CN108070109A - A kind of method for the processing performance and/or mechanical property for improving low polymerization degree cellulosic material - Google Patents
A kind of method for the processing performance and/or mechanical property for improving low polymerization degree cellulosic material Download PDFInfo
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Abstract
The invention discloses a kind of methods for the processing performance and/or mechanical property for improving low polymerization degree cellulosic material.It is using the blend of high polymerization degree cellulosic material and low polymerization degree cellulosic material as raw material that the present invention, which improves the processing performance of low polymerization degree cellulosic material and/or the method for mechanical property,.The present invention can improve the processing performance and mechanical property of low polymerization degree cellulosic material simultaneously, have many advantages, such as that simple for process, pollution-free, energy consumption is small.In the case where using ionic liquid as cellulose solvent, ion liquid solvent synthetic method used is simple, cheap, nontoxic, while solvent recovery is easy, safe.By adding in a small amount of high polymerization degree cellulosic component, the processing performance (film forming and fibre forming property) of cellulose solution is significantly better than low polymerization degree cellulose solution, and the regenerated celulose fibre or thin film strength further obtained is significantly better than the regenerated celulose fibre or film prepared with low polymerization degree cellulosic material.
Description
Technical field
The present invention relates to a kind of methods for the processing performance and/or mechanical property for improving low polymerization degree cellulosic material, relate to
And natural polymer manufacture field.
Background technology
With the drastically exhaustion increasingly sharpened with petroleum-based energy of global problem of environmental pollution, with natural reproducible resource
Research for the high molecular material of raw material is rapidly developed.Cellulose is natural polymer the abundantest on the earth, be easy to get,
It is renewable, while have many advantages, such as cheap, degradable and pollution is not generated to ecological environment.Cellulosic-based material is extensive at present
Applied to traditional industries such as plastics, textile and papers, and in food, chemical industry, daily necessities, medicine, building, oilfield chemistry and biology
Chemical field has obtained important application.It is contemplated that in the future days, cellulosic material will improve the ecological environment, carry
All various aspects such as high human life quality, Development of Novel material are played an important role.
In process of manufacture, in order to ensure the performance of material of regenerated cellulose, cellulosics generally use is high-purity
The cellulose of degree and high polymerization degree is prepared for raw material, including the fiber degree of polymerization such as wood pulps, Cotton Pulp 600~800
Plain raw material.The superior regenerated cellulosics of performance can also use the cellulosic material of more high polymerization degree in order to obtain, including
Cellulosic material of the degree of polymerization more than 1000 including high-quality wood pulps, cotton linter etc..The cellulose of these high polymerization degrees
There are the shortcomings of production cost is high, raw material growth cycle is long for raw material.However, in the production and living of people, also there is a large amount of
The cellulose of cheap low polymerization degree, including the cellulose (polymerization in microcrystalline cellulose (degree of polymerization 220), straw
280) and the waste and old cellulose (degree of polymerization 260) containing in wollen fabrics etc. degree.Since the degree of polymerization of these celluloses is relatively low, cause
Relatively low as material of regenerated cellulose performance made from raw material using it, this severely limits the uses of low polymerization degree cellulose.It takes
Effective ways have important Practical significance and economic value using low polymerization degree cellulosic material.
The content of the invention
The object of the present invention is to provide a kind of processing performances and/or mechanical property for improving low polymerization degree cellulosic material
Method, the i.e. present invention are by by the cellulosic material of a small amount of high polymerization degree (degree of polymerization is typically larger than 1300) and low polymerization degree
Cellulosic material is used together, and can significantly improve the processing performance (film forming and fibre forming property) and again of gained cellulose solution
The mechanical property of raw cellulose fibre or RCF regenerated cellulose film, therefore can be simply and effectively fine by low polymerization degree by the present invention
The plain raw material of dimension prepares high performance material of regenerated cellulose..
It is provided by the present invention improve low polymerization degree cellulosic material processing performance and/or mechanical property method, be
The low polymerization degree fiber is prepared using the blend of high polymerization degree cellulosic material and low polymerization degree cellulosic material as raw material
Cellulosic material.
In above-mentioned method, the degree of polymerization (cupri ethylene diamine method measure) of the high polymerization degree cellulosic material can be 1300~
4000, concretely 1500~3500,1500,2400 or 3500；
The high polymerization degree cellulosic material can be wood pulps, Cotton Pulp, bamboo pulp, cotton linter and bacteria cellulose raw material
At least one of.
In above-mentioned method, the degree of polymerization (cupri ethylene diamine method measure) of the low polymerization degree cellulosic material can be 150~
300, concretely 220~280,220,260 or 280；
The low polymerization degree cellulosic material can be microcrystalline cellulose, cellulose made from straw and waste and old contain cotton spinning
At least one of cellulosic material made from fabric.
In above-mentioned method, the mass ratio of the high polymerization degree cellulosic material and the low polymerization degree cellulosic material can
For 1：4~8, concretely 1：4、1：5、1：7 or 1：8.
In above-mentioned method, make after the high polymerization degree cellulosic material and the low polymerization degree cellulosic material are crushed
With effect is more preferable.
In above-mentioned method, described method includes following steps：The blend is dissolved in solvent obtains fiber through dissolving
Plain solution；
The processing performance (film forming and fibre forming property) of the cellulose solution is significantly better than low polymerization degree cellulose solution；
The solvent can be N-methyl morpholine oxide aqueous solution (NMMO), ionic liquid or ionic liquid and N, N- diformazan
The mixed liquor of at least one of base sulfoxide and N,N-dimethylformamide；
The ionic liquid can be 1- ethyl-3-methylimidazoles villaumite (EMIMCl), 1- propyl -3- methylimidazole villaumites,
1- butyl -3- methylimidazole villaumites (PMIMCl), 1- pi-allyl -3- methylimidazole villaumites (BMIMCl), 1- methacrylics -3-
Methylimidazole villaumite (mAMIMCl), 1- ethyl-3-methylimidazoles acetate (EMIMAc), 1- propyl -3- methylimidazole acetate
(PMIMAc), 1- butyl -3- methylimidazoles acetate (BMIMAc), 1- pi-allyl -3- methylimidazoles acetate (AMIMAc) and
At least one of 1- methacrylic -3- methylimidazoles acetate (mAMIMAc).
In above-mentioned method, the mass percent concentration of the cellulose solution can be 5~20%, concretely 5~
18%th, 5~16%, 5~10%, 5~9%, 5%, 6%, 9%, 10%, 16%, 18% or 20%.
In above-mentioned method, the temperature of the dissolving can be 25~100 DEG C, concretely 80~90 DEG C, 80 DEG C or 90 DEG C.
In above-mentioned method, the method is further included is prepared into regenerated celulose fibre or regeneration by the cellulose solution
The step of cellophane；
The intensity of the regenerated celulose fibre or the RCF regenerated cellulose film is significantly better than with low polymerization degree cellulose
Regenerated celulose fibre or film prepared by raw material or even close to regenerated celulose fibre made from high polymerization degree cellulosic material
Or thin film strength.
In above-mentioned method, the cellulose solution is molded fine up to the regenerated cellulose through spinning and coagulating bath successively
Dimension；
The cellulose solution is molded through spraying film and coagulating bath up to the RCF regenerated cellulose film successively；
The coagulating bath that the coagulating bath shaping uses can be water and/or ethyl alcohol, when using the mixture of water and ethyl alcohol,
The weight ratio of middle water and ethyl alcohol is 95：5~50：50, concretely 80：20.
The molding temperature of coagulating bath is 25~90 DEG C, concretely 25~40 DEG C, 25 DEG C, 35 DEG C or 40 DEG C.
In above-mentioned method, the recyclable recycling of solvent can be by multiple-effect evaporation, UF membrane or that saltouts do
Method recycles.
The method of the present invention can improve the processing performance and mechanical property of low polymerization degree cellulosic material simultaneously, have technique
Simply, pollution-free, the advantages that energy consumption is small.In the case where using ionic liquid as cellulose solvent, ionic liquid used
Dissolvent synthesis method is simple, cheap, nontoxic, while solvent recovery is easy, safe.It is a small amount of high poly- by adding in
DP cellulose component, it is molten that the processing performance (film forming and fibre forming property) of cellulose solution is significantly better than low polymerization degree cellulose
Liquid；By spinning or the processing such as spray film process, coagulating bath shaping, washing, dry, obtained regenerated celulose fibre or film
Intensity is significantly better than with the regenerated celulose fibre of low polymerization degree cellulosic material preparation or film or even fine close to high polymerization degree
Regenerated celulose fibre or thin film strength made from the plain raw material of dimension.So as to greatly expand the use of low polymerization degree cellulose
Scope improves the utilization rate of low polymerization degree cellulose.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1,
The low polymerization degree cellulosic material of selection is microcrystalline cellulose, and the degree of polymerization is measured as 220 by cupri ethylene diamine method,
The high polymerization degree cellulosic material of selection is wood pulps, and the degree of polymerization is measured as 1500 by cupri ethylene diamine method.18.8g is weighed to do
Dry EMIMCl ionic liquids, the microcrystalline cellulose of 1.0g dryings and the wood pulps of 0.2g dryings, are stirred mixed at 90 DEG C
It closes.About after sixty minutes, the brown yellow solution of clear is formed, with being black in the polarized light microscope observing visual field, illustrates fibre
Dimension element is completely dissolved, and the cellulose solution that concentration is 6.0wt%, high polymerization degree and low polymerization degree cellulose weight ratios are thus made
For 1：5.After cellulose mixture solution deaeration 120 minutes, draft flowing deformation test, composite fibre are carried out to cellulose mixture solution
The rupture time of plain solution liquid bridge is 10s.Cellulose mixture solution is uniformly layered on glass pane surface, is put into water as coagulating bath
Coagulation tank in, temperature be 25 DEG C.It is dry by washing, it is thin to obtain the regenerated cellulose containing a small amount of high polymerization degree cellulose
Film, tensile strength 80MPa, elongation at break 15%.The water in coagulating bath is evaporated, the EMIMCl being recycled is molten
Agent.
Comparative example 1,
The low polymerization degree cellulosic material of selection is microcrystalline cellulose, and the degree of polymerization is measured as 220 by cupri ethylene diamine method,
The EMIMCl ionic liquids of 18.8g dryings are weighed, the microcrystalline cellulose of 1.2g dryings is stirred mixing at 90 DEG C.About 60
After minute, the brown yellow solution of clear is formed, with being black in the polarized light microscope observing visual field, illustrates that cellulose is complete
Thus the cellulose solution that concentration is 6.0wt% is made in dissolving.It is fine to crystallite after microcrystalline cellulose solution deaeration 120 minutes
The plain solution of dimension carries out draft flowing deformation test, and the rupture time of cellulose solution liquid bridge is 0.4s.Microcrystalline cellulose solution is uniform
Glass pane surface is layered on, is put into water as in the coagulation tank of coagulating bath, temperature is 25 DEG C.It is dry by washing, it is fine to obtain regeneration
The plain film of dimension, extension test is carried out to microcrystalline cellulose film, and microcrystalline cellulose film is easy to crush in test process, draws
Intensity is stretched for 40MPa, elongation at break 5%.The water in coagulating bath is evaporated, the EMIMCl solvents being recycled.
Embodiment 2,
The low polymerization degree cellulosic material of selection is cellulose made from wheat stalk, and the degree of polymerization passes through cupri ethylene diamine method
280 are measured as, the high polymerization degree cellulosic material of selection is cotton linter, and the degree of polymerization is measured as 3500 by cupri ethylene diamine method,
The PMIMCl ionic liquids of 18.0g dryings are weighed, the cotton of cellulose and 0.4g dryings made from the wheat stalk of 1.6g dryings is short
Suede is stirred mixing at 80 DEG C.About after sixty minutes, the brown yellow solution of clear is formed, uses polarized light microscope observing
It is black in the visual field, illustrates that cellulose is completely dissolved, the cellulose solution that concentration is 10.0wt%, high polymerization degree is thus made
It is 1 with low polymerization degree cellulose weight ratios：4.After cellulose mixture solution deaeration 120 minutes, to cellulose mixture solution into
Row draft flowing deformation is tested, and the rupture time of cellulose mixture solution liquid bridge is 41s.Cellulose mixture solution is set in small-sized spinning
The spinning by way of wet spinning on standby.Orifice diameter is 100 μm, and for water as coagulating bath, temperature is 40 DEG C.By drawing-off, water
It washes, drawing-off, dries, obtain the regenerated celulose fibre containing a small amount of high polymerization degree cellulose, fibre strength 5.2cN/tex.
The water in coagulating bath is evaporated, the PMIMCl solvents being recycled.
Comparative example 2,
The low polymerization degree cellulosic material of selection is cellulose made from wheat stalk, and the degree of polymerization passes through cupri ethylene diamine method
280 are measured as, weighs the PMIMCl ionic liquids of 18.0g dryings, cellulose made from the wheat stalk of 2g dryings, at 80 DEG C
It is stirred mixing.About after sixty minutes, the brown yellow solution of clear is formed, is black in the polarized light microscope observing visual field
Color illustrates that cellulose is completely dissolved, and the cellulose solution that concentration is 10.0wt% is thus made.By cellulose solution deaeration 120
After minute, draft flowing deformation test is carried out to cellulose solution made from wheat stalk, the rupture time of cellulose solution liquid bridge is
1.2s.The spinning by way of wet spinning on small-sized spinning equipment by cellulose solution made from wheat stalk.Orifice diameter
For 100 μm, for water as coagulating bath, temperature is 40 DEG C.Since continuous regenerated celulose fibre can not be obtained, it is fine it is not measured
Tie up intensity.The water in coagulating bath is evaporated, the PMIMCl solvents being recycled.
Embodiment 3,
For the low polymerization degree cellulosic material of selection to be waste and old containing cellulose made from cotton-spinning fabric, the degree of polymerization passes through copper second
Diamines method is measured as 260, and the high polymerization degree cellulosic material of selection is bamboo pulp, and the degree of polymerization is measured as by cupri ethylene diamine method
2400, weigh the NMMO/H of 16.8g2O solvents, the waste and old of 2.8g dryings are dried containing cellulose made from cotton-spinning fabric and 0.4g
Bamboo pulp is stirred mixing at 90 DEG C.About after sixty minutes, the cellulose solution that concentration is 16wt%, Gao Ju is thus made
Right and low polymerization degree cellulose weight ratios are 1：7.It is molten to cellulose mixture after cellulose mixture solution deaeration 120 minutes
Liquid carries out draft flowing deformation test, pure waste and old containing cellulose solution, cellulose mixture made from cotton-spinning fabric compared to same concentrations
The rupture time of solution liquid bridge increases to 48s by 1.5.Cellulose mixture solution is uniformly layered in polytetrafluoro mold, adds in water
As solidification liquid, temperature is 35 DEG C.It is dry by washing, it is thin to obtain the regenerated cellulose containing a small amount of high polymerization degree cellulose
Film, compared to the pure waste and old slim film of regenerated cellulose being prepared containing cellulose made from cotton-spinning fabric for raw material, containing a small amount of
The RCF regenerated cellulose film tensile strength of high polymerization degree cellulose is increased to 97MPa by 50MPa, and elongation at break is improved by 7%
To 19%.Evaporate most of water in coagulating bath, the NMMO/H being recycled2O solvents.
Embodiment 4,
The low polymerization degree cellulosic material of selection is microcrystalline cellulose, and the degree of polymerization is measured as 220 by cupri ethylene diamine method,
The high polymerization degree cellulosic material of selection is cotton linter, and the degree of polymerization is measured as 3500 by cupri ethylene diamine method, weighs 18.0g and do
Dry BMIMAc ionic liquids, the microcrystalline cellulose of 0.8g dryings and the cotton linter of 0.2g dryings, are stirred mixed at 90 DEG C
It closes.About after sixty minutes, the brown yellow solution of clear is formed, with being black in the polarized light microscope observing visual field, illustrates fibre
Dimension element is completely dissolved, and the cellulose solution that concentration is 5.0wt%, high polymerization degree and low polymerization degree cellulose weight ratios are thus made
For 1：4.After cellulose mixture solution deaeration 120 minutes, draft flowing deformation test is carried out to cellulose mixture solution, compared to identical
The microcrystalline cellulose solution of concentration, the rupture time of cellulose mixture solution liquid bridge increase to 22s by 0.3s.Mixed solution is equal
It is even to be layered on glass pane surface, ethyl alcohol is put into as in the coagulation tank of coagulating bath, and temperature is 25 DEG C.It is dry by washing, contained
There is the RCF regenerated cellulose film of a small amount of high polymerization degree cellulose, be the regenerated fiber that raw material is prepared compared to pure microcrystalline cellulose
The slim film of element, the RCF regenerated cellulose film tensile strength containing a small amount of high polymerization degree cellulose are increased to 120MPa by 42MPa, break
It splits elongation and is increased to 18% by 5%.The water in coagulating bath is evaporated, the BMIMAc solvents being recycled.
Embodiment 5,
The low polymerization degree cellulosic material of selection is cellulose made from wheat stalk, and the degree of polymerization passes through cupri ethylene diamine method
280 are measured as, the high polymerization degree cellulosic material of selection is bamboo pulp, and the degree of polymerization is measured as 2400 by cupri ethylene diamine method,
The BMIMAc/DMF mixed solvents of 16.4g dryings are weighed, cellulose and 0.6g are dried made from the wheat stalk of 3.0g dryings
Bamboo pulp is stirred mixing at 90 DEG C.About after sixty minutes, the brown yellow solution of clear is formed, uses petrographic microscope
It is black in field of view, illustrates that cellulose is completely dissolved, the cellulose solution that concentration is 18.0wt%, Gao Ju is thus made
Right and low polymerization degree cellulose weight ratios are 1：5.It is molten to cellulose mixture after cellulose mixture solution deaeration 120 minutes
Liquid carries out draft flowing deformation test, compared to cellulose solution made from the wheat stalk of same concentrations, cellulose mixture solution liquid bridge
Rupture time 55s is increased to by 2.1s.Mixed solution is uniformly layered on glass pane surface, is put into water and alcohol mixeding liquid conduct
In the coagulation tank of coagulating bath, the weight ratio of water and ethyl alcohol is 80:20, temperature is 25 DEG C.It is dry by washing, it obtains containing few
The RCF regenerated cellulose film of high polymerization degree cellulose is measured, is prepared again for raw material compared to cellulose made from pure wheat stalk
Raw cellulose fiber film, the RCF regenerated cellulose film tensile strength containing a small amount of high polymerization degree cellulose are increased to by 53MPa
105MPa, ethyl alcohol and DMF, the BMIMAc solvents being recycled.
Embodiment 6,
The low polymerization degree cellulosic material of selection is microcrystalline cellulose, and the degree of polymerization is measured as 220 by cupri ethylene diamine method,
The high polymerization degree cellulosic material of selection is wood pulps, and the degree of polymerization is measured as 1500 by cupri ethylene diamine method, weighs 18.2g and do
Dry AMIMCl ionic liquids, the microcrystalline cellulose of 1.6g dryings and the wood pulps of 0.2g dryings, are stirred mixed at 90 DEG C
It closes.About after sixty minutes, the brown yellow solution of clear is formed, with being black in the polarized light microscope observing visual field, illustrates fibre
Dimension element is completely dissolved, and the cellulose solution that concentration is 9.0wt%, high polymerization degree and low polymerization degree cellulose weight ratios are thus made
For 1：8.After cellulose mixture solution deaeration 120 minutes, draft flowing deformation test is carried out to cellulose mixture solution, compared to identical
The microcrystalline cellulose solution of concentration, the rupture time of cellulose mixture solution liquid bridge increase to 40s by 1.3s.By cellulose mixture
Solution is in the spinning by way of wet spinning on small-sized spinning equipment.Orifice diameter is 100 μm, and water is as coagulating bath, temperature
For 40 DEG C.By drawing-off, washing, drawing-off dries, obtains the regenerated celulose fibre containing a small amount of high polymerization degree cellulose, and
Pure microcrystalline cellulose can not obtain continuous regenerated celulose fibre element, the regeneration containing a small amount of high polymerization degree cellulose for raw material
The fibre strength of cellulose fibre is 4.5cN/tex.The water in coagulating bath is evaporated, the AMIMCl solvents being recycled.
Embodiment 7
For the low polymerization degree cellulosic material of selection to be waste and old containing cellulose made from cotton-spinning fabric, the degree of polymerization passes through copper second
Diamines method is measured as 260, and the high polymerization degree cellulosic material of selection is cotton linter, and the degree of polymerization is measured as by cupri ethylene diamine method
3500, weigh the mAMIMAc ionic liquids of 14.0g dryings, 5.0g dryings it is waste and old containing cellulose made from cotton-spinning fabric and
The cotton linter of 1.0g dryings, is stirred mixing at 90 DEG C.About after sixty minutes, the brown yellow solution of clear is formed, is used
It is black in the polarized light microscope observing visual field, illustrates that cellulose is completely dissolved, the fiber that concentration is 20.0wt% is thus made
Plain solution, high polymerization degree are 1 with low polymerization degree cellulose weight ratios：5.After cellulose mixture solution deaeration 120 minutes, to mixed
Condensating fiber element solution carries out draft flowing deformation test, pure waste and old containing cellulose solution made from cotton-spinning fabric compared to same concentrations,
The rupture time of cellulose mixture solution liquid bridge increases to 60s by 2.5s.Cellulose mixture solution is uniformly layered on polytetrafluoro mould
In tool, water is added in as solidification liquid, temperature is 25 DEG C.It is dry by washing, it obtains containing a small amount of high polymerization degree cellulose again
Raw cellophane, it is waste and old slim for the regenerated cellulose that raw material is prepared containing cellulose made from cotton-spinning fabric compared to pure
Film, the RCF regenerated cellulose film tensile strength containing a small amount of high polymerization degree cellulose are increased to 101MPa, extension at break by 52MPa
Rate is increased to 20% by 6%.The water in coagulating bath is evaporated, the mAMIMAc solvents being recycled.
Claims (10)
- A kind of 1. method for the processing performance and/or mechanical property for improving low polymerization degree cellulosic material, it is characterised in that：By height The blend of degree of polymerization cellulosic material and low polymerization degree cellulosic material prepares the low polymerization degree fiber material as raw material Material.
- 2. according to the method described in claim 1, it is characterized in that：The degree of polymerization of the high polymerization degree cellulosic material is 1300 ~4000；The high polymerization degree cellulosic material be wood pulps, Cotton Pulp, bamboo pulp, cotton linter and bacteria cellulose raw material at least It is a kind of.
- 3. method according to claim 1 or 2, it is characterised in that：The degree of polymerization of the low polymerization degree cellulosic material is 150~300；The low polymerization degree cellulosic material is microcrystalline cellulose, cellulose made from straw and waste and old contains wollen fabrics system At least one of cellulosic material obtained.
- 4. method according to any one of claim 1-3, it is characterised in that：The high polymerization degree cellulosic material and institute The mass ratio for stating low polymerization degree cellulosic material is 1：4~8.
- 5. according to the described method of any one of claim 1-4, it is characterised in that：Described method includes following steps：It is described Blend is dissolved in solvent obtains cellulose solution through dissolving；The solvent is N-methyl morpholine oxide aqueous solution, ionic liquid or ionic liquid and N, N- dimethyl sulfoxide (DMSO) and N, N- The mixed liquor of at least one of dimethylformamide；The ionic liquid is 1- ethyl-3-methylimidazoles villaumite, 1- propyl -3- methylimidazole villaumites, 1- butyl -3- methyl miaows Azoles villaumite, 1- pi-allyl -3- methylimidazole villaumites, 1- methacrylic -3- methylimidazole villaumites, 1- ethyl-3-methylimidazoles Acetate, 1- propyl -3- methylimidazoles acetate, 1- butyl -3- methylimidazoles acetate, 1- pi-allyl -3- methylimidazole vinegar At least one of hydrochlorate and 1- methacrylic -3- methylimidazole acetate.
- 6. according to the method described in claim 5, it is characterized in that：The mass percent concentration of the cellulose solution for 5~ 20%.
- 7. method according to claim 5 or 6, it is characterised in that：The temperature of the dissolving is 25~100 DEG C.
- 8. according to the method any one of claim 5-7, it is characterised in that：The method is further included the cellulose Solution is prepared into the step of regenerated celulose fibre or RCF regenerated cellulose film.
- 9. according to the method described in claim 8, it is characterized in that：The cellulose solution is molded successively through spinning and coagulating bath Up to the regenerated celulose fibre；The cellulose solution is molded through spraying film and coagulating bath up to the RCF regenerated cellulose film successively.
- 10. low polymerization degree cellulosic material prepared by method any one of claim 1-9.
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