CN103588886B - A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof - Google Patents
A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof Download PDFInfo
- Publication number
- CN103588886B CN103588886B CN201310583175.5A CN201310583175A CN103588886B CN 103588886 B CN103588886 B CN 103588886B CN 201310583175 A CN201310583175 A CN 201310583175A CN 103588886 B CN103588886 B CN 103588886B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- micro crystal
- nano micro
- suspension
- nano
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention provides a kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof, use hydroxyl crosslinking agent modified Nano microcrystalline cellulose, the average grain diameter of obtained Easily-water dispersible nanocrystalline cellulose is 85.3-155.5nm, and particle size polydispersity index is 0.419-0.66.Its preparation method is first preparation of nano microcrystalline cellulose suspension, adds hydroxyl crosslinking agent modified Nano microcrystalline cellulose, is then passed through washing, is dried and prepares.Modified nano micro crystal cellulose can be dispersed in water uniformly and stably, and institute's hydroxyl crosslinker component is few, applied range.
Description
Technical field
The invention belongs to cellulose derivative technology field, be specifically related to one the most water-dispersible
Nano micro crystal cellulose and preparation method thereof.
Background technology
Cellulose is the renewable resource that in nature, reserves are the abundantest, is that one has
The natural macromolecular material of biodegradability.From occurring that oil etc. is non-renewable in the world
Since the crisis of the energy, cellulose has been degraded, deep processing with obtain industrial chemicals and
Intermediate is always the focus of various countries' research.Cellulosic molecule is combined by intermolecular hydrogen bonding
Form fiber precursor.In the place that cellulosic molecule is regularly arranged, hydrogen bond is the most, then
Form crystal region;Some places cellulosic molecule irregular arrangement, forms the chance of hydrogen bond
Few, then form indefinite form district.By sulphuric acid hydrolysis cellulose, corrosion removes noncrystalline
District, i.e. can obtain comprising only a diameter of 1-100nm of crystal region, a length of tens to several
The rigid rod fiber element of hundred nanometers, i.e. nano micro crystal cellulose (NCC).With commonly
Non-nanofiber element compare, due to the high-purity of NCC, high-crystallinity, high Young mould
The characteristics such as amount, high intensity, it has the specific surface that the characteristic of nano particle is the hugest in addition
Long-pending, superpower adsorption capacity and high reactivity and the lightweight of biomaterial, degradable,
Bio-compatible and the characteristic such as renewable so that it is demonstrate huge in high-performance composite materials
Application prospect.
General N CC will transport then redisperse in a dried form, to reduce transport chi
Very little, weight and cost.It is dried and can also suppress bacterium and the growth of fungi in NCC, also
It it is the polymerization disperseing NCC to be modified in a solvent or be dispersed in nano composite material
Steps necessary before thing matrix.But NCC prepared by existing mineral acid hydrolysis method does
When being then added in water after dry, can be well dispersed in when only concentration is about 1wt%
In water, form the preferable suspension of dispersion effect.When NCC addition increases further,
Due to the hydroxyl that its surface is abundant, easily form hydrogen bond and cause reuniting, limit NCC's
Range of application.
At Chinese invention patent (application number: 03114288.5, Authorization Notice No.: CN
Disclose in 100360604C) a kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof and
The colloid that it is formed, this invention is initially with carboxymethylcellulose calcium, hydroxyethylation modification etc.
Method carries out surface modification to NCC, then interpolation accounts for NCC in the NCC of surface modification
The hydrophilic colloid of weight 5-150%, obtained microcrystalline cellulose particle size is 6.3
Between-100nm.The microcrystalline cellulose that this method of modifying obtains is nano microcrystalline fiber
Element and the compound of other colloids, cause range of application narrow.
Summary of the invention
The technical problem to be solved be for present in prior art above-mentioned not
Foot, it is provided that a kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof, technique is simple,
Prepared modified Nano microcrystalline cellulose can be dispersed in water, effectively uniformly and stably
Reduce agglomeration.
Solve the technology of the present invention problem and be employed technical scheme comprise that this easy water dispersion nano is micro-
Crystalline cellulose uses hydroxyl crosslinking agent modified Nano microcrystalline cellulose, obtained easy moisture
The average grain diameter dissipating nano micro crystal cellulose is 85.3-155.5nm, and particle size polydispersity refers to
Number is 0.419-0.66.
Preferably, described hydroxyl crosslinking agent is borax or glutaraldehyde.Borax divides with NCC
Hydroxyl in subchain reacts, formed NCC containing boron complexes borate.Glutaraldehyde
First react generation hemiacetal with NCC, then crosslinking generates acetal compound.
Present invention also offers the preparation method of above-mentioned Easily-water dispersible nanocrystalline cellulose,
Comprise the following steps:
(1) preparation of nano microcrystalline cellulose suspension: mineral acid hydrolysis is processed acquisition
Mixed liquor containing nano micro crystal cellulose is centrifugal, washing dialysis again is the most neutral, and through ultrasonic
Dispersion processes, and obtains nano micro crystal cellulose suspension;
(2) the cross-linking modified nano micro crystal cellulose of hydroxyl: to step (1) gained nanometer
In microcrystalline cellulose suspension, dropping alkali lye or acid solution regulation pH are to suitable scope, then add
Entering hydroxyl crosslinking agent, hydroxyl crosslinking agent addition is to receive in nano micro crystal cellulose suspension
The 10-100wt% of rice microcrystalline cellulose cellulose content, stirs 90-360min in 30-45 DEG C,
Fully washing drying process again, obtain Easily-water dispersible nanocrystalline cellulose.
Preferably, step (1) described mineral acid hydrolysis process be by microcrystalline cellulose with
The 64wt% concentrated sulfuric acid is mixed by the mass ratio of 1:10, and stirs under the conditions of 45 DEG C
Reaction 2h.After mineral acid hydrolysis processes, gained nano micro crystal cellulose average grain diameter is
250-270nm.The gained mixed liquor containing nano micro crystal cellulose is washed by centrifugation and is dialysed
Process, remove impurity and the sulfuric acid of residual.This dialysis treatment is by containing nano microcrystalline fiber
The mixed liquor of element is placed in bag filter and dialyses 3-4 days in deionized water.For preventing
Going mouldy, the mixed liquor containing nano micro crystal cellulose need to be at 0-4 during dialysis and preservation
DEG C preserve.
Preferably, step (1) described ultrasonic disperse processes is to use ultrasonic wave to process
30min.Ultrasonic disperse processes the nano micro crystal cellulose suspension obtained and measures NCC's
After concentration, being diluted with water NCC content in nano micro crystal cellulose suspension is 1-
2wt% carries out cross-linking reaction again.
Preferably, the described dry process of step (2) is at temperature-45 DEG C, pressure 20Pa
Under the conditions of freeze-drying 16h.
Preferably, step (2) described hydroxyl crosslinking agent is borax or glutaraldehyde, step
(2) when using alkali lye regulation, hydroxyl crosslinking agent is borax;When using acid solution regulation, hydroxyl is handed over
Connection agent is glutaraldehyde.
It may further be preferable that step (2) described alkali lye is the NaOH of 0.1mol/L
The aqueous solution, regulation pH to 7 when using alkali lye;Described acid solution is the hydrogen chloride of 0.5mol/L
The aqueous solution, regulation pH to 2 when using acid solution.Proton (the H of low concentration+) friendship to aldehyde
Connection reaction has catalytic action, and in pH value more than 7.5, reaction is suppressed, so penta
Dialdehyde cross-linking reaction need to be carried out in acid condition.
In order to make modified Nano microcrystalline cellulose reach best stablizing when being redispersed in water
Effect, the addition of hydroxyl crosslinking agent has also been carried out preferably by the present invention further.
Preferably, nano micro crystal cellulose content during borax addition is suspension
30wt%。
Preferably, nano micro crystal cellulose content during glutaraldehyde addition is suspension
40wt%.When borax consumption is 30wt% or glutaraldehyde consumption is 40wt%, modification is received
Rice microcrystalline cellulose average grain diameter minimizes value, can reach best cross-linking modified effect.
The invention has the beneficial effects as follows: use simple and easy method modified Nano microcrystalline cellulose,
Nano micro crystal cellulose simple to operate, with low cost and modified can be uniform and stable
Be dispersed in water.This Easily-water dispersible nanocrystalline cellulose average grain diameter is only 85.3-
155.5nm, particle size polydispersity index is 0.419-0.66.And what the present invention was added
Hydroxyl crosslinking agent is less, and only has and participate in cross-linking reaction on a small quantity, major part hydroxyl crosslinking
Agent has neither part nor lot in reaction, and removes in washing process subsequently, the modification therefore obtained
Nano micro crystal cellulose is purer, of many uses, has good market prospects.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, knot below
Close embodiment the present invention is described in further detail.
The embodiment of the present invention provides a kind of nano microcrystalline fiber with superior water dispersibility energy
Element.The nano micro crystal cellulose suspension prepared by mineral acid hydrolysis is regulated by acid/base liquid
To suitable pH value, add hydroxyl crosslinking agent and hand over nano microcrystalline surface hydroxyl
Connection, is washed out and is dried prepared Easily-water dispersible nanocrystalline cellulose.
Microcrystalline cellulose used by the present invention (MCC) is the traditional Chinese medicines group limited public affairs of chemical reagent
The column chromatography type microcrystalline cellulose product that department produces, average grain diameter is more than 80 μm.The present invention
Ultrasonic disperse instrument power used is 80W.
Embodiment one
With MCC as raw material, MCC Yu the 64wt% concentrated sulfuric acid is pressed the mass ratio of 1:10
Mixing, and stirring reaction 2h under the conditions of 45 DEG C, mixing speed is 470 ±
10r/min, then stops heating, adds distilled water diluting, then is placed in centrifuge tube, shakes
Swing washing and be placed in the centrifuge that rotating speed is 10000r/min separation, remove supernatant liquor,
Repeated washing is to no longer producing precipitation, in suspended state, then this suspension is placed in dialysis
Dialyse 3-4 days in deionized water in Dai, be 6-7 to pH, and use ultrasonic wavelength-division
Dissipate 30min, obtain nano micro crystal cellulose suspension.Take this nano micro crystal cellulose of 10g
Suspension is dried in 110 DEG C, the quality of accurate weighing dried powder, so that it is determined that wherein
In nano micro crystal cellulose suspension, the concentration of NCC is 4wt%, then is obtained by dilution
NCC content is the nano micro crystal cellulose suspension of 1.0wt%.
Take the nano micro crystal cellulose suspension prepared by 20g, with the hydrogen-oxygen of 0.1mol/L
Change sodium solution regulation pH to 7, add 0.02g borax and (account for nano micro crystal cellulose quality
10%), stirring reaction 90min at 30 DEG C, then with deionized water centrifuge washing 3 times,
Freeze-drying 16h under the conditions of temperature-45 DEG C, pressure 20Pa, obtains nano microcrystalline fiber
Element powder.
Take dry nano micro crystal cellulose powder, be made into the suspension of 6mg/mL, quiet
Putting 30 days and do not settle, employing ZS3000 nano particle size instrument measures its average grain diameter and is
155.5nm, particle size polydispersity index is 0.66.And above-mentioned cross-linking modified before nanometer micro-
Crystalline cellulose suspension average grain diameter is 251.5nm, and particle size polydispersity index is 0.936,
Stand 30min i.e. to settle, illustrate that the present embodiment uses hydroxyl crosslinking agent to enter NCC
It is less likely to occur between molecule after row crosslinking Treatment to reunite, the modified NCC energy of preparation
It is effectively improved the water dispersible of nano micro crystal cellulose.
Embodiment two
The method identical with embodiment one is used to prepare nano micro crystal cellulose suspension.Take
Nano micro crystal cellulose suspension prepared by 20g, molten with the NaOH of 0.1mol/L
Liquid regulation pH to 7, adds 0.06g borax (accounting for the 30% of nano micro crystal cellulose quality),
Stirring reaction 90min at 30 DEG C, then with deionized water centrifuge washing 3 times, in temperature-45
DEG C, freeze-drying 16h under the conditions of pressure 20Pa, obtain nano micro crystal cellulose powder.
Take dry nano micro crystal cellulose powder, be made into the suspension of 6mg/mL, quiet
Putting 30 days and do not settle, employing ZS3000 nano particle size instrument measures its average grain diameter and is
107.4nm, particle size polydispersity index is 0.492.Modification prepared by the present embodiment is described
After NCC can be effectively improved the water dispersible of nano micro crystal cellulose.
Embodiment three
The method identical with embodiment one is used to prepare nano micro crystal cellulose suspension.Take
Nano micro crystal cellulose suspension prepared by 20g, molten with the NaOH of 0.1mol/L
Liquid regulation pH to 7, adds 0.1g borax (accounting for the 50% of nano micro crystal cellulose quality),
Stirring reaction 90min at 30 DEG C, then with deionized water centrifuge washing 3 times, in temperature-45
DEG C, freeze-drying 16h under the conditions of pressure 20Pa, obtain nano micro crystal cellulose powder.
Take dry nano micro crystal cellulose powder, be made into the suspension of 6mg/mL, quiet
Putting 30 days and do not settle, employing ZS3000 nano particle size instrument measures its average grain diameter and is
153.5nm, particle size polydispersity index is 0.632.Modification prepared by the present embodiment is described
After NCC can be effectively improved the water dispersible of nano micro crystal cellulose.
Embodiment four
The method identical with embodiment one is used to prepare nano micro crystal cellulose suspension.Take
Nano micro crystal cellulose suspension prepared by 20g, adjusts with the hydrochloric acid solution of 0.5mol/L
Joint pH to 2, adds 0.04g glutaraldehyde (accounting for the 20% of nano micro crystal cellulose quality),
Stirring reaction 4h at 40 DEG C, then with deionized water centrifuge washing 3 times, absolute ethanol washing
3 times, freeze-drying 16h under the conditions of temperature-45 DEG C, pressure 20Pa, obtain nanometer micro-
Crystalline cellulose powder.
Take dry nano micro crystal cellulose powder, be made into the suspension of 6mg/mL, quiet
Putting 30 days and do not settle, employing ZS3000 nano particle size instrument measures its average grain diameter and is
107.8nm, particle size polydispersity index is 0.540.Modification prepared by the present embodiment is described
After NCC can be effectively improved the water dispersible of nano micro crystal cellulose.
Embodiment five
The method identical with embodiment one is used to prepare nano micro crystal cellulose suspension.Take
Nano micro crystal cellulose suspension prepared by 20g, adjusts with the hydrochloric acid solution of 0.5mol/L
Joint pH to 2, adds 0.08g glutaraldehyde (accounting for the 40% of nano micro crystal cellulose quality),
Stirring reaction 4h at 40 DEG C, then with deionized water centrifuge washing 3 times, absolute ethanol washing
3 times, freeze-drying 16h under the conditions of temperature-45 DEG C, pressure 20Pa, obtain nanometer micro-
Crystalline cellulose powder.
Take dry nano micro crystal cellulose powder, be made into the suspension of 6mg/mL, quiet
Putting 30 days and do not settle, employing ZS3000 nano particle size instrument measures its average grain diameter and is
85.3nm, particle size polydispersity index is 0.419.Illustrate prepared by the present embodiment modified
NCC can be effectively improved the water dispersible of nano micro crystal cellulose.
Embodiment six
The method identical with embodiment one is used to prepare nano micro crystal cellulose suspension.Take
Nano micro crystal cellulose suspension prepared by 20g, adjusts with the hydrochloric acid solution of 0.5mol/L
Joint pH to 2, adds 0.12g glutaraldehyde (accounting for the 60% of nano micro crystal cellulose quality),
Stirring reaction 4h at 40 DEG C, then with deionized water centrifuge washing 3 times, absolute ethanol washing
3 times, freeze-drying 16h under the conditions of temperature-45 DEG C, pressure 20Pa, obtain nanometer micro-
Crystalline cellulose powder.
Take dry nano micro crystal cellulose powder, be made into the suspension of 6mg/mL, quiet
Putting 30 days and do not settle, employing ZS3000 nano particle size instrument measures its average grain diameter and is
144.9nm, particle size polydispersity index is 0.613.Modification prepared by the present embodiment is described
After NCC can be effectively improved the water dispersible of nano micro crystal cellulose.
By the above detailed description to the embodiment of the present invention, it will be appreciated that the present invention solves
Nano micro crystal cellulose powder is difficult to the suspension forming favorable dispersibility, NCC content is higher
The problem of liquid, and it is few to add hydroxyl cross-linked dosage, and low cost, after not affecting NCC
Continuous use.The average grain diameter of the Easily-water dispersible nanocrystalline cellulose obtained by the present invention is
85.3-155.5nm, particle size polydispersity index is 0.419-0.66, and composition is the purest,
There are wide market prospects, it is adaptable to industrial production.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present
And the illustrative embodiments used, but the invention is not limited in this.For ability
For those of ordinary skill in territory, in the situation without departing from spirit and substance of the present invention
Under, various modification and improvement can be made, these modification and improvement are also considered as the present invention's
Protection domain.
Claims (8)
1. an Easily-water dispersible nanocrystalline cellulose, it is characterised in that: use hydroxyl to hand over
Connection agent borax or glutaraldehyde modified Nano microcrystalline cellulose, obtained easy water dispersion nano
The average grain diameter of microcrystalline cellulose is 85.3-155.5nm, and particle size polydispersity index is
0.419-0.66, its preparation method comprises the following steps:
(1) preparation of nano microcrystalline cellulose suspension: mineral acid hydrolysis is processed acquisition
Mixed liquor containing nano micro crystal cellulose is centrifugal, washing dialysis again is the most neutral, and through ultrasonic
Dispersion processes, and obtains nano micro crystal cellulose suspension;
(2) the cross-linking modified nano micro crystal cellulose of hydroxyl: to step (1) gained nanometer
Microcrystalline cellulose suspension drips alkali lye or acid solution regulation pH to suitable scope, employing
PH to 7 is regulated during alkali lye, regulation pH to 2 when using acid solution, add hydroxyl crosslinking
Agent, when using alkali lye regulation, hydroxyl crosslinking agent is borax;When using acid solution regulation, hydroxyl is handed over
Connection agent is glutaraldehyde, and hydroxyl crosslinking agent addition is to receive in nano micro crystal cellulose suspension
The 10-100wt% of rice microcrystalline cellulose cellulose content, stirs 90-360min in 30-45 DEG C,
Fully washing drying process again, obtain Easily-water dispersible nanocrystalline cellulose.
The preparation side of Easily-water dispersible nanocrystalline cellulose the most according to claim 1
Method, it is characterised in that comprise the following steps:
(1) preparation of nano microcrystalline cellulose suspension: mineral acid hydrolysis is processed acquisition
Mixed liquor containing nano micro crystal cellulose is centrifugal, washing dialysis again is the most neutral, and through ultrasonic
Dispersion processes, and obtains nano micro crystal cellulose suspension;
(2) the cross-linking modified nano micro crystal cellulose of hydroxyl: to step (1) gained nanometer
Microcrystalline cellulose suspension drips alkali lye or acid solution regulation pH to suitable scope, employing
PH to 7 is regulated during alkali lye, regulation pH to 2 when using acid solution, add hydroxyl crosslinking
Agent, described hydroxyl crosslinking agent is borax or glutaraldehyde, hydroxyl crosslinking when using alkali lye regulation
Agent is borax;When using acid solution regulation, hydroxyl crosslinking agent is glutaraldehyde, and hydroxyl crosslinking agent adds
Entering amount is the 10-of nano micro crystal cellulose content in nano micro crystal cellulose suspension
100wt%, stirs 90-360min in 30-45 DEG C, more fully washs and at drying
Reason, obtains Easily-water dispersible nanocrystalline cellulose.
The preparation side of Easily-water dispersible nanocrystalline cellulose the most according to claim 2
Method, it is characterised in that: it is by microcrystalline cellulose that step (1) described mineral acid hydrolysis processes
Mix by the mass ratio of 1:10 with the 64wt% concentrated sulfuric acid, and stir under the conditions of 45 DEG C
Mix reaction 2h.
The preparation side of Easily-water dispersible nanocrystalline cellulose the most according to claim 2
Method, it is characterised in that: it is to use ultrasonic wave to process that step (1) described ultrasonic disperse processes
30min。
The preparation side of Easily-water dispersible nanocrystalline cellulose the most according to claim 2
Method, it is characterised in that: the described dry process of step (2) is at temperature-45 DEG C, pressure
Freeze-drying 16h under the conditions of 20Pa.
6. according to easy the to be water-dispersible nano microcrystalline described in any one in claim 2-5
The preparation method of cellulose, it is characterised in that: step (2) described alkali lye is 0.1mol/L
Sodium hydrate aqueous solution;Described acid solution is the hydrochloride aqueous solution of 0.5mol/L.
The preparation side of Easily-water dispersible nanocrystalline cellulose the most according to claim 6
Method, it is characterised in that: borax addition is nano micro crystal cellulose content in suspension
30wt%.
The preparation side of Easily-water dispersible nanocrystalline cellulose the most according to claim 6
Method, it is characterised in that: glutaraldehyde addition is nano micro crystal cellulose content in suspension
40wt%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310583175.5A CN103588886B (en) | 2013-11-19 | 2013-11-19 | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310583175.5A CN103588886B (en) | 2013-11-19 | 2013-11-19 | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103588886A CN103588886A (en) | 2014-02-19 |
CN103588886B true CN103588886B (en) | 2016-08-17 |
Family
ID=50079233
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310583175.5A Expired - Fee Related CN103588886B (en) | 2013-11-19 | 2013-11-19 | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103588886B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104558211B (en) * | 2014-12-22 | 2016-08-17 | 山东聊城阿华制药股份有限公司 | A kind of microcrystalline Cellulose preparation method |
FI3900699T3 (en) * | 2015-11-25 | 2023-09-25 | JeNaCell GmbH | Biotechnologically-produced cellulose-containing article for dermatological use |
CN106633126B (en) * | 2016-10-15 | 2019-06-18 | 浙江金龙纸业有限公司 | Utilize the method for cation nanometer microcrystalline cellulose enhancing hemicellulose membrane |
CN108530545A (en) * | 2017-03-03 | 2018-09-14 | 重庆市曾东燃纳米科技合伙企业(有限合伙) | A kind of nano-cellulose and preparation method thereof |
CN109397443A (en) * | 2017-08-18 | 2019-03-01 | 阜南县润杨家居有限公司 | A kind of protection willow furniture cracking protection liquid |
CN109487625A (en) * | 2017-09-13 | 2019-03-19 | 东北林业大学 | A kind of preparation method of aldehyde crosslinking nano cellulose paper |
CN107670646B (en) * | 2017-09-22 | 2020-03-10 | 中国科学院合肥物质科学研究院 | Beaded nano zero-valent iron/cellulose composite material and application thereof |
CN107760119A (en) * | 2017-09-29 | 2018-03-06 | 安徽德全新型建材科技有限公司 | A kind of preparation method for the thermal insulation coatings of resistance to cold water pipe |
CN112979830B (en) * | 2021-02-19 | 2022-08-23 | 杭州楠大环保科技有限公司 | Degradable filler for microbial agent and preparation method thereof |
CN113087924B (en) * | 2021-04-13 | 2022-04-05 | 华纺股份有限公司 | Method for preparing nano cellulose suspension by low-temperature hydrothermal method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102080342A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Anionic organic particles and preparation and application thereof |
CN102080343A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Application of anion nano microcrystalline cellulose as paper reinforcer |
CN103374188A (en) * | 2012-04-13 | 2013-10-30 | 施乐公司 | Reinforced fluoropolymer composites comprising surface functionalized nanocrystalline cellulose |
-
2013
- 2013-11-19 CN CN201310583175.5A patent/CN103588886B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102080342A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Anionic organic particles and preparation and application thereof |
CN102080343A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Application of anion nano microcrystalline cellulose as paper reinforcer |
CN103374188A (en) * | 2012-04-13 | 2013-10-30 | 施乐公司 | Reinforced fluoropolymer composites comprising surface functionalized nanocrystalline cellulose |
Non-Patent Citations (3)
Title |
---|
"Surface modification of cotton nanocrystals with a silane agent";Marcia de Oliveira Taipina et al.;《Cellulose》;20121111;第20卷(第1期);第217-226页 * |
"SURFACE MODIFICATION OF NANOCRYSTALLINE CELLULOSE AND ITS APPLICATION IN RETENTION";Qinghua Xu et al.;《第十六届木材、纤维素及制浆化学国际会议论文集(第I卷)》;20110608;第413-417页 * |
"改性纳米结晶纤维素对水性聚氨酯浸润性的研究";佘颖等;《林产化学与工业》;20130428;第33卷(第2期);第77-80页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103588886A (en) | 2014-02-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103588886B (en) | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof | |
Yu et al. | Simple process to produce high-yield cellulose nanocrystals using recyclable citric/hydrochloric acids | |
CN104086783B (en) | A kind of method utilizing ionic liquid to prepare graphene oxide/CNT/cellulose pluralgel | |
CN106832437B (en) | A kind of preparation method of silver-carrying nano cellulose-chitosan complex film | |
CN102935521B (en) | Method for preparing fibroin nano-silver hydrosol | |
JP2018514661A (en) | Multifunctional viscose fiber and preparation method thereof | |
CN106829944B (en) | Graphene compound, preparation method and application thereof | |
CN103752847A (en) | Method for preparing hemicellulose/nano-silver colloid rapidly | |
CN106750388B (en) | A kind of preparation method of Arabic gum hollow nano-sphere | |
CN104987516B (en) | A kind of nano-cellulose strengthens the preparation method of tara gum substrate pH intelligent response film | |
CN106905437B (en) | Redispersible powder Cellulose nanocrystal of high heat resistance and preparation method thereof | |
CN102814502A (en) | Preparation method of silver nanoparticle by using hemicellulose as stabilizer | |
CN106883463B (en) | A kind of preparation method of pattern and size tunable type starch nanometer granule | |
CN111253597B (en) | Chitin nanofiber/polyaniline composite gel film and preparation method thereof | |
CN103061174A (en) | Strong acid pretreatment assisted cellulose nano-filament preparation method | |
CN106810800A (en) | A kind of preparation method of antibiotic property polyvinyl alcohol/cellulose oxidation Graphene PVA/CNC GO composite membranes | |
CN106868629B (en) | A method of preparing the double electrical chitin nano fibers of high yield | |
CN108411401B (en) | Nano-selenium composite fiber and preparation method thereof | |
CN104300164A (en) | Preparation method for complex proton exchange membrane | |
CN104874810B (en) | A kind of quick method for preparing nano silver colloidal sol of bagasse extract green | |
CN109134944A (en) | A kind of porous small ball and its application with different chemical functional groups | |
CN109621851B (en) | Preparation method of gamma-valerolactone/glycerol system high-yield lignin micro-nanospheres | |
CN109485736A (en) | A method of preparing nanocrystal cellulose | |
CN104451930B (en) | A kind of preparation method of whisker reinforcement regenerated celulose fibre | |
CN103421203B (en) | A kind of preparation method of nano-cellulose film of application of heat |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20161119 |
|
CF01 | Termination of patent right due to non-payment of annual fee |