CN110317370A - A kind of cationic surfactant modified nanometer cellulose/native rubber composite material and preparation method thereof - Google Patents
A kind of cationic surfactant modified nanometer cellulose/native rubber composite material and preparation method thereof Download PDFInfo
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- CN110317370A CN110317370A CN201910609862.7A CN201910609862A CN110317370A CN 110317370 A CN110317370 A CN 110317370A CN 201910609862 A CN201910609862 A CN 201910609862A CN 110317370 A CN110317370 A CN 110317370A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of preparation methods of cationic surfactant modified nanometer cellulose/native rubber composite material.This method are as follows: it is modified that surface is carried out to nano-cellulose by surfactant, the modified nano-cellulose suspension in surface is blended with a certain proportion of natural rubber latex again, modified nanometer cellulose/natural rubber blend glue stuff is made in drying to certain mass, then mill is added other rubber chemicals and prepares surface-modified nano cellulose/native rubber composite material.The composite material of this method preparation can be applied to the various vulcanized rubber articles such as manufacture sebific duct, tire.
Description
Technical field
The invention belongs to rubber materials, and in particular to a kind of cationic surfactant modified nanometer cellulose/natural rubber
The preparation method of glue composite material.
Background technique
With the high speed development of automotive engineering, people also propose increasingly higher demands to the performance of automobile tire.And
Carbon black is employed for reinforcement rubber for tire as a kind of effect of rubber industry reinforced filling outstanding already, has very excellent
Reinforcing property.But carbon black depends on petroleum resources, while it also has the deficiencies of high pollution, high energy consumption place.Thus visit
Rope goes out a kind of apparent rubber for tire reinforced filling of environmentally protective and effect, is absolutely the research work with breakthrough meaning,
Also the present age environmentally protective, sustainable development themes of the times are more in line with.In recent years, researcher begins one's study natural material
Material, including halloysite nanotubes, nano-cellulose etc., it is intended to the performances such as the mechanical strength of rubber be continuously improved, to hope as wheel
The reinforced filling of tire rubber.
Cellulose, a kind of natural biopolymer are one of the most abundant natural polymers on the earth.With nanometer
The development of technology, the preparation and application of nano-cellulose are more and more extensive.Wherein, nano micro crystal cellulose possesses more complete knot
Crystal structure, biggish specific surface area and excellent mechanical performance, also have it is from a wealth of sources, low in cost, renewable, degradable,
It is environmental-friendly and the advantages that.Can be from bagasse, waste cellulose plate, stalk, timber extracted and is prepared into the raw materials such as waste paper
To nano-cellulose.As the novel supporting material of rubber, this seminar is multiple to rubber/nano micro crystal cellulose in recent years
Condensation material has carried out a series of research.The patent that is authorized 6 (1. ancient chrysanthemums, Jia Demin, Luo Yuanfang, a kind of rubber of Li Xionghui/
Modified microcrystalline cellulose composite material and preparation method thereof Chinese invention patent number: ZL200810219532.9；2. ancient chrysanthemum,
Lin Lu, Xu Suhua, Luo Yuanfang, a kind of preparation side of cellulose nanocrystal/carbon black/natural rubber composite Judd people
Method Chinese invention patent number: 201010522109.3；3. ancient chrysanthemum, Xu Suhua, Luo Yuanfang, a kind of nano microcrystalline of Judd people are fine
Dimension element/white carbon black/rubber composite material preparation method Chinese invention patent number: 201010522126.7；4. ancient chrysanthemum, yellow bodyguard
A kind of preparation method Chinese invention patent number of Cellulose nanocrystal and its rubber composite material based on stalk of literary:
ZL201510971009.1；5. ancient chrysanthemum, the preparation side of a kind of bagasse nano-cellulose of Liang little Rong and its rubber composite material
Method Chinese invention patent number: 201510971007.2；6. ancient chrysanthemum, a kind of bagasse nano-cellulose of Liang little Rong, Li Caixin
Preparation method Chinese invention patent number: 201610376820.X (applying date 2016-5-31,2018-1-5 authorization)).Hair
(1.Ju Gu*, Wanjuan Chen, Lu Lin, Yuan-fang Luo, the De-min Jia. Effect of of table paper 16
Nanocrystalline Cellulose on the Curing Characteristics and Aging Resistance
Properties of Carbon Black reinforced Natural Rubber, Chinese Journal of
Polymer Science, 2013,31 (10): 1382-1393；2. ancient chrysanthemum, Lin Lu, Luo Yuanfang, Judd people's nano microcrystalline
Influence macromolecule journal of the cellulose to black-reinforced natural rubber mechanical property and dynamic property, 2012 (8): 852-860；
3. ancient chrysanthemum, Lin Lu, Luo Yuanfang, the south China Judd people nano micro crystal cellulose alternative carbon black reinforcement natural rubber science and engineering are big
Learn journal, 2012,40 (4): 101-106；4. S.H. Xu, J. Gu*, Y.F. Luo, D.M. Jia. Effects
of partial replacement of Silica with surface modified nanocrystalline
cellulose on properties of natural rubber nanocomposites. Express Polymer
Letters, 2012,6 (1): 14-25；5. Xu Suhua, Gu Ju *, Luo Yuanfang, Judd people's nano micro crystal cellulose is to hard charcoal
The influence composite material journal of black/native rubber composite material performance, 2011,28 (6): 39-44；6. ancient chrysanthemum *, beam are small
Hold, Huang Fei, Wang Juan, Huang Shiwen nano-cellulose reinforced rubber progress, South China Science & Engineering University's journal, 2016.44 (2):
124-132；7. Xu Yingni; Li Caixin; Gu Ju. Effects of MAH/St grafted
nanocellulose on the properties of carbon reinforced styrene butadiene
rubber, Journal of Polymer Engineering, 2019, 39(5): 450-458；8. Caixin Li,
Fei Huang, Juan Wang, Xiaorong Liang, Shiwen Huang, Ju Gu*. Effects of
partial replacement of Carbon Black with nanocrystalline cellulose on
properties of natural rubber nanocomposites. Journal of Polymer Engineering,
2018, 38(2): 137-146；9. Shen Peiyao, Liang little Rong, Li Caixin, Gu Ju alkaline process prepare bagasse nano-cellulose/butylbenzene
Rubber composite material performance, Journal of Chemical Industry and Engineering, 2018,69 (6): 2759-2766；10. Li Caixin, Liang little Rong, Gu Ju * bagasse
The preparation and representation of nano-cellulose, Chemical Journal of Chinese Universities, 2017,38 (7): 1286-1294；11. Huang Shiwen, ancient
The interface interaction of chrysanthemum * stalk nano cellulose and black-reinforced natural gum, polymer material science and engineering, 2017,33
(11): 93-100；12. ancient chrysanthemum *, Huang Shiwen, as if friend, Xiao Haiyan wood powder nano micro crystal cellulose reinforcement NR/SBR/BR is used in combination
The research of glue, South China Science & Engineering University's journal, 2017.45 (2): 122-129；13. ancient chrysanthemum *, Lin Lu, Luo Yuanfang, Judd people's silicon
Alkane coupling agent KH-550 is to the influence of nanocrystalline cellulose/carbon black/native rubber composite material performance, rubber industry, and 2017.64
(5): 279-284；14. Wang Juan, Huang Fei, Huang Shiwen, Liang little Rong, Li Caixin, Gu Ju * waste paper fibre element are nanocrystalline to carbon black
The vulcanization characteristics of reinforcement natural rubber and the influence of processing performance, polymer material science and engineering, 2016,32 (12): 43-
48；15.Suhua Xu, Ju Gu*, Yuanfang Luo, Demin Jia, Lin Yan. Influence of
Nanocrystalline Cellulose on Structure and Properties of Natural Rubber/
Silica Composites. Polymer Composites, 2015, 36(5): 861-868；16.W. J. Chen, J.
Gu*, S. H. Xu. Exploring nanocrystalline cellulose as a green alternative of
carbon black in natural rubber/butadiene rubber/styrene-butadiene rubber
Blends, Express Polymer Letters, 2014,8 (9): 659-668).Wherein, nano-cellulose reinforcing effect
Dispersion and interface cohesion situation mainly by nano-cellulose in rubber matrix.
Inventor notices that the nano-cellulose of oxidizing process preparation since part of hydroxyl is oxidized to carboxyl, thus makes nanometer
Cellulose surface has negative electrical charge, thus it is modified to nano-cellulose progress surface that cationic surfactant can be selected.It is modified
Nano-cellulose afterwards can be well dispersed in natural rubber matrix, simultaneously because modified nano-cellulose has alkane
Cardinal extremity, thus the interface cohesion of nano-cellulose and natural rubber is improved, to show reinforcing effect outstanding.It is this
The modified nano-cellulose applying filler in surface is in reinforcement natural rubber, as can developed the novel supporting material for tire,
Partially or completely replace carbon black or white carbon black, huge economic benefit and social benefit will be brought to rubber industry.
Summary of the invention
It is an object of the invention to defects aiming at the problems existing in the prior art, provide a kind of cationic surfactant
Modified nanometer cellulose/native rubber composite material preparation method.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of cationic surfactant modified nanometer cellulose/native rubber composite material, first passes through dual
Raw material is oxidized to nano-cellulose by oxidizing process, then cationic surfactant modified nanometer cellulose, then by modified Nano
Cellulose/Heveatex passes through emulsion blending process flow.
In the above method, raw material is oxidized to nano-cellulose by the dual oxidizing process, comprising the following steps: uses raw material
After the NaOH solution that mass fraction is 5 %-30% impregnates 5 ~ 30 min, blends, filtration washing obtains slurry, add slurry into matter
Amount score is that 10%-30% ammonium persulfate solution stirs sufficiently reaction 1-5h at 50-100 DEG C, after the reaction was completed centrifuge washing；It adjusts
Section pH is 9-11, and under the conditions of 50-80 DEG C, H is added2O2, ultrasonic oxidation 10-30min；Product dialysis 5-7d after being centrifuged, then
Product after dialysis is broken up into 5-10min with beating crusher, the nano-cellulose suspension for taking supernatant to prepare after centrifugation.
In the above method, the revolving speed of the centrifugation is 3000-5000r/min, centrifugation time 3-5min；The dialysis of use
The molecular weight of film retention is 14000.
In the above method, the cationic surfactant modified nanometer cellulose, step includes: to take nano-cellulose
Suspension is in three-necked flask, and under 40-80 DEG C of condition of water bath heating, cationic surfactant is added, reacts 2-4h, instead
The unadsorbed activating agent on nano-cellulose surface is removed in 3000-5000r/min centrifugation 3-5min after answering, finally obtains surface
Modified nano-cellulose.
In the above method, the cationic surfactant is hexadecane trimethyl ammonium bromide, cetrimonium chlorination
Ammonium, phenyl trimethicone ammonium chloride, dodecane trimethylammonium bromide, glycidyltrimetiiylammonium ammonium chloride, diallydimethyl
One or more of ammonium chloride；The cationic surfactant additional amount is 0.5-2 times of nano-cellulose quality.
In the above method, for the modified nanometer cellulose/Heveatex by emulsion blending, step includes: by 2-
The modified nano-cellulose in the surface 8g is added in 15-30g Heveatex, and 10-30 min is stirred at room temperature, keeps two-phase uniform
Mixture, is then placed in 40-60 DEG C of constant temperature blast drying oven by mixing, obtains blend glue stuff after drying to constant weight；Again will
Blend glue stuff is kneaded on a mill, park after 24-36h the vulcanization at 140-145 DEG C obtain the modified nano-cellulose in surface/
Native rubber composite material.
In the above method, the solid content of the Heveatex is 55-65%.
The present invention is had the following advantages and beneficial effects: compared with existing technology
1, using deionized water as solvent, by cationic surfactant modified nanometer cellulose, have easy to operate, be easy to anti-
It answers, low power consumption and other advantages, and modified effect is obvious, rubber matrix can be well dispersed in, and improve two-phase interface effect.
2, surfactant-modified nano-cellulose/native rubber composite material prepared by the present invention has outstanding
Reinforcing effect makes it can partially or completely conventional fillers such as alternative carbon black.
Detailed description of the invention
Fig. 1 is the Zeta potential figure of nano-cellulose (using microcrystalline cellulose as raw material)；
Fig. 2 is straw pulp (a), the FTIR map of nano-cellulose (b) and modified nanometer cellulose (c)；
Fig. 3 is nano-cellulose (left side) and modified nanometer cellulose (right side) comparison diagram；
Fig. 4 is the Zeta potential figure of nano-cellulose (a) and modified nanometer cellulose (b) sum；
Fig. 5 is the mechanism figure that nano-cellulose (NCC) adsorbs cetyl trimethylammonium bromide；
Fig. 6 is the thermal multigraph of nano-cellulose (a) and modified nanometer cellulose (b) and surfactant (c)；
Fig. 7 is the X-ray diffractogram of nano-cellulose (a) and modified nanometer cellulose (b)；
Fig. 8 is influence diagram of the surfactant to compounded rubber mechanical property.
Specific embodiment
The present invention will be further specifically described in detail with reference to specific embodiments, but embodiments of the present invention are not
It is limited to this, for not specifically specified technological parameter, can refer to routine techniques progress.
Embodiment 1
Using eucalyptus pulp as raw material, after impregnating 10 min of paper pulp with the NaOH solution that mass fraction is 10 %, blend, filtration washing
Obtain slurry.Slurry is uniformly mixed with mass fraction for 20% ammonium persulfate solution, 80 DEG C of stirrings are heated under water bath condition and are filled
Divide reaction 2 h, after the reaction was completed centrifuge washing；It adjusts pH and H is added under the conditions of 70 DEG C to alkalinity2O2, ultrasonic agitation；Reaction
4000r/min is centrifuged 5min after completely, by regenerated cellulose dialysis membrane (14000 molecular weight of retention) the dialysis 5- of product after centrifugation
7d.Then the product after dialysis is broken up into 5-10min with beating crusher, 3min is centrifuged under the conditions of 4000r/min, is taken after centrifugation
Clear liquid is the nano-cellulose suspension prepared.
Taking 100mL concentration is 15mg/mL nano-cellulose suspension in three-necked flask, in 60 DEG C of condition of water bath heating
Under, it is slowly added to 2g phenyl trimethicone ammonium chloride, reacts 3h, it is unadsorbed in NCC in 4000r/min centrifugation 3min removing after reaction
The activating agent on surface obtains the modified nano-cellulose in surface.
The modified nano-cellulose in the surface 2g is added in Heveatex (20g), 20 min are stirred at room temperature, make two-phase
Mixture, is then placed in 60 DEG C of constant temperature blast drying oven by uniformly mixing, obtains blend glue stuff after drying to constant weight；Again will
Blend glue stuff is kneaded on a mill, and the modified Eucalyptus-nanofiber in surface can be obtained in vulcanization at 143 DEG C after parking 24 well
Element/native rubber composite material.
Embodiment 2
Using microcrystalline cellulose as raw material, after impregnating 10 min of microcrystalline cellulose with the NaOH solution that mass fraction is 10 %, blend,
Filtration washing.The ammonium persulfate solution that mass fraction is 20% is added in the microcrystalline cellulose after alkali process again, under water bath condition
80 DEG C of stirrings sufficiently reaction 1.5h is heated, after the reaction was completed centrifuge washing；It adjusts pH and is added under the conditions of 70 DEG C to alkalinity
H2O2, ultrasonic agitation；4000r/min is centrifuged 3min after fully reacting, by the regenerated cellulose dialysis membrane (retention of product after centrifugation
14000 molecular weight) dialysis 5-7d.Then the product after dialysis is broken up into 5-10min with beating crusher, under the conditions of 4000r/min
It is centrifuged 3min, the nano-cellulose suspension for taking supernatant to prepare after centrifugation.
Fig. 1 is the Zeta potential figure of the nano-cellulose prepared by raw material of microcrystalline cellulose, surface portion hydroxyl quilt
It is oxidized to carboxyl, to make surface with negative electrical charge (Zeta potential -39.2mV).
Embodiment 3
Using needle wood pulp as raw material, after impregnating 10 min of paper pulp with the NaOH solution that mass fraction is 10 %, blends, crosses diafiltration
It washs to obtain slurry.Slurry is uniformly mixed with the ammonium persulfate solution that mass fraction is 20%, 80 DEG C is heated under water bath condition and stirs
Sufficiently reaction 1.5h is mixed, after the reaction was completed centrifuge washing；It adjusts pH and H2O2 is added under the conditions of 70 DEG C to alkalinity, ultrasound is stirred
It mixes；4000r/min is centrifuged 3min after fully reacting, by regenerated cellulose dialysis membrane (14000 molecules of retention of product after centrifugation
Amount) dialysis 5-7d.Then the product after dialysis is broken up into 5-10min with beating crusher, is centrifuged 3min under the conditions of 4000r/min,
The nano-cellulose suspension for taking supernatant to prepare after centrifugation.
Taking 100mL concentration is 20mg/mL nano-cellulose 2g in three-necked flask, under 60 DEG C of condition of water bath heating,
It is slowly added to 2g hexadecane trimethyl ammonium bromide (CTMAB), reacts 3h, do not inhaled after reaction in 4000r/min centrifugation 3min removing
It is attached to the CTMAB on the surface NCC, obtains the modified nano-cellulose in surface.
The modified nano-cellulose in the surface 2g is added in the Heveatex of 20g, 20 min are stirred at room temperature, make two-phase
Mixture, is then placed in 60 DEG C of constant temperature blast drying oven by uniformly mixing, obtains blend glue stuff after drying to constant weight；Again will
Blend glue stuff is kneaded on a mill, and vulcanization obtains the modified nano-cellulose/natural rubber in surface at 143 DEG C after parking 24 well
Glue composite material.
Fig. 2 is paper pulp raw material (a), and the FTIR map of nano-cellulose (b) and modified nanometer cellulose (c) is modified
There is new peak at 3020,2850cm -1 in nano-cellulose, belongs to the CH2 and CH3 at CTMAB alkyl end；At 1480cm-1
It is attributed to the methyl of cationic substituent；Simultaneously 2900 on NCC map at peak value to 2930 offsets；Surfactant is successfully inhaled
Invest nano-cellulose surface.
Fig. 3 is nano-cellulose (left side) and modified nanometer cellulose (right side) comparison diagram, modified through surfactant surface
NCC is dispersed in water, and NCC can be fallen in water.This also shows negatively charged NCC and successfully inhales that append cationic surface living
Property agent, NCC settled from water be attributed to surfactant alkyl end hydrophobicity.
Fig. 4 be nano-cellulose (NCC) and modified nanometer cellulose (m-NCC) and Zeta potential figure, Fig. 5 is Nanowire
Tie up the mechanism figure of plain (NCC) absorption cetyl trimethylammonium bromide；Have from nano-cellulose surface known to Zeta potential test
There is negative electrical charge (current potential is -45.2mV), this is mainly the NCC of oxidizing process preparation since part of hydroxyl is oxidized to carboxyl.Through sun
Ionic surface active agent is modified, due to cationic surfactant by Electrostatic Absorption on NCC, to change NCC's
Surface charging property.NCC surface potential after modified be+23.6mV, this result also further demonstrated that surfactant at
Function acts on nano-cellulose.
Fig. 6 is the thermogravimetric of nano-cellulose (NCC) and modified nanometer cellulose (m-NCC) and surfactant (TCMAB)
Figure；It is about 20 wt% that final residual amount, which can calculate and be adsorbed on the quality of the cationic surfactant on the surface NCC,.
Fig. 7 is the X-ray diffractogram of nano-cellulose (NCC) and modified nanometer cellulose (m-NCC)；It can be seen that nanometer
The diffracted primary peak of cellulose respectively corresponds (1-1 0), (2 0 0) and (4 at the angle of diffraction 2 θ=15 o, 22.6 °, 34.6 °
The diffraction of 0 0) crystal face is the diffraction maximum of cellulose I type.Through XRD test it is found that NCC is modified through cationic surfactant,
The crystal form and crystallinity of NCC is almost unchanged, illustrates that influence of the surfactant to crystal form and crystallinity is little.
Fig. 8 is influence of the surfactant to compounded rubber mechanical property；The stretching that the addition of NCC significantly improves NR is strong
Degree, is mainly prepared for the preferable NCC of performance and purity, NCC imparts the certain intensity of NR, to make the drawing of composite material
Intensity is stretched to be improved.And after NR is added in surface-modified NCC, increase the mechanical property (12.6MPa) of NR more than one times,
27.2MPa is reached.This may be because NCC after modified, can be better dispersed in natural rubber, at the same the surface NCC inhale
Specific surface area is increased after attached cationic surfactant, to increase the acting surface with rubber matrix, while improving boundary
Face, so as to improve the mechanical property of NCC/NR compounded rubber.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (8)
1. a kind of preparation method of cationic surfactant modified nanometer cellulose/native rubber composite material, feature exist
In: dual oxidizing process is first passed through by raw material and is oxidized to nano-cellulose, then cationic surfactant modified nanometer cellulose,
Modified nanometer cellulose/Heveatex is passed through into emulsion blending process flow again.
2. cationic surfactant modified nanometer cellulose/native rubber composite material preparation according to claim 1
Method, it is characterised in that: raw material is oxidized to nano-cellulose by the dual oxidizing process, comprising the following steps: by raw material matter
It measures after the NaOH solution that score is 5 %-30% impregnates 5 ~ 30 min, blends, filtration washing obtains slurry, add slurry into quality
Score is that 10%-30% ammonium persulfate solution stirs sufficiently reaction 1-5h at 50-100 DEG C, after the reaction was completed centrifuge washing；It adjusts
PH is 9-11, and under the conditions of 50-80 DEG C, H is added2O2, ultrasonic oxidation 10-30min；Product dialysis 5-7d, then will after being centrifuged
Product after dialysis breaks up 5-10min with beating crusher, the nano-cellulose suspension for taking supernatant to prepare after centrifugation.
3. cationic surfactant modified nanometer cellulose/native rubber composite material preparation according to claim 2
Method, it is characterised in that: the revolving speed of the centrifugation is 3000-5000r/min, centrifugation time 3-5min；The dialysis membrane of use
The molecular weight of retention is 14000.
4. cationic surfactant modified nanometer cellulose/native rubber composite material preparation according to claim 1
Method, it is characterised in that: the cationic surfactant modified nanometer cellulose, step include: to take nano-cellulose outstanding
Supernatant liquid is in three-necked flask, and under 40-80 DEG C of condition of water bath heating, cationic surfactant is added, and reacts 2-4h, reaction
The unadsorbed activating agent on nano-cellulose surface is removed in 3000-5000r/min centrifugation 3-5min afterwards, surface is finally obtained and changes
The nano-cellulose of property.
5. cationic surfactant modified nanometer cellulose/native rubber composite material preparation according to claim 4
Method, it is characterised in that: the cationic surfactant be hexadecane trimethyl ammonium bromide, hexadecyltrimethylammonium chloride,
Phenyl trimethicone ammonium chloride, dodecane trimethylammonium bromide, glycidyltrimetiiylammonium ammonium chloride, diallyidimethylammonium chloride
One or more of ammonium；The cationic surfactant additional amount is 0.5-2 times of nano-cellulose quality.
6. cationic surfactant modified nanometer cellulose/native rubber composite material preparation according to claim 1
Method, it is characterised in that: for the modified nanometer cellulose/Heveatex by emulsion blending, step includes: by 2-8g table
The modified nano-cellulose in face is added in 15-30g Heveatex, and 10-30 min is stirred at room temperature, mixes two-phase uniformly
It closes, is then placed in mixture in 40-60 DEG C of constant temperature blast drying oven, obtain blend glue stuff after drying to constant weight；It will mix again
It closes sizing material to be kneaded on a mill, parks after 24-36h that vulcanization obtains the modified nano-cellulose/day in surface at 140-145 DEG C
Right rubber composite material.
7. cationic surfactant modified nanometer cellulose/native rubber composite material preparation according to claim 6
Method, it is characterised in that: the solid content of the Heveatex is 55-65%.
8. the cationic surfactant modified nano fiber that any preparation method described in -7 is prepared according to claim 1
Element/native rubber composite material.
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| CN111393720A (en) * | 2020-04-26 | 2020-07-10 | 太仓荣南密封件科技有限公司 | Nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and preparation method thereof |
| CN113150309A (en) * | 2021-03-26 | 2021-07-23 | 湖北福力德鞋业有限责任公司 | Method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose |
| CN113549333A (en) * | 2021-08-16 | 2021-10-26 | 长沙新立硅材料科技有限公司 | Nano-cellulose and polymer composite modified thermoplastic asphalt material and preparation method thereof |
| CN114134597A (en) * | 2021-12-13 | 2022-03-04 | 罗莱生活科技股份有限公司 | Latex-lyocell composite fiber and preparation method thereof |
| CN114134597B (en) * | 2021-12-13 | 2023-10-31 | 罗莱生活科技股份有限公司 | Latex-lyocell composite fiber and preparation method thereof |
| WO2023219077A1 (en) * | 2022-05-10 | 2023-11-16 | 東亞合成株式会社 | Intermediate and intermediate production method |
| CN115417931A (en) * | 2022-09-22 | 2022-12-02 | 上海同化益生纤生物科技有限公司 | Preparation method and application of temperature-resistant cellulose |
| CN115417931B (en) * | 2022-09-22 | 2024-03-22 | 上海同化益生纤生物科技有限公司 | Preparation method and application of temperature-resistant cellulose |
| CN115536921A (en) * | 2022-10-24 | 2022-12-30 | 中国化工集团曙光橡胶工业研究设计院有限公司 | Natural rubber material and preparation method thereof |
| CN115536921B (en) * | 2022-10-24 | 2023-09-26 | 中国化工集团曙光橡胶工业研究设计院有限公司 | Natural rubber material and preparation method thereof |
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