissolving spinning device.
Embodiment 1:
The vacuum-drying 24h at 70 ℃ by Mierocrystalline cellulose and acetic anhydride, by Mierocrystalline cellulose 10wt%, [BMIM] Cl50wt% and acetic anhydride 40wt% add homogenizer to mix, the mixture of gained is reacted to 0.5h at 80 ℃ under the microwave irradiation of power 500w, products therefrom is washed away to ionic liquid with deionized water, recording acid anhydride-grafted rate is 48.4%, by the vacuum-drying 24 hours at 70 ℃ of the modified-cellulose of gained, 50g NaOH is joined in 800g deionized water, stir at normal temperatures, then add 100g urea and 50g thiocarbamide, high-speed stirring obtains transparent uniform double solvents, 150g modified-cellulose is added in double solvents while stirring, after mixing 30min, obtain uniform cellulose suspension, join in the twin screw extruder that precooling is good, twin screw rotating speed is 230rpm/min, length-to-diameter ratio is 1: 35, cross-head pressure is 3MPa, vacuum pump pressure is 0.8MPa, each section of temperature is: first paragraph :-12 ℃, second segment :-8 ℃, the 3rd section :-4 ℃, the 4th section: 0 ℃, head: 0 ℃, after twin screw extruder dissolves, obtain uniform cellulose solution, cellulose concentration is 15wt%, and viscosity is 620PaS.
Embodiment 2:
The vacuum-drying 24h at 70 ℃ by Mierocrystalline cellulose and maleic anhydride, by Mierocrystalline cellulose 15wt%, [BMIM] Cl60wt% and maleic anhydride 35wt% add homogenizer to mix, the mixture of gained is reacted to 1h at 100 ℃ under the microwave irradiation of power 800w, products therefrom is washed away to ionic liquid with deionized water, recording acid anhydride-grafted rate is 32.5%, by the vacuum-drying 24 hours at 70 ℃ of the modified-cellulose of gained, 80gNaOH is joined in 770g deionized water, stir at normal temperatures, then add 100g urea and 50g thiocarbamide, high-speed stirring obtains transparent uniform double solvents, 200g modified-cellulose is added in double solvents while stirring, after mixing 30min, obtain uniform cellulose suspension, join in the twin screw extruder that precooling is good, twin screw rotating speed is 250rpm/min, length-to-diameter ratio is: 1: 40, cross-head pressure is 0.9MPa, vacuum pump pressure is 4MPa, each section of temperature is: first paragraph :-12 ℃, second segment :-6 ℃, the 3rd section: 0 ℃, the 4th section: 2 ℃, head: 5 ℃, after twin screw extruder dissolves, obtain uniform cellulose solution, cellulose concentration is 20wt%, and viscosity is 710PaS.
Embodiment 3:
The vacuum-drying 24h at 70 ℃ by Mierocrystalline cellulose and Tetra hydro Phthalic anhydride, by Mierocrystalline cellulose 20wt%, [EMIM] Ac 60wt% and Tetra hydro Phthalic anhydride 20wt% add homogenizer to mix, the mixture of gained is reacted to 1h at 120 ℃ under the microwave irradiation of power 1000w, products therefrom is washed away to ionic liquid with deionized water, recording acid anhydride-grafted rate is 10.9%, by the vacuum-drying 24 hours at 70 ℃ of the modified-cellulose of gained, 100g NaOH is joined in 700g deionized water, stir at normal temperatures, then add 150g urea and 50g thiocarbamide, high-speed stirring obtains transparent uniform double solvents, 180g modified-cellulose is added in double solvents while stirring, after mixing 30min, obtain uniform cellulose suspension, join in the twin screw extruder that precooling is good, twin screw rotating speed is 300rpm/min, length-to-diameter ratio is: 1: 55, cross-head pressure is 5MPa, vacuum pump pressure is 1MPa, each section of temperature is: first paragraph :-6 ℃, second segment :-2 ℃, the 3rd section: 0 ℃, the 4th section: 2 ℃, head: 5 ℃, after twin screw extruder dissolves, obtain uniform cellulose solution, cellulose concentration is 18wt%, and viscosity is 890PaS.
The step that the inventive method is prepared acid anhydrides microwave modification Mierocrystalline cellulose and dissolution in low temperature thereof is simple, needs solvent low price, and high-shear dissolution is easy to implement the method continuously, and the cellulose solution solid content of preparation improves, and can obviously prepare good cellulose spin dope.
Claims (9)
1. the dissolving method of Mierocrystalline cellulose after acid anhydrides microwave modification, is characterized in that, concrete steps comprise:
Step 1: by Mierocrystalline cellulose and the vacuum-drying of acid anhydrides small molecules;
Step 2: the raw material that comprises Mierocrystalline cellulose, ionic liquid and acid anhydrides small molecules is mixed by the proportioning of 10-20%: 50-70%: 20-40%;
Step 3: the mixture of step 2 gained after reacting by heating certain hour, is obtained to anhydride modified Mierocrystalline cellulose after product is washed, is dried under microwave irradiation;
Step 4: the anhydride modified Mierocrystalline cellulose of step 3 gained is joined in the double solvents that comprises sodium hydroxide, urea, thiocarbamide and water, mix rear feeding twin screw extruder, extrude at-12-6 ℃, obtain anhydride modified cellulose solution.
2. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the microwave irradiation power in described step 3 is 500w-1000w, and Heating temperature is 80 ℃-120 ℃, and the reaction times is 0.5-3h.
3. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the anhydride modified cellulosic acid anhydride-grafted rate in described step 3 is at 10-50%.
4. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the Mierocrystalline cellulose in described step 1 is common cotton fiber, and the polymerization degree is at 300-600.
5. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the ionic liquid in described step 2 is at least one in 1-butyl-3-Methylimidazole villaumite and 1-ethyl-3-methylimidazole acetate.
6. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the acid anhydrides small molecules in described step 1 is at least one in acetic anhydride, maleic anhydride and Tetra hydro Phthalic anhydride.
7. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the double solvents in described step 4 is comprised of sodium hydroxide 5-10wt%, urea 5-15wt%, thiocarbamide 5-15wt% and deionized water 70-80wt%.
8. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, is characterized in that, the concentration of the anhydride modified Mierocrystalline cellulose in described step 4 in low temperature double solvents is 15-20%.
9. the dissolving method of Mierocrystalline cellulose as claimed in claim 1 after acid anhydrides microwave modification, it is characterized in that, in described step 4, the screw speed of twin screw extruder is 200-400rpm, and twin screw length-to-diameter ratio is 1: 35-1: 55, and cross-head pressure is 3-5MPa, vacuum pump pressure is 0.8-1MPa, each section of temperature is: first paragraph :-12～-6 ℃, and second segment :-8～-2 ℃, the 3rd section :-4～2 ℃, the 4th section: 0～5 ℃, head: 0～5 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562632A (en) * | 2015-01-12 | 2015-04-29 | 哈尔滨工业大学 | Method for preparing heavy metal ion exchange fibers by virtue of roundpod jute capable of being modified by microwave and application |
| CN105220475A (en) * | 2015-10-10 | 2016-01-06 | 江南大学 | A kind of COTTON FABRIC hydrophobic finishing method based on acetic anhydride-esters of acrylic acid-electron beam technology |
| CN105803556A (en) * | 2016-03-31 | 2016-07-27 | 东华大学 | Cellulose diacetate grafted copolymer capable of achieving melt spinning and preparation method thereof |
| CN109897554A (en) * | 2018-06-27 | 2019-06-18 | 湖北工业大学 | The modified assembling type outer wall plate splicing seams of Cellulose nanocrystal are bonded and sealed material |
| CN111393717A (en) * | 2020-03-10 | 2020-07-10 | 宝兴精密(深圳)有限公司 | Degradable plastic and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290503A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Process and devices for chemical modification of cellulose and for continuous low temperature solution spinning |
-
2014
- 2014-07-01 CN CN201410309653.8A patent/CN104045839A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290503A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Process and devices for chemical modification of cellulose and for continuous low temperature solution spinning |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562632A (en) * | 2015-01-12 | 2015-04-29 | 哈尔滨工业大学 | Method for preparing heavy metal ion exchange fibers by virtue of roundpod jute capable of being modified by microwave and application |
| CN104562632B (en) * | 2015-01-12 | 2016-08-24 | 哈尔滨工业大学 | A kind of microwave quickly modified Corchorus olitorius L. prepares method and the application of heavy metal ion exchange fiber |
| CN105220475A (en) * | 2015-10-10 | 2016-01-06 | 江南大学 | A kind of COTTON FABRIC hydrophobic finishing method based on acetic anhydride-esters of acrylic acid-electron beam technology |
| CN105803556A (en) * | 2016-03-31 | 2016-07-27 | 东华大学 | Cellulose diacetate grafted copolymer capable of achieving melt spinning and preparation method thereof |
| CN105803556B (en) * | 2016-03-31 | 2018-06-26 | 东华大学 | A kind of cellulose diacetate graft copolymer of melt-spinnable and preparation method thereof |
| CN109897554A (en) * | 2018-06-27 | 2019-06-18 | 湖北工业大学 | The modified assembling type outer wall plate splicing seams of Cellulose nanocrystal are bonded and sealed material |
| CN109897554B (en) * | 2018-06-27 | 2021-01-12 | 湖北工业大学 | Cellulose nanocrystalline modified assembled external wall panel splicing seam bonding sealing material |
| CN111393717A (en) * | 2020-03-10 | 2020-07-10 | 宝兴精密(深圳)有限公司 | Degradable plastic and preparation method thereof |
| CN111393717B (en) * | 2020-03-10 | 2022-05-10 | 宝兴精密(深圳)有限公司 | Degradable plastic and preparation method thereof |
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