CN110452402A - A kind of method that Mechanical Method prepares hydrophobic high permeable fiber film - Google Patents
A kind of method that Mechanical Method prepares hydrophobic high permeable fiber film Download PDFInfo
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- CN110452402A CN110452402A CN201910724350.5A CN201910724350A CN110452402A CN 110452402 A CN110452402 A CN 110452402A CN 201910724350 A CN201910724350 A CN 201910724350A CN 110452402 A CN110452402 A CN 110452402A
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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Abstract
The invention discloses a kind of methods that Mechanical Method prepares hydrophobic high permeable fiber film, belong to biomass green fiber material and environment-friendly materials field.The present invention by cellulosic material pass sequentially through enzymatic hydrolysis pretreatment, mechanical lapping and shaping and drying and etc. finally obtain hydrophobic high permeable fiber film.The cellulose membrane structure of the method for the present invention preparation is closely knit, and mechanical performance is excellent, and transparency is high, and hydrophobicity is strong, and water contact angle average value can be to 106 °, and gas permeability is up to 75.77s/ (in2·100cc·1.22KPa)；Chemicals is not used in cellulose membrane preparation process of the invention, does not need complicated chemical reaction process, without complicated technique and high equipment investment；The water contact angle of gained cellulose membrane has preferable water resistance, can use in high humidity environment up to 106 °.
Description
Technical field
The invention belongs to green fiber material and environmentally friendly micro-nano material field, specifically a kind of Mechanical Method preparation is dredged
The method of the high permeable fiber film of water.
Background technique
Cellulose is the most abundant boiomacromolecule on the earth, it is primarily present in the cell wall of higher plant.Micro-nano
Rice cellulose not only has that raw material sources are wide, intensity is high, large specific surface area, good biocompatibility, biodegradable, renewable
The advantages that recycling；Simultaneously because diameter is in a few to tens of nano-scale ranges, length in a few to tens of micro-meter scales, diameter
It is small, draw ratio is big, also have both excellent mechanical property.These significant characteristics make its potential transparent micro-nano cellulose be made
Film paper, for packing, the high-end fields such as high-temperature flexible electronic component substrate, micro-fluid chip.
However, a large amount of functional group-hydroxyls are contained on nano-cellulose surface, easily absorb water, transparent nano paper is caused to absorb water
Property it is high, direct apply in fields such as packaging, electronic device, micro-fluid chips is restricted.
Currently, cellulose nanometer film surface made from common methods has the presence of a large amount of hydrophilic radicals, cellulose membrane material
Usually to humidity sensitive, to water poor resistance, cellulose membrane will appear swollen deformation, strength reduction and barrier property after moisture absorption and become
The problems such as poor.In addition, when preparing composite material, there is also ask with other hydrophobic base poor compatibilities for hydrophilic cellulose
Topic.Has lot of documents report for the hydrophobically modified of nano-cellulose, physical absorption and chemical modification are common methods.Object
Managing adsorption is mainly the effect by aqueous affinity, electrostatic attraction, hydrogen bond or Van der Waals force, in CNF adsorption
Surfactant, electrically opposite substance or polymer dielectric are realized.Chemical modification is by way of covalent linkage
Various small molecules or macromolecular are introduced in cellulose surface.However, these processing methods are typically necessary heating or longer
The processing time, it is sometimes desirable to some virose chemical reagent are added, and treatment effeciency is not high, it is difficult to large-scale production.
In conclusion the hydrophobicity research process of cellulose membrane still remains many problems, cellulose microfibrillation processes according to
So there is production and application that many problems hamper its scale, such as: the preprocessing process period is long, not environmentally, chemicals
The problems such as expensive, difficult recycling, preparation cost is high.In addition, the cellulose nanometer film water resistance of conventional method preparation is poor, it is not easy
It is used under wet environment.To carry out hydrophobically modified, need to carry out complicated, the disagreeableness subsequent processing of at high cost or environment.Cause
This, there is an urgent need to develop a kind of efficient, sustainable, inexpensive and environment amenable methods to prepare high performance cellulose
Film.Therefore the present invention proposes that a kind of Mechanical Method prepares the preparation method of hydrophobic high permeable fiber film, it is real to overcome above-mentioned problems
Existing production process green, energy-saving and environmental protection, make new material be expected to be widely applied to packaging, micro-fluid chip, high-temperature flexible electronics
The high-end fields such as component substrate.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Aiming at the defects existing in the prior art, the purpose of the present invention is prepare a kind of dredge with simple technique
Aqueous high permeable fiber film solves high energy consumption, the Gao Chengben, the technical issues of can not producing in enormous quantities of existing method preparation.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of method that Mechanical Method prepares hydrophobic high permeable fiber film, comprising the following steps:
(1) enzymatic hydrolysis pretreatment: cellulosic material is subjected to enzymatic hydrolysis pretreatment with cellulase under condition of water bath heating, is obtained
To slurry；
(2) Mechanical Method is ground: after slurry obtained by step (1) is rinsed, carrying out mill to cellulose using high concentration plate mill
Mechanical Method milled processed makes cellulose fibrillation and realizes the destruction of cellulosic sections amorphous region, cellulose surface molecule
It is partly dissolved the dissolution with hemicellulose, obtains micrometer/nanometer cellulose suspension；
(3) shaping and drying: carrying out forming processes using the tape casting for micrometer/nanometer cellulose suspension obtained by step (2),
The hydrophobic high permeable fiber film is obtained after drying.
Preferably, cellulosic material described in step (1) is bagasse, cotton, wheat straw, reed, Sang Pi or jute；Institute
Cellulosic material is stated to alleviate machine 40000rpm using cellulose and carry out dispersion pretreatment.
Preferably, cellulase pretreatment condition described in step (1) are as follows: enzymolysis time 30min, hydrolysis temperature 50
℃。
Preferably, when handling cellulose suspension using high concentration plate mill in step (2), between high concentration plate mill mill
Spacing be 0.01-0.07mm；Content of cellulose is 5-30wt% in cellulose suspension；Grinding number is 5-30 times.
Preferably, to micrometer/nanometer cellulose suspension obtained by step (2) before the molding of the tape casting described in step (3)
Carry out ultrasonic treatment and magnetic agitation processing；The magnetic agitation rotating speed is 600rpm；The micrometer/nanometer cellulose suspension
Quantification of 15g/cm2。
Preferably, drying process described in step (3) carries out in air dry oven.
Preferably, the air dry oven drying temperature is 35-45 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
Cellulose membrane prepared by the present invention is had excellent performance, and structure is closely knit, intensity is high, transparency is high, and hydrophobicity is good, is breathed freely
Property is up to 75.77s/ (in2.100cc.1.22KPa)；And cellulose membrane of the invention is handled without any hydrophobically modified,
It does not need complicated chemical reaction, need expensive chemical reagent and instrument and equipment, it is fine in mechanical treatment and film forming procedure
Molecular rearrangement and recrystallization can be occurred by tieing up plain surface；The water contact angle of gained nano-cellulose film, can be in high humility up to 106 °
It is used under environment.
Detailed description of the invention
Fig. 1 is the hydrophobic angle picture of the hydrophobic high ventilating cellulose film of gained in embodiment 1；
Fig. 2 is the scanning electron microscopic picture of the hydrophobic high ventilating cellulose film of gained in embodiment 1；
Fig. 3 is the hydrophobic angle picture of the hydrophobic high ventilating cellulose film of gained in embodiment 2；
Fig. 4 is the scanning electron microscopic picture of the hydrophobic high ventilating cellulose film of gained in embodiment 2；
Fig. 5 is the hydrophobic angle picture of the hydrophobic high ventilating cellulose film of gained in embodiment 3；
Fig. 6 is the scanning electron microscopic picture of the hydrophobic high ventilating cellulose film of gained in embodiment 3.
Specific embodiment
The present invention will be better understood with reference to the following example, the embodiment provided does not limit the scope of the invention.
Embodiment 1
(1) bagasse slurry is alleviated into machine 40000rpm using cellulose and carries out dispersion pretreatment, after discongesting, use cellulose
Enzyme carries out enzymatic hydrolysis 30min under 50 DEG C of condition of water bath heating, using cellulase；
(2) by a large amount of distilled water flushings of the cellulose paste after enzymatic hydrolysis, enzyme solution is removed, using high concentration plate mill to fiber
Element carries out disc refiner mechanical method milled processed, and the spacing between high concentration plate mill mill is 0.07mm；Fiber in cellulose suspension
Cellulose content is 30wt%；Grinding number is 20 times.Grinding makes cellulose fibrillation and realizes the broken of cellulosic sections amorphous region
Bad, cellulose surface molecule the dissolution being partly dissolved with hemicellulose, obtains micrometer/nanometer cellulose suspension；
(3) micrometer/nanometer cellulose suspension is subjected to magnetic agitation processing, magnetic agitation rotating speed 600rpm, with micro-
The quantification of 15g/cm of rice/nano-cellulose suspension2Forming processes are carried out using the tape casting, place is dried in air dry oven
Reason, drying temperature are 35 DEG C, obtain the hydrophobic high permeable fiber film after dry.
Embodiment 2
(1) bagasse slurry is alleviated into machine 40000rpm using cellulose and carries out dispersion pretreatment, after discongesting, use cellulose
Enzyme carries out enzymatic hydrolysis 30min under 50 DEG C of condition of water bath heating, using cellulase；
(2) by a large amount of distilled water flushings of the cellulose paste after enzymatic hydrolysis, enzyme solution is removed, using high concentration plate mill to fiber
Element carries out disc refiner mechanical method milled processed, and the spacing between high concentration plate mill mill is 0.07mm；Fiber in cellulose suspension
Cellulose content is 30wt%；Grinding number is 25 times.Grinding makes cellulose fibrillation and realizes the broken of cellulosic sections amorphous region
Bad, cellulose surface molecule the dissolution being partly dissolved with hemicellulose, obtains micrometer/nanometer cellulose suspension；
(3) micrometer/nanometer cellulose suspension is subjected to magnetic agitation processing, magnetic agitation rotating speed 600rpm, with micro-
The quantification of 15g/cm of rice/nano-cellulose suspension2Forming processes are carried out using the tape casting, place is dried in air dry oven
Reason, drying temperature are 35 DEG C, obtain the hydrophobic high permeable fiber film after dry.
Embodiment 3
(1) bagasse slurry is alleviated into machine 40000rpm using cellulose and carries out dispersion pretreatment, after discongesting, use cellulose
Enzyme carries out enzymatic hydrolysis 30min under 50 DEG C of condition of water bath heating, using cellulase；
(2) by a large amount of distilled water flushings of the cellulose paste after enzymatic hydrolysis, enzyme solution is removed, using high concentration plate mill to fiber
Element carries out disc refiner mechanical method milled processed, and the spacing between high concentration plate mill mill is 0.07mm；Fiber in cellulose suspension
Cellulose content is 30wt%；Grinding number is 30 times.Grinding makes cellulose fibrillation and realizes the broken of cellulosic sections amorphous region
Bad, cellulose surface molecule the dissolution being partly dissolved with hemicellulose, obtains micrometer/nanometer cellulose suspension；
(3) micrometer/nanometer cellulose suspension is subjected to magnetic agitation processing, magnetic agitation rotating speed 600rpm, with micro-
The quantification of 15g/cm of rice/nano-cellulose suspension2Forming processes are carried out using the tape casting, place is dried in air dry oven
Reason, drying temperature are 35 DEG C, obtain the hydrophobic high permeable fiber film after dry.
Performance test
The thickness of cellulose membrane, elasticity modulus obtained by test 1-3 of the embodiment of the present invention, folding strength, contact angle and thoroughly respectively
Gas, test result see the table below 1.
Cellulose membrane performance test obtained by 1 1-3 of the embodiment of the present invention of table
As it can be seen from table 1 cellulose membrane prepared by the present invention is had excellent performance, structure is closely knit, and intensity is high, transparency
Height, hydrophobicity is good, and gas permeability is up to 75.77s/ (in2.100cc.1.22KPa).
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (7)
1. a kind of method that Mechanical Method prepares hydrophobic high permeable fiber film, which comprises the following steps:
(1) enzymatic hydrolysis pretreatment: cellulosic material is subjected to enzymatic hydrolysis pretreatment with cellulase under condition of water bath heating, is starched
Material；
(2) after slurry obtained by step (1) is rinsed, disc refiner mechanical method mechanical lapping: is carried out to cellulose using high concentration plate mill
Milled processed makes cellulose fibrillation and realizes that the destruction of cellulosic sections amorphous region, the part of cellulose surface molecule are molten
The dissolution of solution and hemicellulose, obtains micrometer/nanometer cellulose suspension；
(3) shaping and drying: carrying out forming processes using the tape casting for micrometer/nanometer cellulose suspension obtained by step (2), dry
The hydrophobic high permeable fiber film is obtained afterwards.
2. the method that Mechanical Method according to claim 1 prepares hydrophobic high permeable fiber film, which is characterized in that step (1)
Described in cellulosic material be bagasse, cotton, wheat straw, reed, Sang Pi or jute；The cellulosic material is relaxed using cellulose
Solution machine 40000rpm carries out dispersion pretreatment.
3. the method that Mechanical Method according to claim 1 prepares hydrophobic high permeable fiber film, which is characterized in that step (1)
Described in cellulase pretreatment condition are as follows: enzymolysis time 30min, 50 DEG C of hydrolysis temperature.
4. the method that Mechanical Method according to claim 1 prepares hydrophobic high permeable fiber film, which is characterized in that step (2)
When the middle processing cellulose suspension using high concentration plate mill, the spacing between high concentration plate mill mill is 0.01-0.07mm；Fiber
Content of cellulose is 5-30wt% in plain suspension；Grinding number is 5-30 times.
5. the method that Mechanical Method according to claim 1 prepares hydrophobic high permeable fiber film, which is characterized in that step (3)
Described in micrometer/nanometer cellulose suspension obtained by step (2) is carried out at ultrasonic treatment and magnetic agitation before the tape casting molding
Reason；The magnetic agitation rotating speed is 600rpm；The quantification of 15g/cm of micrometer/nanometer cellulose suspension2。
6. the method that Mechanical Method according to claim 1 prepares hydrophobic high permeable fiber film, which is characterized in that step (3)
Described in be dried and carried out in air dry oven.
7. the method that Mechanical Method according to claim 6 prepares hydrophobic high permeable fiber film, which is characterized in that the air blast
Drying box drying temperature is 35-45 DEG C.
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| CN201910724350.5A CN110452402A (en) | 2019-08-07 | 2019-08-07 | A kind of method that Mechanical Method prepares hydrophobic high permeable fiber film |
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| CN201910724350.5A CN110452402A (en) | 2019-08-07 | 2019-08-07 | A kind of method that Mechanical Method prepares hydrophobic high permeable fiber film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140288296A1 (en) * | 2013-03-25 | 2014-09-25 | Fpinnovations | Cellulose films with at least one hydrophobic or less hydrophilic surface |
| CN107287956A (en) * | 2016-04-01 | 2017-10-24 | 中国林业科学研究院木材工业研究所 | A kind of method that enzyme pretreatment prepares nano-cellulose with reference to mechanical lapping |
| CN108299714A (en) * | 2018-01-12 | 2018-07-20 | 成都新柯力化工科技有限公司 | A kind of high-strength composite plastic canopy film and preparation method thereof |
| CN109811569A (en) * | 2019-03-08 | 2019-05-28 | 广西大学 | A method of high yield pulp1 cellulose nanometer microfibril is prepared using enzyme auxiliary mechanical lapping low energy consumption |
| CN109867803A (en) * | 2019-01-28 | 2019-06-11 | 广西大学 | A kind of method that high concentration plate mill prepares hemicellulose film |
-
2019
- 2019-08-07 CN CN201910724350.5A patent/CN110452402A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140288296A1 (en) * | 2013-03-25 | 2014-09-25 | Fpinnovations | Cellulose films with at least one hydrophobic or less hydrophilic surface |
| CN107287956A (en) * | 2016-04-01 | 2017-10-24 | 中国林业科学研究院木材工业研究所 | A kind of method that enzyme pretreatment prepares nano-cellulose with reference to mechanical lapping |
| CN108299714A (en) * | 2018-01-12 | 2018-07-20 | 成都新柯力化工科技有限公司 | A kind of high-strength composite plastic canopy film and preparation method thereof |
| CN109867803A (en) * | 2019-01-28 | 2019-06-11 | 广西大学 | A kind of method that high concentration plate mill prepares hemicellulose film |
| CN109811569A (en) * | 2019-03-08 | 2019-05-28 | 广西大学 | A method of high yield pulp1 cellulose nanometer microfibril is prepared using enzyme auxiliary mechanical lapping low energy consumption |
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