CN105037749A - Cellulose solution and preparation method thereof - Google Patents
Cellulose solution and preparation method thereof Download PDFInfo
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- CN105037749A CN105037749A CN201510416141.6A CN201510416141A CN105037749A CN 105037749 A CN105037749 A CN 105037749A CN 201510416141 A CN201510416141 A CN 201510416141A CN 105037749 A CN105037749 A CN 105037749A
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Abstract
The invention discloses a cellulose solution and a preparation method thereof. The cellulose solution comprises the following components, by weight: 5.5-6.5% of degraded cellulose pulp, 7.5-8.5% of sodium hydroxide, and 0.8-0.9% of zinc oxide, with the balance being water. The cellulose solution is prepared through adding cellulose pulp, sodium hydroxide, and zinc oxide into water, and performing stirring. According to the invention, defects that the cellulose sulfonate method produces severe pollution; a solvent in the organic solvent NNMO method is difficult to recycle, and cost of the organic solvent NNMO method is high; and the cellulose solubility is low in the ionic liquid method are overcome in the prior art. The preparation method of the cellulose solution is mild in condition and is environment-friendly without pollution.
Description
Technical field
The invention belongs to textile industry material technology field, be specifically related to a kind of cellulose solution and preparation method thereof.
Background technology
Mierocrystalline cellulose is a kind of reproducible Biological resources be made up of glucose that the earth extensively exists, fewer and feweri along with Nonrenewable energy resources such as oil, and the mankind are to the active demand of resource, cellulosic exploitation and use are more and more caused to the concern of people, relevant research also gets more and more, and is especially that the regenerated cellulose fibre of raw material production has greatly catered to consumer demand with its excellent quality with Mierocrystalline cellulose.But due to the structure that Mierocrystalline cellulose is special, pile up closely as having in very strong molecule with intermolecular hydrogen bonding, molecular structure, be difficult to melt-processed, common solvent is also difficult to dissolve, cause being that the technique of raw material production regenerated cellulose fibre is also not general with Mierocrystalline cellulose, early stage research mainly contains viscose process and cuprammonium process, but all there is the problem defect of environmental protection and cost, never come by popularization.
In recent years, along with cellulose prods is more and more subject to liking of people, relevant research also gets more and more, the especially research of novel dissolvent.
Method disclosed in Chinese patent CN89106762.0 be a kind of with N-methylmorpholine N-oxide compound for cellulose solution method prepared by solvent, the cellulose solution that the method prepares is uniform and stable and have good viscosity, there is good spinning properties, be successfully applied in production practice, simultaneously this solvent also have environmental protection can 100% reclaim feature.But due to the restriction of technology, the cost of current solvent recuperation is very expensive, and hence, limit the popularization of the method.
Method disclosed in Chinese patent CN200710063741.4 is the mixing solutions of a kind of imidazole type ion liquid and organic solvent is the method that cellulose solution prepared by solvent, this system intermediate ion liquid is a kind of comparatively stable and solvent that solubility property is extremely strong, also there is the features such as high temperature resistant easy recovery simultaneously, utilize the cellulose solution of the method stable in properties.But need the solubility property that will improve ionic liquid further improved, also need the production cost reducing its costliness further simultaneously.
A kind of method disclosed in Chinese patent CN200810038024.0 is a kind of at room temperature in the method for the mixed system dissolving cellulos of sodium hydroxide, thiocarbamide, urea and water.The feature of the method at room temperature just can obtain the higher cellulose solution of solid content, also has good strainability simultaneously.But it is limited that the method also exists dissolving power, and high/low temperature easily forms irreversible gel.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and provide a kind of cellulose solution and preparation method thereof, this preparation method is environment friendly and pollution-free, mild condition, and cost is low.
A kind of cellulose solution, is made up of the following component according to weight percent meter: cellulose degradation slurry cypress 5.5 ~ 6.5%, sodium hydroxide 7.5 ~ 8.5%, zinc oxide 0.8 ~ 0.9%, and all the other are water;
Described cellulose degradation slurry cypress prepares by the following method: first pulverized by cellulose pulp, add in water, obtain suspension, then add cellulase reaction, after washing, suction filtration, oven dry, to obtain final product.
As the further improvement of foregoing invention, described cellulose pulp is the one of Cotton Pulp, bamboo pulp or wood pulps.
As the further improvement of foregoing invention, the cellulose pulp particle diameter after described pulverizing is at 100 ~ 500 orders.
As the further improvement of foregoing invention, in outstanding described supernatant liquid, the massfraction of cellulose pulp is 5%.
As the further improvement of foregoing invention, described cellulase is powdery, and enzyme work is at 100000 ~ 150000u/mg, and its consumption is 1 ~ 5% of cellulose pulp quality.
As the further improvement of foregoing invention, the temperature of cellulase reaction is 45 ~ 50 DEG C, and the time is 3 ~ 5h, pH is 4.8 ~ 5.0.
The preparation method of above-mentioned cellulose solution, be cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, stir, to obtain final product.
As the further improvement of foregoing invention, the temperature of whipping process is 3 DEG C.
Cellulase be one group can the general name of the glucogenic enzyme of degraded cellulose, different according to the mode of action, generally cellulase can be divided into 3 classes: circumscribed β-1, 4-dextran glycosides enzyme (being called for short CBH), inscribe β-1, 4-dextran glycosides enzyme (being called for short EG) and β-1, 4-glucuroide (being called for short BG), wherein, inscribe β-1, the effect of 4-dextran glycosides enzyme is that native cellulolytic is become amorphous cellulose, circumscribed β-1, the effect of 4-dextran glycosides enzyme is continued to be hydrolyzed into cell-oligosaccharide by amorphous cellulose, β-1, the effect of 4-glucuroide is that cell-oligosaccharide is hydrolyzed into glucose.Substratspezifitaet, the ratio of each component all there are differences.Under the synergy of these 3 kinds of enzymes, Mierocrystalline cellulose is finally broken down into glucose, and the cellulase that the present invention uses is the mixture of above-mentioned three kinds of cellulases.By utilizing the characteristic deterioration Mierocrystalline cellulose of cellulase, reduce the cellulosic polymerization degree, thus improve Mierocrystalline cellulose solubility property in alkaline solution, prepare uniform and stable cellulose solution.
In order to prevent cellulase to cellulosic excessive degradation, adopting the cellulase washing in mixing solutions, avoiding the cellulase remained to make Mierocrystalline cellulose further hydrolysis reaction occur.The sodium ion of sodium hydroxide exists with the form of " hydration sodium ion " in aqueous, and radius is little, can enter between cellulosic molecule, destroys the reactive force between macromole, makes Mierocrystalline cellulose be dissolved in alkali lye.Zinc oxide, as activator, makes the activity of cellulose macromolecule chain increase, thus promotes cellulosic further dissolving.
Preparation method of the present invention avoids that cellulose sulfonate method in prior art is seriously polluted, organic solvent NNMO method difficult solvent recovery and cost intensive, the shortcoming that ionic liquid cellulose dissolution degree is low, provides the preparation method of the environment friendly and pollution-free cellulose solution of a kind of mild condition.
Embodiment
Embodiment 1
First, by the Cotton Pulp mechanical disintegration of 50g, gained slurry cypress particle diameter is at 100 ~ 500 orders; Then, the pulp after pulverizing is added in the water of 950g, after fully stirring, adds 0.5g cellulase, regulate pH to 4.8 ~ 5.0, at 45 DEG C of reaction 3h, after carry out washing, suction filtration, oven dry; Finally, be under the condition of 3 DEG C in envrionment temperature, cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, after stirring, filter, vacuum defoamation under the condition of 0 DEG C, obtain cellulose solution, in the solution configured, the massfraction of cellulose degradation slurry cypress is 5.5%, and the massfraction of sodium hydroxide is 7.5%, and the massfraction of zinc oxide is 0.8%.
The viscosity of gained cellulose solution is 750PaS.
Embodiment 2
First, by the bamboo pulp mechanical disintegration of 50g, gained slurry cypress particle diameter is at 100 ~ 500 orders; Then, the pulp after pulverizing is added in the water of 950g, after fully stirring, adds 1g cellulase, regulate pH to 4.8 ~ 5.0, at 48 DEG C of reaction 4h, after carry out washing, suction filtration, oven dry; Finally, be under the condition of 3 DEG C in envrionment temperature, cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, after stirring, filter, vacuum defoamation under the condition of 0 DEG C, obtain cellulose solution, in the solution configured, the massfraction of cellulose degradation slurry cypress is 6%, and the massfraction of sodium hydroxide is 8%, and the massfraction of zinc oxide is 0.85%.
The viscosity of gained cellulose solution is 1000PaS.
Embodiment 3
First, by the wood pulps mechanical disintegration of 50g, gained slurry cypress particle diameter is at 100 ~ 500 orders; Then, the pulp after pulverizing is added in the water of 950g, after fully stirring, adds 0.5g cellulase, regulate pH to 4.8 ~ 5.0, at 50 DEG C of reaction 5h, after carry out washing, suction filtration, oven dry; Finally, be under the condition of 3 DEG C in envrionment temperature, cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, after stirring, filter, vacuum defoamation under the condition of 0 DEG C, obtain cellulose solution, in the solution configured, the massfraction of cellulose degradation slurry cypress is 6.5%, and the massfraction of sodium hydroxide is 8.5%, and the massfraction of zinc oxide is 0.0%.
The viscosity of gained cellulose solution is 1250PaS.
Comparative example 1
The difference of the present embodiment and embodiment 2 is: the consumption of cellulase is 0.5% of cellulose pulp quality.
First, by the bamboo pulp mechanical disintegration of 50g, gained slurry cypress particle diameter is at 100 ~ 500 orders; Then, the pulp after pulverizing is added in the water of 950g, after fully stirring, adds 0.25g cellulase, regulate pH to 4.8 ~ 5.0, at 48 DEG C of reaction 4h, after carry out washing, suction filtration, oven dry; Finally, be under the condition of 3 DEG C in envrionment temperature, cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, after stirring, filter, vacuum defoamation under the condition of 0 DEG C, obtain cellulose solution, in the solution configured, the massfraction of cellulose degradation slurry cypress is 6%, and the massfraction of sodium hydroxide is 8%, and the massfraction of zinc oxide is 0.85%.
The viscosity of gained cellulose solution is 200PaS.
Comparative example 2
The difference of the present embodiment and embodiment 2 is: the consumption of cellulase is 10% of cellulose pulp quality.
First, by the bamboo pulp mechanical disintegration of 50g, gained slurry cypress particle diameter is at 100 ~ 500 orders; Then, the pulp after pulverizing is added in the water of 950g, after fully stirring, adds 5g cellulase, regulate pH to 4.8 ~ 5.0, at 48 DEG C of reaction 4h, after carry out washing, suction filtration, oven dry; Finally, be under the condition of 3 DEG C in envrionment temperature, cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, after stirring, filter, vacuum defoamation under the condition of 0 DEG C, obtain cellulose solution, in the solution configured, the massfraction of cellulose degradation slurry cypress is 6%, and the massfraction of sodium hydroxide is 8%, and the massfraction of zinc oxide is 0.85%.
The viscosity of gained cellulose solution is 3000PaS.
The viscosity size of cellulose solution determines the rheological quality of solution, and the viscosity of solution is larger, and its rheological property is poorer, and shear-stress also increases thereupon, and the spinning property of solution also decreases; The viscosity of solution is less, and its rheological property is better, and shear-stress is corresponding reduction also, and the fibre-forming performance of solution reduces.The present invention controls the degree of degradation of cellulose pulp by the consumption controlling cellulase, thus effectively controls the cellulosic polymerization degree in prepared cellulose solution, obtains desirable cellulose solution.
Claims (8)
1. a cellulose solution, is characterized in that: be made up of the following component according to weight percent meter: cellulose degradation slurry cypress 5.5 ~ 6.5%, sodium hydroxide 7.5 ~ 8.5%, zinc oxide 0.8 ~ 0.9%, and all the other are water;
Described cellulose degradation slurry cypress prepares by the following method: first pulverized by cellulose pulp, add in water, obtain suspension, then add cellulase reaction, after washing, suction filtration, oven dry, to obtain final product.
2. cellulose solution according to claim 1, is characterized in that: described cellulose pulp is the one in Cotton Pulp, bamboo pulp or wood pulps.
3. cellulose solution according to claim 1, is characterized in that: the cellulose pulp particle diameter after pulverizing is at 100 ~ 500 orders.
4. cellulose solution according to claim 1, is characterized in that: in described suspension, the massfraction of cellulose pulp is 5%.
5. cellulose solution according to claim 1, is characterized in that: described cellulase is powdery, and enzyme work is at 100000 ~ 150000u/mg, and its consumption is 1 ~ 5% of cellulose pulp quality.
6. cellulose solution according to claim 1, is characterized in that: the temperature of cellulase reaction is 45 ~ 50 DEG C, and the time is 3 ~ 5h, pH is 4.8 ~ 5.0.
7. the preparation method of cellulose solution according to claim 1, is characterized in that: cellulose degradation is starched cypress, sodium hydroxide, zinc oxide adds in water, stir, to obtain final product.
8. the preparation method of cellulose solution according to claim 8, is characterized in that: the temperature of whipping process is 3 DEG C.
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| CN201510416141.6A CN105037749A (en) | 2015-07-16 | 2015-07-16 | Cellulose solution and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106012070A (en) * | 2016-07-04 | 2016-10-12 | 浙江理工大学 | Novel slow-release antibacterial cellulose fibers and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6106763A (en) * | 1997-11-20 | 2000-08-22 | Institute Of Chemical Fibres | Process for producing cellulosic mouldings |
| CN1526318A (en) * | 2003-09-19 | 2004-09-08 | 汤兴然 | Edible cellulose preparing process and product |
| CN102037019A (en) * | 2008-05-06 | 2011-04-27 | 坦佩雷理工大学 | A method for dissolving cellulose and a cellulosic product obtained from a solution comprising dissolved cellulose |
| CN102875821A (en) * | 2012-10-10 | 2013-01-16 | 湖北天思科技股份有限公司 | Method for dissolving cellulose |
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2015
- 2015-07-16 CN CN201510416141.6A patent/CN105037749A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6106763A (en) * | 1997-11-20 | 2000-08-22 | Institute Of Chemical Fibres | Process for producing cellulosic mouldings |
| CN1526318A (en) * | 2003-09-19 | 2004-09-08 | 汤兴然 | Edible cellulose preparing process and product |
| CN102037019A (en) * | 2008-05-06 | 2011-04-27 | 坦佩雷理工大学 | A method for dissolving cellulose and a cellulosic product obtained from a solution comprising dissolved cellulose |
| CN102875821A (en) * | 2012-10-10 | 2013-01-16 | 湖北天思科技股份有限公司 | Method for dissolving cellulose |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106012070A (en) * | 2016-07-04 | 2016-10-12 | 浙江理工大学 | Novel slow-release antibacterial cellulose fibers and preparation method thereof |
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Address after: 226300 Jiangsu city of Nantong province Tongzhou District Industrial Park building sun Zhihao Applicant after: JIANGSU GOLDSUN TEXTILE TECHNOLOGY CO., LTD. Address before: 226300 Jiangsu city of Nantong province Tongzhou District Industrial Park building sun Zhihao Applicant before: Goldsun Holding Group Co., Ltd. |
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Application publication date: 20151111 |