CN106750554A - A kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film and preparation method - Google Patents
A kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film and preparation method Download PDFInfo
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- CN106750554A CN106750554A CN201611093018.6A CN201611093018A CN106750554A CN 106750554 A CN106750554 A CN 106750554A CN 201611093018 A CN201611093018 A CN 201611093018A CN 106750554 A CN106750554 A CN 106750554A
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- cellulose nanocrystal
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 100
- 239000001913 cellulose Substances 0.000 title claims abstract description 99
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000007731 hot pressing Methods 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000013305 flexible fiber Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- -1 alkyl glyoxaline cation Chemical class 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims 1
- WFYJISLZGVEJAE-UHFFFAOYSA-N [Cl].C(C)N1CN(C=C1)C Chemical compound [Cl].C(C)N1CN(C=C1)C WFYJISLZGVEJAE-UHFFFAOYSA-N 0.000 claims 1
- 230000008595 infiltration Effects 0.000 abstract description 6
- 238000001764 infiltration Methods 0.000 abstract description 6
- 239000008187 granular material Substances 0.000 abstract description 4
- 235000010980 cellulose Nutrition 0.000 description 81
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 241000894007 species Species 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000000873 masking effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- 206010007247 Carbuncle Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010016035 Face presentation Diseases 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention provides a kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film and preparation method thereof.The method uses negative-pressure ward first, a small amount of ionic liquid is uniformly attached to nano-crystalline granule surface, then carries out hot-pressing processing to film again, you can flame retardant type heat-resistant flexible Cellulose nanocrystal colour film is obtained.The made Cellulose nanocrystal colour film limited oxygen index of the present invention can reach 29 31, and its color can be regulated and controled by changing negative-pressure ward infiltration treatment mass fraction of the ionic liquid in its aqueous solution used.
Description
【Technical field】
The present invention relates to a kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film and preparation method, belong to biological high score
Sub- material film preparation field.
【Background technology】
The rod-like fibre element extracted from cellulose with sulfuric acid solution method is nanocrystalline, and the suspension of stabilization is formed in water
Liquid.When higher than critical concentration, Cellulose nanocrystal suspension be spontaneously separated into the unordered phase on upper strata and the chiral of lower floor to
Row liquid crystalline phase, this orderly liquid crystal structure can be retained in Cellulose nanocrystal solid film after moisture evaporation scatters and disappears, from
And film is showed iris under natural light.This schemochrome colour stable of Cellulose nanocrystal colour film and it is unique,
There is very wide application prospect in terms of anti-counterfeiting mark.Pure Cellulose nanocrystal colour film is the nanocrystalline particle of rigidity
Between be combined together by hydrogen bond action and formed, limited with hard fragility its application.By Cellulose nanocrystal with
It is the hard fragility most common method for improving Cellulose nanocrystal colour film that high molecular polymer is combined common assembling.Such as Publication No.
The Chinese invention patent of CN102449052A describes the water soluble polyhydroxy polymer by Cellulose nanocrystal and low-molecular-weight
The composite concrete placement method that assembling prepares the flexible fiber nanocrystalline colour film of element altogether.Additionally, in Publication No. CN105670044A
Prefabricated Cellulose nanocrystal colour film is carried out chemical processing by state's invention patent notes with concentrated base, makes Cellulose nanocrystal
The crystal formations of Form II are changed into from the crystal formations of Form I, amorphous region content in material is improved, so as to obtain the cellulose nanometer of high-strength and high ductility
The method of brilliant colour film.
The present invention penetrates into prefabricated Cellulose nanocrystal colour film by by a small amount of ionic liquid at room temperature negative-pressure ward,
Then the method for carrying out hot-pressing processing, obtaining can be with the flexible colour film of brake forming.Measuring mechanical property analysis shows from
Sub- liquid serves the effect of plasticizer in composite membrane, and the result of elementary analysis shows Cellulose nanocrystal surface in composite membrane
Sulfonate moieties be removed.Heat analysis are tested and combustion testing shows that the heat resistance and heatproof oxidation performance of gained composite membrane can be obtained
Raising is arrived.Limited oxygen index reaches 29-31；Maximum heat degradation rate temperature is up to 260-290 DEG C.The color of colour film with
Ionic liquid used in its aqueous solution the change of mass fraction and present regularity change.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film.
Another object of the present invention is also resided in and provides a kind of system of the flame retardant type heat-resistant flexible Cellulose nanocrystal colour film
Preparation Method.
It is a kind of by changing negative-pressure ward infiltration solvent for use intermediate ion liquid that another object of the present invention also resides in offer
Mass fraction come the method that regulates and controls colour film color.
Another object of the present invention also resides in offer one kind to be made ionic liquid penetrate into cellulose to receive by negative-pressure ward
The brilliant colour film of rice, then by hot-pressing processing, the method to improve colored film heat resistance and heatproof oxidation performance.
[technical scheme]
The invention provides a kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film and preparation method thereof, the method is first
A small amount of ionic liquid at room temperature negative-pressure ward is first penetrated into prefabricated Cellulose nanocrystal colour film, then by composite membrane in 100-
150 DEG C, hot-pressing processing 5-20 minutes under 5-10MPa.Cellulose nanocrystal surface contains great amount of hydroxy group and has hydrophily, is adopted
Ionic liquid can be with water with arbitrarily than miscible, under negative-pressure ward effect, and the mixed solution of ionic liquid and water can be with
Penetrate through Cellulose nanocrystal prefabricated membrane, the zwitterion of ionic liquid and the sulfonic group on Cellulose nanocrystal surface rapidly
Group, hydroxyl are combined together by electrostatic interaction, hydrogen bond action.In later stage drying process, unnecessary moisture evaporation,
And the ionic liquid that can not be volatilized has been stayed in inside colour film.Negative-pressure ward infiltration makes ionic liquid uniformly be attached to nanocrystalline
Grain surface, has intercepted the interaction of hydrogen bond between Cellulose nanocrystal particle, plays a part of plasticizer.The ion for being used
Liquid is a kind of active solvent of cellulose, and cellulose can be dissolved at high temperature.Hot-pressing processing makes nanocrystalline in colour film
The cellulosic sections on grain surface are dissolved in ionic liquid, and the cellulosic molecule for dissolving under external pressure is mutually through fusion.When
When colour film is subject to external carbuncle, this partly soluble cellulose plays a part of dispersive stress between nano-crystalline granule, so that
The pliability of colour film is set further to improve.And due to the sulfonate radical on Cellulose nanocrystal surface in composite membrane in the process
Part is removed, and the heat resistance of film is improved, and the halogen chlorine contained in ionic liquid has fire retardation, the heat-resisting oxygen of film
Change performance to be improved.The color of film can permeate the mass fraction of solvent intermediate ion liquid used by changing negative-pressure ward
Regulated and controled.
The present invention can be achieved through the following technical solutions：
A kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film, it is characterised in that：The colour film is fine by 65-93wt%
Dimension element is nanocrystalline and 7-35wt% ionic liquids are constituted, and with anti-flammability, oxygen index (OI) is 29-31, and thermal degradation rate temperature is
260-290℃。
A kind of preparation method of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film, it is characterised in that the colour film is logical
It is the prefabricated film forming of raw material to cross first with Cellulose nanocrystal, then by concentration for the ionic liquid aqueous solution of 5-30wt% is taken out with negative pressure
Suction method penetrates into the prefabricated membrane, then carries out hot-pressing processing to colour film, so as to obtain flame retardant type heat-resistant flexible cellulose nanometer
Brilliant colour film, the color of the film with ionic liquid used in its aqueous solution the difference of mass fraction and regular change is presented
Change.
The preparation method of described flame retardant type heat-resistant flexible Cellulose nanocrystal colour film, it is characterised in that the method includes
Following steps：
(1) preparation of Cellulose nanocrystal suspension：The concentrated sulfuric acid is added in comminuted fibres element raw material, heating stirring
Deionized water terminating reaction, standing is used to remove supernatant liquor after carrying out acidolysis, by lower floor's cloudy mixture centrifugation washing, system
Obtain Cellulose nanocrystal suspension；
(2) Cellulose nanocrystal suspension that above-mentioned steps are obtained is diluted to 0.2-3wt%, is then sonicated 5-60 points
Clock；Take it is ultrasonically treated after Cellulose nanocrystal suspension with negative-pressure ward remove moisture, obtain Cellulose nanocrystal colour film；
(3) it is the ionic liquid aqueous solution of 5-30wt% to add concentration to above-mentioned colour film surface, continues negative-pressure ward extremely
The upper surface noresidue liquid of colour film, drying is taken out by gained colour film, obtains Cellulose nanocrystal colour film；
(4) by above-mentioned nanocrystalline colour film at 100-150 DEG C, 5-10MPa hot-pressing processings 5-20 minutes are obtained high heat-resisting soft
Property Cellulose nanocrystal colour film.
Another preferred embodiment of the invention, it is characterised in that ionic liquid used is by positive and negative ion group
Into wherein cation is optionally substituted glyoxaline cation, and anion is chlorion.
Another preferred embodiment of the invention, it is characterised in that ionic liquid is 1- pi-allyl -3- methyl miaows
Azoles villaumite, 1- butyl -3- methylimidazole villaumites, 1- ethyl 3- methylimidazole villaumites.
Another preferred embodiment of the invention, it is characterised in that the color of colour film can be by changing ion
The solution concentration of liquid is regulated and controled.
Another preferred embodiment of the invention, it is characterised in that cellulosic material used derives from plant
Such as：Stalk, bamboo, trees, fruits and vegetables.
The preparation method of the described flexible fiber nanocrystalline colour film of element is further described below：
(1) preparation of Cellulose nanocrystal suspension：The concentrated sulfuric acid of 64wt% or so is added in comminuted fibres element,
It is 13.5-17.5 milliliters that every gram of paper cellulose adds the amount of the concentrated sulfuric acid.Mixture is stirred into acidolysis 50-60 at 40-50 DEG C
Minute, stir speed (S.S.) is 600-800rpm.Afterwards with a large amount of deionized water terminating reactions, topple over after stratification and remove upper liquid,
Lower floor's cloudy mixture is repeated centrifugation washing, to upper strata liquid turns turbid, Cellulose nanocrystal suspension is obtained.
(2) Cellulose nanocrystal suspension is diluted to 0.2-3wt%, the suspension that will have been diluted is ultrasonically treated to outstanding
Supernatant liquid is by muddy bleach.
(3) preparation of Cellulose nanocrystal colour film：Above-mentioned ultrasonically treated Cellulose nanocrystal suspension negative pressure is taken to take out
Moisture removal is sucked, the Cellulose nanocrystal colour film of filter membrane support is obtained.
(4) preparation of the nanocrystalline colour film of flexible fiber element：To the Cellulose nanocrystal colour film table that above-mentioned filter membrane is supported
Face adds the ionic liquid aqueous solution of 5-30wt%, after continuing negative-pressure ward to surface noresidue liquid, is placed in 50-90 DEG C of baking
After drying 1-2h in case, removal filter membrane obtains Cellulose nanocrystal colour film.By colour film in 100-150 DEG C, 5-10MPa hot pressing
Treatment 5-20 minutes, obtains flame retardant type heat-resistant flexible Cellulose nanocrystal colour film high.
[beneficial effect]
Due to taking above-mentioned technical proposal, it has advantages below to the present invention：
1st, flexibility, plasticity, the transparency：The Cellulose nanocrystal colour film of acquisition is because of the plasticization of a small amount of ionic liquid
And fusion between nanocrystalline caused by hot pressing and there is excellent pliability.Elongation at break and toughness increase, colour film
It is transparent further to improve.
2nd, it is heat-resist：The maximum heat degradation rate temperature of the flexible fiber nanocrystalline colour film of element after treatment, relative to
Before processing can improve 100 DEG C or so.
3rd, anti-flammability：Made Cellulose nanocrystal colour film has anti-flammability, and limited oxygen index reaches 30-35.
4th, Color tunable control：The color of the nanocrystalline colour film of flexible fiber element can be processed by changing negative-pressure ward infiltration
Mass fraction of the ionic liquid used in its aqueous solution regulates and controls.
5th, environmental protection：The ionic liquid for being used is a kind of fire retardant room temperature fused salt, stablizes non-volatile, miscible with water, green ring
Protect.
【Brief description of the drawings】
Fig. 1 is the process chart for preparing the flexible fiber nanocrystalline colour film of element.
Fig. 2 is the photo in kind of the made flexible fiber nanocrystalline colour film of element of embodiment 1,2,3,4 (respectively from Vertical Square
To shooting)；The thermal degradation speed of embodiment 2 and the made colour film of comparative example 5 and Relations with Temperature figure.Wherein highest peak on curve
Peak value corresponding to temperature be maximum heat degradation rate temperature.
Fig. 3 embodiments 1,2,3,4 made flexible colour film and comparative example 5 UV-vis spectrograms.
Fig. 4 is reflection embodiment 1,2,3,4 and comparative example 1, the photo in kind of 2,3,4 made colour film transparencies；
Fig. 5 is the measuring mechanical property datagram of embodiment 2 and the made colour film of comparative example 5.
【Specific embodiment】
The present invention is further described with reference to embodiment, but protection scope of the present invention is not limited to that.
Embodiment 1.
Take during 175 milliliter 64% of sulfuric acid is added to 10 grams of comminuted cellulosics and be well mixed, after stirring 1h at 45 DEG C, plus
Enter 1500 ml deionized water terminating reactions, will mixed liquor stand 24h after be layered, discard supernatant liquor, by lower sediment with
The rotating speed centrifugation 10min of 8000rpm/min, adds water washing for several times repeatedly, muddy to upper strata after last time centrifugally operated,
Cellulose nanocrystal suspension will be obtained and be diluted to 1wt%, and taken 18 milliliters and be placed in ice-water bath ultrasound to solution went clear, with negative
Pressure suction removes moisture, obtains the Cellulose nanocrystal colour film of filter membrane support, weighs the quality of prepared film.
The Cellulose nanocrystal colour film surface supported to above-mentioned filter membrane adds the ionic liquid aqueous solution of 5wt%, negative pressure
After being pumped to surface noresidue liquid, removed together with filter membrane and be placed in when being dried in 70 DEG C of baking oven after 1-2h, remove filter membrane
The Cellulose nanocrystal colour film of self-supporting is obtained, the quality of prepared film is weighed, calculating ionic liquid with difference weight method exists
Content in film is about 1wt%.Again by this film in 100-150 DEG C, 5-10MPa hot pressing 5-20 minutes.The made colour of the present embodiment
The photo in kind of film is as shown in Fig. 2 film surface is faced in light red, and a length of 670nm of its maximum reflection light wave as shown in Figure 3 is left
The right side, limited oxygen index is 29, and tensile property data are shown in Table 1.
The tensile property of the Cellulose nanocrystal colour film of table 1.
Embodiment 2.
Material therefor species, consumption and technological process are with embodiment 1, the difference is that generating Cellulose nanocrystal colour film
Afterwards, the Cellulose nanocrystal colour film surface for being supported to filter membrane adds the ionic liquid aqueous solution of 15wt%, continues negative-pressure ward extremely
Colour film upper surface noresidue liquid, is removed after being placed in and drying 1-2h in 70 DEG C of baking oven together with filter membrane, and removal filter membrane is obtained
To the Cellulose nanocrystal colour film of self-supporting, the quality of prepared film is weighed, ionic liquid is calculated in film with difference weight method
In content be about 10wt%.Again by this film in 100-150 DEG C, 5-10MPa hot pressing 5-20 minutes.The made colour film of the present embodiment
Photo in kind as shown in Fig. 2 film is faced, presentation is blue, 700nm or so is arrived in its maximum reflection optical wavelength red shift as shown in Figure 3,
Limited oxygen index is 29.7, and tensile property data are shown in Table 1.
Embodiment 3.
Material therefor species, consumption and technological process are with embodiment 1, the difference is that forming Cellulose nanocrystal colour film
Afterwards, the Cellulose nanocrystal colour film surface for being supported to filter membrane adds the ionic liquid aqueous solution of 25wt%, continues negative-pressure ward
To colour film upper surface noresidue liquid, removed together with filter membrane after being placed in and drying 1-2h in 70 DEG C of baking oven, remove filter membrane
The Cellulose nanocrystal colour film of self-supporting is obtained, the quality of prepared film is weighed, calculating ionic liquid with difference weight method exists
Content in film is about 27wt%.Again by this film at 100-150 DEG C, hot pressing 5-20 minutes under the conditions of 5-10MPa.The present embodiment institute
The photo in kind of colour film processed is presented light blue as shown in Fig. 2 film surface is faced, its maximum reflection light wave progress as shown in Figure 3
750nm or so is arrived in one step red shift, and limited oxygen index is 30.2, and tensile property data are shown in Table 1.
Embodiment 4.
Material therefor species, consumption and technological process with embodiment 1, unlike formed Cellulose nanocrystal film after, to
The Cellulose nanocrystal colour film surface of filter membrane support adds the ionic liquid aqueous solution of 30wt%, continues negative-pressure ward to colour
Film upper surface noresidue liquid, removes after being placed in and drying 1-2h in 70 DEG C of baking oven together with filter membrane, removal filter membrane obtain from
The Cellulose nanocrystal colour film of support, weighs the quality of prepared film, and ionic liquid is calculated in film with the method again that differs from
Content is about 28wt%.Again by this film at 100-150 DEG C, hot pressing 5-20 minutes under the conditions of 5-10MPa.The made colour of the present embodiment
As shown in Fig. 2 the color of film becomes light compared with the sample in embodiment 3, it is maximum anti-as shown in Figure 3 for the photo in kind of film
Penetrate optical wavelength red shift and arrive 820nm or so, limited oxygen index is 31, and tensile property data are shown in Table 1.
Comparative example 1.
The preparation technology flow of material therefor species, consumption and flexible colour film is not carried out at hot pressing with embodiment 1
Reason.The transparency of institute's masking is significantly lower than embodiment 1, sees Fig. 5, and tensile property test data is shown in Table 1.
Comparative example 2.
The preparation technology flow of material therefor species, consumption and flexible colour film is not carried out at hot pressing with embodiment 2
Reason.The transparency of institute's masking is significantly lower than embodiment 2, sees Fig. 5, and tensile property test data is shown in Table 1.
Comparative example 3.
The preparation technology flow of material therefor species, consumption and flexible colour film is not carried out at hot pressing with embodiment 3
Reason.The transparency of institute's masking is significantly lower than embodiment 3, sees Fig. 5, and tensile property test data is shown in Table 1.
Comparative example 4.
The preparation technology flow of material therefor species, consumption and flexible colour film is not carried out at hot pressing with embodiment 4
Reason.The transparency of institute's masking is significantly lower than embodiment 4, sees Fig. 5, and tensile property test data is shown in Table 1.
Comparative example 5.
Take 175 milliliters of 64wt% sulfuric acid be added to 10 grams crushing paper celluloses in be well mixed, stirred at 45 DEG C
After mixing 1h, 1500 ml deionized water terminating reactions are added, be layered after mixed liquor is stood into 24h, supernatant liquor is discarded, by lower floor
Precipitation adds water washing for several times repeatedly with the rotating speed centrifugation 10min of 8000rpm/min, to last time centrifugation, on
Layer is muddy.The Cellulose nanocrystal suspension that will be prepared is diluted to 1wt%, takes 18 milliliters and is placed in ice-water bath ultrasound to solution
Bleach, moisture is removed with negative-pressure ward, obtains the Cellulose nanocrystal colour film of filter membrane support.Resulting membrane material is firmly crisp
There is slight crack, pictorial diagram is shown in Fig. 1 and Fig. 2, face presentation yellow, limited oxygen index is 24, its maximum reflection optical wavelength as shown in Figure 3
In 650nm or so.
Comparative example 6.
Material therefor species, consumption with embodiment 1, unlike Cellulose nanocrystal suspension ultrasonic disperse it is uniform after,
Ionic liquid aqueous solution is added drop-wise in the suspension of Cellulose nanocrystal and be well mixed, this mixed liquor is removed with negative-pressure ward
Liquid prepares Cellulose nanocrystal film.Because the negatively charged nano-crystalline granule in the zwitterion influence surface of ionic liquid exists
Self assembly in solution, resulting film water white transparency, is not presented iris.
The content of institute's masking intermediate ion liquid is can be seen that with the concentration increase of ionic liquid used from embodiment 1-4
Also there is corresponding change therewith in increase, the color of film.The extension test as shown by data of embodiment in table 1, with ionic liquid constitution
The increase of fraction is measured, resulting flexible colour film elongation at break and fracture toughness increase, and illustrate ionic liquid in membrane material
In serve the effect of plasticising.Be can be seen that from the photo in kind and Fig. 3 of Fig. 2, with the ionic liquid water of different quality containing
Solution makes ionic liquid penetrate into Cellulose nanocrystal colour film by negative-pressure ward, then carries out hot-pressing processing and can prepare
Flexible colour film, the color of film can be regulated and controled by ionic liquid mass fraction in aqueous；Figure it is seen that
The nanocrystalline colour film obtained using infiltration treatment after the ionic liquid aqueous solution of certain mass fraction has good plasticity, can
With bending or Texturized；The test result of heat endurance TGA shows water-soluble using the ionic liquid of certain mass fraction in Fig. 2
Liquid post processing Cellulose nanocrystal colour film can make the heat resisting temperature of colour film improve 100 DEG C or so than before processing, from Fig. 2 from
The EDX spectrograms of sample after sub- Liquid Penetrant before processing, it can be seen that after ionic liquid infiltration treatment, the sulfur content in colour film is bright
Aobvious to reduce, the raising for thus inferring heat resisting temperature is because Cellulose nanocrystal particle surface sulfur-containing group is by partial removal；Fig. 4
Extension test in the DMA extension tests figure and table 1 of the photo in kind and Fig. 5 of middle comparative example 1,2,3,4 and embodiment 1,2,3,4
Result shows, the flexible nano crystalline substance colour film obtained using the ionic liquid aqueous solution post processing of certain mass fraction, by heat
Pressure treatment can further improve the transparency and toughness of colour film.This is due to the cellulose nano particle side under hot pressing function
The a small amount of cellulose in boundary surface can be dissolved in ionic liquid and merge, and crystallinity declines, and the scattering process to light weakens, colour film
Toughness and transparency further improve.Pure CNC colour films prepared by comparative example 5, hard crisp frangible, thermally-stabilised difference.Comparative example 6
Using the technique that ionic liquid and Cellulose nanocrystal suspension are directly mixed common assembling, do not obtain iris film, be because
For the zwitterion of ionic liquid has an impact to nano-crystalline granule self assembly of the surface with negative electrical charge, it is impossible to form orderly liquid
Crystal structure.Thus, processing method provided by the present invention and technique are obtained in that flexible Cellulose nanocrystal colour film.Do not wave
The ionic liquid of hair serves the effect of plasticizer in colour film.In last handling process, Cellulose nanocrystal particle surface
Sulfonate moieties be removed, be improved the heat endurance of film.Ionic liquid is the non-derivative solvent of cellulose, normal temperature
The method of lower use ionic liquid aqueous solution post processing will not destroy the ordered lamellar structure of its self assembly, and what is only changed is to receive
The pitch of the brilliant chirality self assembly ordered structure of rice, so that matter of the color of colour film with ionic liquid used in aqueous
The change of amount fraction difference and presentation regularity, in the ultra-violet absorption spectrum of flexible colour film, maximum reflection optical wavelength is gradually red
Move.
Claims (8)
1. a kind of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film, it is characterised in that：The colour film is by 65-93wt% fibers
Nanocrystalline and 7-35wt% the ionic liquid of element is constituted, and oxygen index (OI) is 29-31, and thermal degradation temperature is 260-290 DEG C.
2. the flame retardant type heat-resistant flexible Cellulose nanocrystal colour film described in claim 1, it is characterised in that the colour film is logical
It is the prefabricated film forming of raw material to cross first with Cellulose nanocrystal, then by concentration for the ionic liquid aqueous solution of 5-30wt% is penetrated into
The prefabricated membrane, then carries out hot-pressing processing to colour film, so as to obtain flame retardant type heat-resistant flexible Cellulose nanocrystal colour film.
3. the preparation method of the flame retardant type heat-resistant flexible Cellulose nanocrystal colour film described in claim 1, it is characterised in that
The method comprises the following steps：
(1) preparation of Cellulose nanocrystal suspension：The concentrated sulfuric acid is added in comminuted fibres element raw material, heating stirring is carried out
Deionized water terminating reaction is used after acidolysis, by lower floor's cloudy mixture centrifugation washing, Cellulose nanocrystal suspension is obtained；
(2) Cellulose nanocrystal suspension that above-mentioned steps are obtained is diluted to 0.2-3wt%, is then sonicated 5-60 minutes；
Take it is ultrasonically treated after Cellulose nanocrystal suspension with negative-pressure ward remove moisture, obtain Cellulose nanocrystal colour film；
(3) it is the ionic liquid aqueous solution of 5-30wt% to add concentration to above-mentioned colour film surface, continues negative-pressure ward to colour
The upper surface noresidue liquid of film, drying is taken out by gained colour film, obtains Cellulose nanocrystal colour film；
(4) by above-mentioned nanocrystalline colour film at 100-150 DEG C, 5-10MPa hot-pressing processings 5-20 minutes are obtained heat-resistant flexible fiber
The nanocrystalline colour film of element.
4. the preparation method of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film according to claim 3, its feature exists
It is made up of positive and negative ion in ionic liquid used, wherein cation is alkyl glyoxaline cation, and anion is chlorion.
5. the preparation method of flame retardant type heat-resistant flexible Cellulose nanocrystal colour film according to claim 4, its feature exists
In ionic liquid be 1- pi-allyl -3- methylimidazole villaumites, 1- butyl -3- methylimidazole villaumites, 1- ethyl 3- methylimidazole chlorine
Salt.
6. flame retardant type heat-resistant flexible Cellulose nanocrystal according to claim 3 colour membrane preparation method, it is characterised in that
Prepared colour film most degradation rate temperature can improve 100 DEG C, and limited oxygen index can reach 29-31.
7. the nanocrystalline colored membrane preparation method of flexible fiber according to claim 3 element, it is characterised in that the face of colour film
Color can be regulated and controled by changing the solution concentration of ionic liquid.
8. the preparation process of the Cellulose nanocrystal suspension according to claim 3 step (1), it is characterised in that used
Cellulosic material derives from plant such as：Stalk, bamboo, trees, fruits and vegetables.
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| CN111040225A (en) * | 2019-12-05 | 2020-04-21 | 中山大学 | Repeatedly erasable anti-counterfeiting film based on photonic crystal structural color and preparation method and application thereof |
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| CN105419012A (en) * | 2015-12-19 | 2016-03-23 | 华南理工大学 | Preparation method for straw-based crystalline cellulose nanocrystals and rubber composite material of straw-based crystalline cellulose nanocrystals |
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| CN105419012A (en) * | 2015-12-19 | 2016-03-23 | 华南理工大学 | Preparation method for straw-based crystalline cellulose nanocrystals and rubber composite material of straw-based crystalline cellulose nanocrystals |
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| CN111040225A (en) * | 2019-12-05 | 2020-04-21 | 中山大学 | Repeatedly erasable anti-counterfeiting film based on photonic crystal structural color and preparation method and application thereof |
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