CN108383916A - II crystal form Cellulose nanocrystal of one kind and preparation method thereof - Google Patents
II crystal form Cellulose nanocrystal of one kind and preparation method thereof Download PDFInfo
- Publication number
- CN108383916A CN108383916A CN201810334049.9A CN201810334049A CN108383916A CN 108383916 A CN108383916 A CN 108383916A CN 201810334049 A CN201810334049 A CN 201810334049A CN 108383916 A CN108383916 A CN 108383916A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- sodium
- oxometallate
- preparation
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 184
- 239000001913 cellulose Substances 0.000 title claims abstract description 180
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 114
- 239000013078 crystal Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 206010042674 Swelling Diseases 0.000 claims abstract description 8
- 230000008961 swelling Effects 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 235000010980 cellulose Nutrition 0.000 claims description 179
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 7
- -1 Fluorine monohydroxide potassium Chemical compound 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- FRHWVPSOGPPETO-UHFFFAOYSA-N O[I][K] Chemical compound O[I][K] FRHWVPSOGPPETO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004153 Potassium bromate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- 239000008104 plant cellulose Substances 0.000 claims description 2
- 229940094037 potassium bromate Drugs 0.000 claims description 2
- 235000019396 potassium bromate Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 claims description 2
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims 2
- 239000000123 paper Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 42
- 239000002994 raw material Substances 0.000 abstract description 32
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- OFQCQIGMURIECL-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl]-2',6'-dimethylspiro[isoquinoline-4,4'-oxane]-1,3-dione;phosphoric acid Chemical compound OP(O)(O)=O.O=C1N(CCN(CC)CC)C(=O)C2=CC=CC=C2C21CC(C)OC(C)C2 OFQCQIGMURIECL-UHFFFAOYSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 27
- 235000011121 sodium hydroxide Nutrition 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000835 fiber Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present embodiments relate to a kind of II crystal form Cellulose nanocrystals and preparation method thereof.The preparation method includes the following steps：After cellulosic material is carried out swelling treatment and is crushed, washing；It is reacted being dispersed in the aqueous slkali containing oxometallate by pretreated cellulosic material, wherein concentration >=1.5M of alkali；Reaction product is post-processed, the II crystal form Cellulose nanocrystal suspensions of stable dispersion are obtained.Should preparation method is simple, using I crystal cellulose as raw material, by build oxometallate alkaline reaction system to one-pot oxidation hydrolyze directly preparation II crystal form Cellulose nanocrystals；And this method is environmentally protective, without using a large amount of organic solvents.
Description
Technical field
The present invention relates to field of nano material preparation, more particularly to a kind of II crystal form Cellulose nanocrystal and its preparation side
Method.
Background technology
Cellulose is the maximum natural biologic material of amount in nature, is widely present in green plants, marine animal
In equal organisms.By removing the amorphous area in cellulosic material, the Cellulose nanocrystal of nano-scale can be obtained.From natural
Cellulose nanocrystal is extracted in cellulose, helps to study the structure of cellulose and nanocrystalline aggregated structure, is improved fine
Tie up the respond of element；With water can be anti-with appropriate monomer in addition, Cellulose nanocrystal can be stably dispersed in aqueous phase system
Medium is answered to be grafted, this, which is other form celluloses, to accomplish.
Research shows that the macroscopic property of II crystal form cellulose is more stablized than I crystal form cellulose, II crystal form cellulose is received
Meter Jing also more stablizes than the macroscopic property of I crystal form Cellulose nanocrystal.
I crystal form cellulose is mainly first transformed into II crystal form fiber by the existing method for preparing II crystal form Cellulose nanocrystal
Element, then II crystal form Cellulose nanocrystals are prepared as raw material using II crystal form cellulose.Two-step method is used in this method, and will
I crystal form cellulose is transformed into generally use solvent regeneration process during II crystal form cellulose：I crystal cellulose dissolution is existed
In appropriate solvent, and so that the series arrangement of cellulose molecular chain is changed in this solvent, then makes II with precipitating reagent appropriate
Crystal form cellulose product is precipitated out from solvent.A large amount of organic solvents, obtained II crystal form fibers are used in solvent regeneration process
The product crystal form and crystallinity of element are bad, and serious pollution can be caused also manufacturing cost to be made higher to environment.
Therefore, a kind of environmentally protective efficient II crystal form Cellulose nanocrystal of exploitation and preparation method thereof has important meaning
Justice.
Being disclosed in the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without answering
It has been the prior art well known to persons skilled in the art when being considered as recognizing or imply that the information is constituted in any form.
Invention content
Goal of the invention
The goal of the invention of the present invention is to provide II crystal form Cellulose nanocrystal of one kind and preparation method thereof；This method is simple
It is easy, it can be using I crystal cellulose as raw material, by building the alkaline reaction system of oxometallate to which one-pot oxidation hydrolyzes
Directly prepare II crystal form Cellulose nanocrystals；This method is environmentally protective simultaneously, need not use a large amount of organic solvents.
Technical solution
To realize the above goal of the invention, an embodiment of the present invention provides a kind of preparation sides of II crystal form Cellulose nanocrystal
Method comprising following steps：
Pretreatment：After cellulosic material is carried out swelling treatment and is crushed, washing；
Oxydrolysis：It will be dispersed in the aqueous slkali containing oxometallate and be carried out instead by pretreated cellulosic material
It answers；
Post-processing：Reaction product is post-processed, II crystal form Cellulose nanocrystal suspension of stable dispersion is obtained；
Wherein：When preparing the aqueous slkali containing oxometallate, used alkali includes sodium hydroxide, hydroxide
One or more of potassium, lithium hydroxide, saleratus, sodium bicarbonate；
And in the aqueous slkali containing oxometallate, concentration >=1.5M of alkali.
In a kind of possible embodiment, the oxometallate include potassium ferrate, Na2Fe04, potassium permanganate,
Sodium permanganate, potassium nitrate, sodium nitrate, potassium chlorate, sodium chlorate, potassium hyperchlorate, sodium perchlorate, potassium bromate, sodium bromate, hyperbromic acid
One or more of potassium, hyperbromic acid sodium, bismuthic acid potassium, sodium bismuthate.
In a kind of possible embodiment, the alkali containing oxometallate will be dispersed in by pretreated cellulosic material
In solution, and hypohalite is added and is reacted.
In a kind of possible embodiment, the hypohalite includes Fluorine monohydroxide potassium, Fluorine monohydroxide sodium, postassium hypochlorite, secondary
One or more of sodium chlorate, potassium hypobromite, sodium hypobromite, hypoiodous acid potassium, hypoiodous acid sodium.
In a kind of possible embodiment, in the aqueous slkali containing oxometallate, the concentration of 1.5M≤alkali≤
10M。
In a kind of possible embodiment, the mass ratio of cellulosic material and oxometallate is 1:0.1~9, it is optional
It is 1:0.5~7, further alternative is 1:1~5.
In a kind of possible embodiment, the mass ratio of oxometallate and hypohalite used is 1:0.5~50, it can
Choosing is 1:5~40, further alternative is 1:10~20.
In a kind of possible embodiment, the quality percentage of oxometallate in the aqueous slkali containing oxometallate
A concentration of 0.1%~30%, it is optionally 1%~25%, further alternative is 2%~20%.
In a kind of possible embodiment, the reaction is to be reacted under conditions of heating stirring；Optionally, institute
The temperature for stating reaction is 30~100 DEG C, and the time of reaction is 3~48h；It is further alternative, the temperature of the reaction is 40~
60 DEG C, the time of reaction is 6~8h.
In a kind of possible embodiment, the cellulosic material includes microcrystalline cellulose, plant cellulose, paper pulp fibre
Dimension element or alpha-cellulose；It can also be native cellulose common in nature.
In a kind of possible embodiment, when preparing the aqueous slkali containing oxometallate, institute includes hydrogen using alkali
One or more of sodium oxide molybdena, potassium hydroxide, lithium hydroxide.
In a kind of possible embodiment, the swelling treatment is to carry out immersion swelling to cellulosic material with lye,
Lye used is mass percentage 1%~8%, is optionally 2%~7%, the further alternative hydrogen-oxygen for being 3%~5%
Change sodium water solution, potassium hydroxide aqueous solution or sodium bicarbonate aqueous solution.
In a kind of possible embodiment, the time for carrying out impregnating swelling to cellulosic material with lye is 1~48h,
Be optionally 5~36h, it is further alternative be 8~for 24 hours.
In a kind of possible embodiment, when cellulosic material is swollen with dipping by lye, cellulosic material and lye
Amount ratio be 10~80g:1L, i.e., every 10~80g cellulosic materials need 1L lye.
In a kind of possible embodiment, described to be broken for stirring broken；It is described washing for be washed with deionized to
PH is close or identical with deionized water.
In a kind of possible embodiment, it is described to reaction product carry out post-processing be：Reaction product is centrifuged,
It is in light blue or milk-white coloured suspension state to take precipitation deionized water to wash centrifugation to upper liquid repeatedly, upper liquid is taken to dialyse,
Ultrasonic disperse.
In a kind of possible embodiment, when reaction product is centrifuged, centrifuge speed be 3000~
12000rpm, centrifugation number 2~8 times.
In a kind of possible embodiment, upper liquid dialyse when, dialyse to upper liquid pH it is close with deionized water or
It is identical.
The embodiment of the present invention additionally provides the II crystal form Cellulose nanocrystals obtained by above-mentioned preparation method, and yield is super
70% is crossed, average length is 150~300nm, a diameter of 5~30nm.
Advantageous effect
1, the embodiment of the present invention has the property of strong oxidizing property using oxometallate in alkaline environment, passes through to build and wrap
Amorphous area in I crystal cellulose is aoxidized water by reaction system of the cellulose containing I crystal as raw material, oxometallate and alkali
Solution removes；And in specific alkaline environment provided by the present application, moreover it is possible to which the transformation for realizing crystal form obtains in water stablizing
II crystal form Cellulose nanocrystal of dispersion.In the method, it is no longer necessary to first be turned I crystal cellulose using a large amount of organic solvents
Become II crystal form celluloses, then hydrolyzes again and obtain II crystal form Cellulose nanocrystals, but by one-step method directly with I crystal fibre
Dimension element obtains the Cellulose nanocrystal with crystal form of cellulose II as raw material.
2, the highly basic being added in reaction system can not only provide alkaline environment, also for the oxometallate in reaction system
It can make to realize that cellulose chain is transformed into II crystal form fiber from I crystal form cellulose chain during preparing II crystal form Cellulose nanocrystals
Plain chain is to prepare II crystal form Cellulose nanocrystal.
3, hypohalogenous acids is additionally added in the reaction system comprising I crystal cellulose as raw material, oxometallate and alkali
Salt can utilize the Specific Interactions between hypohalite and oxometallate to realize the recycling of oxometallate, make metal
The usage amount of oxygen hydrochlorate reduces 80%, and the pollution to environment is reduced while reducing manufacturing cost, can be used for magnanimity system
Standby II crystal form Cellulose nanocrystals.
4, controllable by regulating and controlling addition, alkali concentration, the addition of hypohalite of oxometallate in reaction system
The major diameter of gained II crystal form Cellulose nanocrystals when yield, the length of obtained II crystal form Cellulose nanocrystals is 150~
The yield of 300nm, a diameter of 5~30nm, Cellulose nanocrystal can be more than 70%.
5, oxometallic acid salt oxidizing agent used is green, environmentally friendly reagent, and environmental pollution is small, and is industrialization production
Product, it is cheap；It has superpower oxidisability in alkaline environment, and can be stabilized the long period, is that reaction system is high
Effect prepares II crystal form Cellulose nanocrystals and provides condition.
6, hypohalite used is also green, environmentally friendly reagent, and environmental pollution is small, and is industrialization product, price
It is cheap.
Description of the drawings
According to below with reference to the accompanying drawings becoming to detailed description of illustrative embodiments, other feature of the invention and aspect
It is clear.One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary illustrations
The restriction to embodiment is not constituted.
Fig. 1 is the atomic force microscopy of II crystal form Cellulose nanocrystal prepared by the embodiment of the present invention 1.
Fig. 2 is the grading curve of II crystal form Cellulose nanocrystal prepared by the embodiment of the present invention 1.
Fig. 3 is the x-ray diffraction pattern of II crystal form Cellulose nanocrystal prepared by the embodiment of the present invention 1, and three lines are from upper
II crystal form Cellulose nanocrystals, II crystal forms cellulose and I crystal cellulose are respectively represented under.
Fig. 4 is the thermal stability curve of II crystal form Cellulose nanocrystal prepared by the embodiment of the present invention 1.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
Unless otherwise explicitly stated, otherwise in entire disclosure and claims, term " comprising " or its change
It changes such as "comprising" or " including " etc. and will be understood to comprise stated element or component, and do not exclude other members
Part or other component parts.
Any embodiment is removed and is non-clearly supported below, otherwise should not necessarily be construed as preferred or advantageous over other embodiments.
In addition, in order to better illustrate the present invention, numerous details is given in specific implementation mode below.
It will be appreciated by those skilled in the art that without certain details, the present invention can equally be implemented.In some instances, for
Method well known to those skilled in the art, means, element are not described in detail, in order to highlight the purport of the present invention.
Embodiment 1
Pretreatment：The sodium hydroxide solution immersion that 5g paper celluloses are added to 250mL a concentration of 4% is carried out for 24 hours molten
It is broken into flocculence with blender after swollen, is filtered, and rear drying identical as deionized water to its pH is washed with deionized；
It is swollen in this step and broken sequencing is not notable on result influence, both can first be swollen and be crushed again, and also can first be crushed again
Swelling.
Oxydrolysis：Again will by above-mentioned pretreated cellulosic material be scattered in the aqueous slkali containing oxometallate into
Row oxydrolysis, the aqueous slkali containing oxometallate by 300mL deionized waters, 0.5g potassium ferrates, 5g sodium hypochlorite and
18g sodium hydroxides form, and are scattered in the aqueous slkali containing oxometallate by pretreated cellulosic material and carry out oxidation water
The process of solution is：It will be placed in the above-mentioned aqueous slkali containing oxometallate by pretreated cellulosic material, 50 DEG C of stirring oxygen
Change and cellulosic hydrolysate is centrifuged by 10min with the rotating speed of 8000rpm/min with supercentrifuge after hydrolyzing 3h, then uses precipitation
It is in light blue or milk-white coloured suspension state that deionized water washs centrifugation to upper liquid repeatedly, and Cellulose nanocrystal is dispersed in
In layer liquid.It takes upper liquid deionized water dialysis, the pH of dialysis to upper layer suspension identical as deionized water, then upper liquid is surpassed
Sound obtains stable II crystal form Cellulose nanocrystal suspensions, is about through measuring gained Cellulose nanocrystal average length
300nm, average diameter are about 25nm, and yield 34%, (calculating of PDI is with gained fibre in the application for particle size dispersion index (PDI)
The nanocrystalline distribution of lengths of dimension element indicates) it is 0.2.
Pattern, particle diameter distribution such as Fig. 1 and Fig. 2 of Cellulose nanocrystal in prepared Cellulose nanocrystal suspension,
Prepared Cellulose nanocrystal crystalline structure characterization such as Fig. 3, the thermal stability characterization of prepared Cellulose nanocrystal is as schemed
4.As can be seen from Figure 1 the Cellulose nanocrystal that prepared by this method is in typical club shaped structure, and is in monodisperse status, is said
Without assembling between light fibers element is nanocrystalline；As can be seen from Figure 2 prepared Cellulose nanocrystal particle diameter distribution refers to
Number is relatively narrow, illustrates that prepared Cellulose nanocrystal distribution of lengths is relatively uniform；As seen from Figure 3, by comparing institute of the present invention
The x-ray diffraction pattern for stating the Cellulose nanocrystal and raw material I crystal cellulose of method preparation, there it can be seen that raw fibre
The crystalline structure of element is in cellulose Ⅰ crystal form, is in cellulose Ⅱ crystal form using the Cellulose nanocrystal prepared by this method, and obtain
Product through X-ray diffraction detection have sharp peak type；Figure 4, it is seen that prepared Cellulose nanocrystal has
Higher thermal stability.
Embodiment 2
The dosage of potassium ferrate used is 5g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) with
Embodiment 1 is identical, obtains stable Cellulose nanocrystal suspension, is about through measuring gained Cellulose nanocrystal average length
263nm, average diameter are about 20nm, and yield 49%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 3
The dosage of potassium ferrate used is 10g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.)
It is same as Example 1, stable Cellulose nanocrystal suspension is obtained, is about through measuring gained Cellulose nanocrystal average length
251nm, average diameter are about 18nm, and yield 57%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 4
The dosage of sodium hypochlorite used is 25g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.)
It is same as Example 2, stable Cellulose nanocrystal suspension is obtained, is about through measuring gained Cellulose nanocrystal average length
259nm, average diameter are about 19nm, and yield 56%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 5
The dosage of sodium hypochlorite used is 50g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.)
It is same as Example 2, stable Cellulose nanocrystal suspension is obtained, is about through measuring gained Cellulose nanocrystal average length
207nm, average diameter are about 16nm, and yield 63%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 6
The dosage of sodium hypochlorite used is 100g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.)
It is same as Example 2, stable Cellulose nanocrystal suspension is obtained, is about through measuring gained Cellulose nanocrystal average length
189nm, average diameter are about 12nm, and yield 69%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 7
Amount of sodium hydroxide used is 24g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) with reality
It applies that example 1 is identical, obtains stable Cellulose nanocrystal suspension, be about through measuring gained Cellulose nanocrystal average length
271nm, average diameter are about 26nm, and yield 43%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 8
The dosage of sodium hydroxide used is 48g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.)
It is same as Example 1, stable Cellulose nanocrystal suspension is obtained, is about through measuring gained Cellulose nanocrystal average length
256nm, average diameter are about 18nm, and yield 49%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 9
The amount that sodium hydroxide is added is 24g, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) with
Embodiment 5 is identical, obtains stable Cellulose nanocrystal suspension, is about through measuring gained Cellulose nanocrystal average length
195nm, average diameter are about 12nm, and yield 67%, PDI 0.2, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 10
The time that oxydrolysis is stirred when preparing Cellulose nanocrystal is 12h, remaining all conditions is (such as：Raw material kind
Class, dosage and technological process etc.) it is same as Example 2, stable Cellulose nanocrystal suspension is obtained, it is fine through measuring gained
The nanocrystalline average length of dimension element is about 241nm, and average diameter is about 23nm, yield 59%, PDI 0.2, prepared fiber
Nanocrystalline element is in cellulose Ⅱ crystalline structure.
Embodiment 11
The time that oxydrolysis is stirred when preparing Cellulose nanocrystal is 8h, remaining all conditions is (such as：Raw material kind
Class, dosage and technological process etc.) it is same as Example 9, stable Cellulose nanocrystal suspension is obtained, it is fine through measuring gained
The nanocrystalline average length of dimension element is about 155nm, and average diameter is about 6nm, yield 72%, PDI 0.2, prepared fiber
Nanocrystalline element is in cellulose Ⅱ crystalline structure.
Embodiment 12
The temperature that oxydrolysis is stirred when preparing Cellulose nanocrystal is 30 DEG C, remaining all conditions is (such as：Raw material kind
Class, dosage and technological process etc.) it is same as Example 2, stable Cellulose nanocrystal suspension is made, it is fine through measuring gained
The nanocrystalline average length of dimension element is about 285nm, and average diameter is about 28nm, yield 42%, PDI 0.3, prepared fiber
Nanocrystalline element is in cellulose Ⅱ crystalline structure.
Embodiment 13
The temperature that oxydrolysis is stirred when preparing Cellulose nanocrystal is 100 DEG C, remaining all conditions is (such as：Raw material
Type, dosage and technological process etc.) it is same as Example 2, stable Cellulose nanocrystal suspension is made, through measuring gained
Cellulose nanocrystal average length is about 275nm, and average diameter is about 25nm, yield 46%, PDI 0.3, prepared fibre
Nanocrystalline dimension element is in cellulose Ⅱ crystalline structure.
Embodiment 14
Soaking time of the paper cellulose in sodium hydroxide solution is extended into 72h, remaining all conditions is (such as：Raw material
Type, dosage and technological process etc.) it is same as Example 2, stable Cellulose nanocrystal suspension is obtained, through measuring gained
Cellulose nanocrystal average length is about 220nm, and average diameter is about 17nm, yield 53%, PDI 0.2, prepared fibre
Nanocrystalline dimension element is in cellulose Ⅱ crystalline structure.
Embodiment 15
The quality of paper cellulose is increased into 100g, potassium ferrate, sodium hypochlorite, sodium hydroxide, water dosage also phase
Proportional increase is answered, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) it is same as Example 9, after reaction
Processing obtains stable Cellulose nanocrystal suspension also with embodiment 9, is about through measuring gained Cellulose nanocrystal average length
161nm, average diameter are about 7nm, and yield 71%, PDI 0.4, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 16
The quality of paper cellulose is increased into 500g, potassium ferrate, sodium hypochlorite, sodium hydroxide, water dosage also phase
Proportional increase is answered, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) it is same as Example 9, after reaction
Processing obtains stable Cellulose nanocrystal suspension also with embodiment 9, is about through measuring gained Cellulose nanocrystal average length
165nm, average diameter are about 8nm, and yield 69%, PDI 0.3, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 17
The quality of paper cellulose is increased into 1000g, potassium ferrate, sodium hypochlorite, sodium hydroxide, water dosage also phase
Proportional increase is answered, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) it is same as Example 9, after reaction
Processing obtains stable Cellulose nanocrystal suspension also with embodiment 9, is about through measuring gained Cellulose nanocrystal average length
190nm, average diameter are about 12nm, and yield 66%, PDI 0.5, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 18
Oxometallate used is sodium bismuthate, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) with
Embodiment 1 is identical, obtains stable Cellulose nanocrystal suspension, is about through measuring gained Cellulose nanocrystal average length
255nm, average diameter are about 18nm, and yield 52%, PDI 0.3, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 19
Oxometallate used is potassium nitrate, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) with
Embodiment 1 is identical, obtains stable Cellulose nanocrystal suspension, is about through measuring gained Cellulose nanocrystal average length
325nm, average diameter are about 22nm, and yield 49%, PDI 0.3, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 20
Oxometallate used is potassium chlorate, remaining all conditions is (such as：Raw material type, dosage and technological process etc.) with
Embodiment 1 is identical, obtains stable Cellulose nanocrystal suspension, is about through measuring gained Cellulose nanocrystal average length
265nm, average diameter are about 20nm, and yield 50%, PDI 0.3, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
Embodiment 21
Oxometallate used is hyperbromic acid potassium, remaining all conditions is (such as：Raw material type, dosage and technological process etc.)
It is same as Example 1, stable Cellulose nanocrystal suspension is obtained, is about through measuring gained Cellulose nanocrystal average length
215nm, average diameter are about 18nm, and yield 54%, PDI 0.3, prepared Cellulose nanocrystal is in cellulose Ⅱ crystal form
Structure.
By the content summary of embodiment 1-21 in table 1, easy-to-read comparison.
Comparative example 1
It is added without sodium hypochlorite, all conditions such as remaining raw material type, dosage and technological process are same as Example 2,
Cellulose nanocrystal obtained by oxidized hydrolysis is in cellulose Ⅱ crystalline structure, average length 625nm, and average diameter is about
35nm, and the yield of gained Cellulose nanocrystal is 25%, PDI 0.5.Compared with Example 2, identical in other conditions
In the case of, the average length of gained Cellulose nanocrystal is shorter after addition sodium hypochlorite, yield higher, and its distribution of lengths is more
It is narrow.
Likewise, applicant has attempted to be added without other situations that sodium hypochlorite prepares II crystal form Cellulose nanocrystals.It protects
Embodiment 1 and the experiment condition of 3-21 are held, sodium hypochlorite is only added without, can equally generate II crystal form Cellulose nanocrystals.
Comparative example 2
The addition of highly basic can improve the oxidisability of oxometallate and product is made to be II crystal form celluloses, be added without certain dense
The transformation of crystal form will not occur for the highly basic of degree.
It is added without sodium hydroxide in the aqueous solution of oxometallate, the reaction system of hydrolysis is made to be in neutrality environment, remaining institute
Having ready conditions, (raw material type, dosage and technological process etc.) is same as Example 1, and cellulose fento obtained by oxidized hydrolysis is I
Crystal form cellulose fento, average length are 4.9 μm, and average diameter is about 100nm, much larger than gained cellulose in embodiment 1
Nanocrystalline average length, and the yield of cellulose fento is 8%, the yield being far below in embodiment 1, and its distribution of lengths
Also wider, PDI 1.0.
1M sodium hydroxides (12g sodium hydroxides are added i.e. in 300mL water), remaining institute are added in the aqueous solution of oxometallate
Having ready conditions, (raw material type, dosage and technological process etc.) is same as Example 1, and cellulose fento is also obtained by oxidized hydrolysis
I crystal cellulose fento, average length 882nm, average diameter are about 45nm, much larger than gained cellulose in embodiment 1
Nanocrystalline average length, and the yield of cellulose fento is 18%, and far below the yield in embodiment 1, and its length is divided
Cloth is also wider, PDI 0.6.
Comparative example 3
When strong base concentrations are higher than 10M, the presence of excess base makes to generate more to precipitate inside system to be covered in fiber surface,
It is unfavorable for hydrolysis progress.In aqueous slkali containing oxometallate the addition of sodium hydroxide be 120g, remaining raw material type,
The various conditions such as dosage and technological process are same as Example 1, and the average length of cellulose fento obtained by oxidized hydrolysis is
1.5 μm, average diameter is about 84nm, and much larger than the average length of gained Cellulose nanocrystal in embodiment 1, and cellulose is micro-
Fine yield is 14%, and far below the yield in embodiment 1, and its distribution of lengths is also wider, PDI 1.0.
Comparative example 4
Alkali is swollen pre-processing the fento that can make cellulose to cellulose, and hydrolyzate is contributed to enter fiber
It is plain internal to promote hydrolysis to carry out.Without the swelling pretreatment of alkali, remaining raw materials used type, dosage and technique stream
The all conditions such as journey are same as Example 1, and the length of Cellulose nanocrystal obtained by oxidized hydrolysis is 750nm, average diameter
About 41nm is more than the average length of gained Cellulose nanocrystal in embodiment 1, and the yield of Cellulose nanocrystal is
16%, far below the yield in embodiment 1, PDI 0.5.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of II crystal form Cellulose nanocrystal, includes the following steps：
After cellulosic material is carried out swelling treatment and is crushed, washing；
It is reacted being dispersed in the aqueous slkali containing oxometallate by pretreated cellulosic material；
Reaction product is post-processed, the II crystal form Cellulose nanocrystal suspensions of stable dispersion are obtained；
Wherein：When preparing the aqueous slkali containing oxometallate, used alkali includes sodium hydroxide, potassium hydroxide, hydrogen
One or more of lithia, saleratus, sodium bicarbonate；
And in the aqueous slkali containing oxometallate, concentration >=1.5M of alkali.
2. preparation method according to claim 1, it is characterised in that：The oxometallate includes potassium ferrate, high ferro
Sour sodium, potassium permanganate, sodium permanganate, potassium nitrate, sodium nitrate, potassium chlorate, sodium chlorate, potassium hyperchlorate, sodium perchlorate, potassium bromate,
One or more of sodium bromate, hyperbromic acid potassium, hyperbromic acid sodium, bismuthic acid potassium, sodium bismuthate.
3. preparation method according to claim 1, it is characterised in that：It will be dispersed in and contain by pretreated cellulosic material
In the aqueous slkali of oxometallate, and hypohalite is added and is reacted；Optionally, the hypohalite include Fluorine monohydroxide potassium,
One or more of Fluorine monohydroxide sodium, postassium hypochlorite, sodium hypochlorite, potassium hypobromite, sodium hypobromite, hypoiodous acid potassium, hypoiodous acid sodium.
4. preparation method according to claim 1, it is characterised in that：In the aqueous slkali containing oxometallate, 1.5M
Concentration≤10M of≤alkali.
5. preparation method according to claim 1, it is characterised in that：The mass ratio of cellulosic material and oxometallate is
1:0.1~9, it is optionally 1:0.5~7, further alternative is 1:1~5.
6. preparation method according to claim 3, it is characterised in that：The mass ratio of oxometallate and hypohalite used
It is 1:0.5~50, it is optionally 1:5~40, further alternative is 1:10~20.
7. preparation method according to claim 1, it is characterised in that：Metal oxygen in the aqueous slkali containing oxometallate
The mass percentage concentration of hydrochlorate is 0.1%~30%, is optionally 1%~25%, further alternative is 2%~20%.
8. preparation method according to claim 1, it is characterised in that：The reaction is to be carried out under conditions of heating stirring
Reaction；Optionally, the temperature of the reaction is 30~100 DEG C, and the time of reaction is 3~48h；It is further alternative, it is described anti-
The temperature answered is 40~60 DEG C, and the time of reaction is 6~8h.
9. preparation method according to claim 1, it is characterised in that：
The cellulosic material includes microcrystalline cellulose, plant cellulose, paper cellulose or alpha-cellulose；
And/or when preparing the aqueous slkali containing oxometallate, used alkali includes sodium hydroxide, potassium hydroxide, hydrogen
One or more of lithia.
10. the Cellulose nanocrystal that a kind of preparation method according to one of claim 1-9 obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810334049.9A CN108383916B (en) | 2018-04-14 | 2018-04-14 | II-crystal-form cellulose nanocrystal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810334049.9A CN108383916B (en) | 2018-04-14 | 2018-04-14 | II-crystal-form cellulose nanocrystal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108383916A true CN108383916A (en) | 2018-08-10 |
| CN108383916B CN108383916B (en) | 2020-12-22 |
Family
ID=63073857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810334049.9A Active CN108383916B (en) | 2018-04-14 | 2018-04-14 | II-crystal-form cellulose nanocrystal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108383916B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109036623A (en) * | 2018-06-29 | 2018-12-18 | 华南理工大学 | A kind of cellulose base ion conductive material of purine-containing structure and preparation method thereof |
| CN110627914A (en) * | 2019-09-27 | 2019-12-31 | 浙江跃维新材料科技有限公司 | Preparation method of nano-cellulose |
| CN111363050A (en) * | 2020-04-27 | 2020-07-03 | 青岛科技大学 | I crystal form biomass nano-cellulose and ultra-fast preparation method thereof |
| CN112375404A (en) * | 2020-10-24 | 2021-02-19 | 青岛科技大学 | Method for removing impurities and modifying waste tire pyrolysis carbon black |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724078A (en) * | 2009-11-26 | 2010-06-09 | 贵州金玖生物技术有限公司 | Method for preparing oxidized cellulose |
| CN102558367A (en) * | 2012-01-11 | 2012-07-11 | 东北林业大学 | Method for ultrasound assisted preparation of uniform rod-like nano-cellulose |
| US20150297371A1 (en) * | 2012-11-19 | 2015-10-22 | Washington State University Research Foundation | Nanocrystalline cellulose materials and methods for their preparation |
| CN105131130A (en) * | 2015-09-24 | 2015-12-09 | 江苏蓝湾生物科技有限公司 | Synthetic method of oxidized cellulose |
| CN105625018A (en) * | 2016-03-22 | 2016-06-01 | 盐城工学院 | Preparation method and application of modified natural bamboo fiber materials |
| CN107056954A (en) * | 2017-03-22 | 2017-08-18 | 青岛科技大学 | A kind of efficient Cellulose nanocrystal preparation method |
-
2018
- 2018-04-14 CN CN201810334049.9A patent/CN108383916B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724078A (en) * | 2009-11-26 | 2010-06-09 | 贵州金玖生物技术有限公司 | Method for preparing oxidized cellulose |
| CN102558367A (en) * | 2012-01-11 | 2012-07-11 | 东北林业大学 | Method for ultrasound assisted preparation of uniform rod-like nano-cellulose |
| US20150297371A1 (en) * | 2012-11-19 | 2015-10-22 | Washington State University Research Foundation | Nanocrystalline cellulose materials and methods for their preparation |
| CN105131130A (en) * | 2015-09-24 | 2015-12-09 | 江苏蓝湾生物科技有限公司 | Synthetic method of oxidized cellulose |
| CN105625018A (en) * | 2016-03-22 | 2016-06-01 | 盐城工学院 | Preparation method and application of modified natural bamboo fiber materials |
| CN107056954A (en) * | 2017-03-22 | 2017-08-18 | 青岛科技大学 | A kind of efficient Cellulose nanocrystal preparation method |
Non-Patent Citations (5)
| Title |
|---|
| 周为群等: "《普通化学（第二版）》", 30 September 2014, 苏州大学出版社 * |
| 广州军区军医学校主编: "《无机化学（第1版）》", 31 May 1981, 中国人民解放军战士出版社 * |
| 朱洪法等: "《无机化工产品手册（第1版）》", 31 December 2008, 金盾出版社 * |
| 李发顺: "《身边的化学原理（第1版）》", 30 April 2017, 知识产权出版社 * |
| 江泽慧主编: "《中国林业工程（第1版）》", 31 May 2002, 济南出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109036623A (en) * | 2018-06-29 | 2018-12-18 | 华南理工大学 | A kind of cellulose base ion conductive material of purine-containing structure and preparation method thereof |
| CN110627914A (en) * | 2019-09-27 | 2019-12-31 | 浙江跃维新材料科技有限公司 | Preparation method of nano-cellulose |
| CN111363050A (en) * | 2020-04-27 | 2020-07-03 | 青岛科技大学 | I crystal form biomass nano-cellulose and ultra-fast preparation method thereof |
| CN112375404A (en) * | 2020-10-24 | 2021-02-19 | 青岛科技大学 | Method for removing impurities and modifying waste tire pyrolysis carbon black |
| WO2022083090A1 (en) * | 2020-10-24 | 2022-04-28 | 青岛科技大学 | Impurity removal and modification method for pyrolysis carbon black of waste tires |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108383916B (en) | 2020-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108383916A (en) | II crystal form Cellulose nanocrystal of one kind and preparation method thereof | |
| CN108373511B (en) | Cellulose nanocrystal and preparation method thereof based on redox system | |
| JP5456269B2 (en) | Method for producing cellulose dispersion | |
| CN109019675A (en) | A kind of nanostructure titanate and its preparation method and application | |
| CN105330755B (en) | A kind of ultra-fine polysaccharide nanofiber and preparation method thereof | |
| US20220033528A1 (en) | Production of Crystalline Cellulose | |
| WO2010078820A1 (en) | Titania composite and preparing method thereof | |
| CN111363050B (en) | I crystal form biomass nano-cellulose and ultra-fast preparation method thereof | |
| CN107056954A (en) | A kind of efficient Cellulose nanocrystal preparation method | |
| CN105600818B (en) | The method and products obtained therefrom of a kind of stannic oxide nanometer powder prepared rich in Lacking oxygen | |
| WO2016136763A1 (en) | Dispersion of titanium oxide particles in organic solvent, and production method for same | |
| CN106117379A (en) | A kind of Oxytarch and its preparation method and application | |
| WO2016136765A1 (en) | Method for producing organic solvent dispersion of titanium oxide particles | |
| CN109666208A (en) | A kind of graphene oxide@SiO2The method of modified poly ethylene film | |
| CN110467218A (en) | The method for bleaching of metatitanic acid in a kind of Titanium White Production By Sulfuric Acid Process | |
| CN108192113B (en) | Preparation of high-concentration wet-state and dry-state chitin nano fiber/whisker and redispersion method thereof | |
| CN105417575B (en) | A kind of preparation method of the single dispersing tin dioxide quantal-point hydrosol | |
| CN215975001U (en) | Water recycling system for preparing sulfuric acid method titanium dioxide calcining seed crystal | |
| CN110152640A (en) | The process of zirconium dioxide capsule membrane coated red schorl type titanium dioxide | |
| WO2023017687A1 (en) | Type ii unmodified cellulose microfibers, and method for manufacturing type ii unmodified cellulose microfibers and compact of same | |
| CN114230680B (en) | Multi-carboxylated cellulose nanocrystals, and preparation method and application thereof | |
| JP2024522734A (en) | One-pot generation of cellulose nanocrystals | |
| CN108359016A (en) | A kind of environmentally friendly nano micro crystal cellulose preparation method | |
| CN109021170A (en) | A kind of preparation method of salt-resistance Nano/micron filament fibers element gel | |
| CN107827162B (en) | Method for producing chemical treating agent potassium permanganate for sand washing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |