CN114539639A - Preparation method of dopamine-modified microcrystalline cellulose-reinforced natural rubber - Google Patents
Preparation method of dopamine-modified microcrystalline cellulose-reinforced natural rubber Download PDFInfo
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- CN114539639A CN114539639A CN202210295696.XA CN202210295696A CN114539639A CN 114539639 A CN114539639 A CN 114539639A CN 202210295696 A CN202210295696 A CN 202210295696A CN 114539639 A CN114539639 A CN 114539639A
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- microcrystalline cellulose
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- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 40
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 40
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 59
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 59
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 59
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 59
- 229960003638 dopamine Drugs 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 29
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 239000007853 buffer solution Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002313 adhesive film Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 6
- 229920001690 polydopamine Polymers 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CWGFSQJQIHRAAE-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.OCC(N)(CO)CO CWGFSQJQIHRAAE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of dopamine modified microcrystalline cellulose reinforced natural rubber, which is characterized by comprising the following steps: preparing buffer solution with the pH value of 8.5 by using tris (hydroxymethyl) aminomethane hydrochloride, adding dopamine and microcrystalline cellulose, and stirring for reaction; secondly, grinding the zinc oxide, the rubber additive and the sulfur to obtain uniform slurry-like mixed liquid; thirdly, respectively adding the mixed liquid prepared in the first step and the second step into the natural latex, continuously stirring the mixture for curing, pouring the mixture on a smooth glass vessel, and placing the mixture in an oven for dehydration; fourthly, the dry adhesive film prepared in the step three is processed at the temperature of 140-90Vulcanizing on a flat vulcanizing machine under the condition of (1) to obtain the dopamine modified microcrystalline cellulose/natural rubber composite material. Modified microcrystalline cellulose reinforced Natural rubber of the inventionHas good physical and mechanical properties, obviously improves the tensile strength and the tearing strength, and greatly improves the dispersion of the filler.
Description
Technical Field
The invention belongs to the field of rubber materials, relates to modified natural rubber and a preparation method thereof, and particularly relates to dopamine-modified microcrystalline cellulose-reinforced natural rubber and a preparation method thereof.
Background
Cellulose is a natural biodegradable material that is present in the largest natural stocks (annual production of 10)10-1011Ton), about 45% in wood, about 60% in flax and about 85% in cotton, are important constituents of plant cell walls and have the advantages of low density and low price. The microcrystalline cellulose (MCC) keeps a complete crystalline structure and excellent mechanical property of cellulose, and has the characteristics of simple preparation method and low cost, so the MCC can be used as a green reinforcing filler.
MCC has very strong hydrophilic properties due to the presence of a large number of hydroxyl groups on the surface of the MCC particles. The surface interaction between polar fillers and non-polar Natural Rubber (NR) matrices is very weak, which is also undesirable for many composite applications. However, the interfacial interactions between rubber and filler are critical factors in determining the final properties of filled rubber composites. The effectiveness of the rubber-filler interaction depends largely on the nature of the filler surface groups.
At present, the hydrophilicity of MCC is improved mainly by two methods, namely, a surfactant is added to wrap particles and separate the particles; secondly, surface chemical modification is carried out to reduce the hydroxyl on the surface. However, the second method of surface chemical modification usually requires complex multi-step reactions, and some may even produce toxic by-products. For example, patent document CN111138724A discloses a maleic anhydride modified nano microcrystalline cellulose reinforced natural rubber and a preparation method thereof, comprising the following steps: (1) adding a maleic anhydride/toluene solution into an NCC aqueous dispersion, wherein the mass ratio of maleic anhydride to NCC is 1.2-1.8, uniformly mixing, and reacting at 90-110 ℃ for 4.5-5.5 h; (2) and (3) using hot water to perform water-resisting cooking to coagulate the grafted product, and after a large amount of solvent and unreacted substance are evaporated until no liquid exists, performing vacuum drying on the modified product at 40-60 ℃ to a constant amount to obtain a grafted product of maleic anhydride grafted NCC: NCC-g-MAH; (3) preparing the prepared NCC-g-MAH and a proper solvent into sol, and uniformly mixing the sol with natural rubber emulsion, wherein the mass ratio of the NCC-g-MAH to the natural rubber emulsion is 0.6-1%, stirring for 20-28h under the action of a magnetic stirrer, pouring the mixture into a glass dish, and drying for 36-60h at the temperature of 50-70 ℃ in a drying oven to obtain the maleic anhydride modified nano microcrystalline cellulose reinforced natural rubber.
The above patent documents modify microcrystalline cellulose to enhance the interfacial interaction between rubber and filler and improve dispersibility. However, the modification method of the microcrystalline cellulose needs to be carried out for multiple times of reaction, is relatively complex, and is used for preparing the rubber composite material by adopting a traditional mixing method subsequently, and various additives are added to ensure the physical and mechanical properties of the composite rubber. At present, no simpler and more convenient preparation method and product of modified microcrystalline cellulose reinforced rubber are available.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of dopamine modified microcrystalline cellulose reinforced natural rubber, which is characterized by comprising the following steps:
preparing buffer solution with the pH value of 8.5 by taking Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCL), adding Dopamine (DA) and microcrystalline cellulose (MCC), and stirring for reaction;
secondly, grinding the zinc oxide, the rubber additive and the sulfur to obtain uniform slurry-like mixed liquid;
thirdly, respectively adding the mixed liquid prepared in the first step and the second step into the natural latex, continuously stirring the mixture for curing, pouring the mixture on a smooth glass vessel, and placing the mixture in an oven for dehydration;
fourthly, the dry adhesive film prepared in the step three is processed at the temperature of 140-90Vulcanizing on a flat vulcanizing machine under the condition of (1) to obtain the dopamine modified microcrystalline cellulose/natural rubber composite material.
The invention also aims to provide a preparation method of the dopamine modified microcrystalline cellulose reinforced natural rubber, which is characterized by comprising the following steps:
preparing buffer solution with the pH value of 8.5 by taking Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCL), adding Dopamine (DA) and microcrystalline cellulose (MCC), and stirring for reaction;
secondly, grinding the zinc oxide, the rubber additive and the sulfur to obtain uniform slurry-like mixed liquid;
thirdly, respectively adding the mixed liquid prepared in the first step and the second step into the natural latex, continuously stirring the mixture for curing, pouring the mixture on a smooth glass vessel, and placing the mixture in an oven for dehydration;
mixing the dry rubber film prepared in the step (c) to obtain a dopamine modified microcrystalline cellulose/natural rubber master batch;
fifthly, mixing the master batch with a certain amount of natural rubber at the temperature of 140-90Vulcanizing on a flat vulcanizing machine under the condition of (1) to obtain the dopamine modified microcrystalline cellulose/natural rubber composite material.
Preferably, the mass ratio of the dopamine to the microcrystalline cellulose in the step (i) is (0.1-2):1, the stirring reaction time is 3-7h, and the stirring reaction temperature is 20-30 ℃.
Preferably, the rubber auxiliary in the step (II) is 1-5 parts of dispersion stabilizer, 0.5-3 parts of accelerator, 1-3 parts of sulfur and 2-5 parts of zinc oxide.
Preferably, the grinding time in the step (II) is 1 to 3 hours.
Preferably, in the third step, the weight ratio of the first step to the mixed liquid prepared in the second step is 1:2-1:8, and the weight ratio of the two mixed liquids to the natural latex is 1:1-1: 10.
Preferably, the stirring reaction condition in the third step is that the stirring time is 3-6h at 60 ℃ and the dehydration temperature is 80-90 ℃.
Preferably, the natural rubber latex in the step (c) is a natural rubber emulsion with 60% of solid content.
Preferably, in the step (iv), the mixing temperature is 80 ℃ and the mixing time is 20 min.
The invention also aims to provide the dopamine modified microcrystalline cellulose reinforced natural rubber prepared by the preparation method.
Compared with the prior art, the method adopts dopamine as a modifier, utilizes the technology of dopamine oxidation autopolymerization and physical modification to modify the surface of microcrystalline cellulose to obtain microcrystalline cellulose which only improves the surface physical property without damaging the internal crystalline region structure, adopts natural latex as a matrix, and adopts a latex blending wet process to successfully prepare the natural latex/microcrystalline cellulose/polydopamine (NRL/MCC/PDA) composite material. Meanwhile, the preparation method provided by the invention has no strict requirements on reaction conditions and generates no harmful substances.
Detailed Description
The invention will be further described with reference to specific examples:
examples 1 to 10
Preparing buffer solution with the pH value of 8.5 by using Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCL), adding Dopamine (DA) and microcrystalline cellulose (MCC) in different proportions, and stirring and reacting for 4 hours at the temperature of 25 ℃;
secondly, grinding zinc oxide, casein (dispersion stabilizer), accelerant and sulfur in a grinder for 2 hours according to a proportion to obtain uniform slurry-like mixed liquor;
thirdly, the mixed liquid prepared in the first step and the second step is respectively added into natural latex (with solid content of 60 percent), and is continuously stirred for 6 hours at the temperature of 60 ℃ for ripening, so that the modified cellulose is fully mixed and compatible with the natural latex particles, and the interaction between cellulose molecules and natural latex molecules is improved due to the affinity action of dopamine and protein around the natural latex particles; then pouring the mixture on a smooth glass dish, and placing the mixture in an oven at 80 ℃ for dehydration;
fourthly, the dry adhesive film prepared in the third step is multiplied by t at 140 DEG C90Vulcanizing on a flat vulcanizing machine under the condition of (1) to obtain the dopamine modified microcrystalline cellulose/natural rubber composite material.
Examples 1-5 the formulations were as follows:
TABLE 1 formulation of NRL/MCC/PDA composites with different dopamine amounts
Examples 6-10 the formulations were as follows:
TABLE 2 formulation of NRL/MCC/PDA composite materials with different microcrystalline cellulose dosages
Examples 1 and 6 are rubber samples prepared for unmodified microcrystalline cellulose filled natural latex (NRL) composites as a blank control. Dopamine aggregates to form polydopamine during the reaction.
The mechanical properties of examples 1 to 5 are as follows:
TABLE 3 mechanical Properties of NRL/MCC/PDA composite materials
As can be seen from Table 3, the MCC/PDA ratio is 1:0.3, and the composite material has the best performance. The mechanical property of the natural latex filled with the dopamine modified microcrystalline cellulose is obviously improved compared with that of a control group.
The mechanical properties of examples 6 to 10 are as follows:
TABLE 4 mechanical Properties of NRL/MCC/PDA composite materials
As can be seen from Table 4, when the ratio of MCC/PDA is 1:0.3, the mechanical properties of the composite material prepared are improved correspondingly with the increase of the addition amount of MCC. Similarly, the mechanical property of the natural latex filled with the dopamine modified microcrystalline cellulose is obviously improved compared with that of a control group.
Example 11
Taking Tris-HCl, preparing a buffer solution with the pH value of 8.5, adding DA and MCC in different proportions (see table 5 specifically), and continuously stirring for 5 hours in a magnetic stirrer at the temperature of 25 ℃;
secondly, grinding zinc oxide, casein (dispersion stabilizer), accelerant and sulfur in a grinder for 1 hour according to the proportion (see table 5 specifically) to obtain uniform slurry-like mixed liquor;
thirdly, adding the mixed solution obtained in the first step and the second step into natural latex (with solid content of 60%), continuously stirring for 5 hours at the temperature of 60 ℃ for ripening, pouring the mixture on a smooth glass dish, and placing the glass dish in a drying oven at the temperature of 90 ℃ for dehydration;
mixing the dry rubber film prepared in the step (III) in a Haake mixer at the mixing temperature of 80 ℃ for 20min to obtain the dopamine modified microcrystalline cellulose/natural rubber master mix;
TABLE 5 formulation of NRL/MCC/PDA composite materials
Fifthly, mixing 1852g of the master batch obtained in the step (iv) with 7148g of natural rubber at 143 ℃ for t90Was vulcanized on a press vulcanizer to obtain a dopamine-modified microcrystalline cellulose/natural rubber composite material, which was designated as sample 1.
The sample prepared according to the preparation method of example 1 with the same formulation as in example 11 is labeled as sample 2. The same formulation as in example 11 was followed in a conventional rubber preparation process by adding the formulation proportions of the various adjuvants to the natural rubber using a two-roll mill and then vulcanizing to give a sample designated sample 3.
Table 6 is a comparison of the mechanical properties of the three samples.
TABLE 6 mechanical Properties of composites prepared by different preparation Processes
As can be seen from Table 6, the samples made using the masterbatch process performed the highest performance, while the samples made using the conventional process performed the worst performance.
Claims (8)
1. A preparation method of dopamine modified microcrystalline cellulose reinforced natural rubber is characterized by comprising the following steps:
preparing buffer solution with the pH value of 8.5 by using tris (hydroxymethyl) aminomethane hydrochloride, adding dopamine and microcrystalline cellulose, and stirring for reaction;
secondly, grinding the zinc oxide, the rubber additive and the sulfur to obtain uniform slurry mixed liquor;
thirdly, respectively adding the mixed liquid prepared in the first step and the second step into the natural latex, continuously stirring the mixture for curing, pouring the mixture on a smooth glass vessel, and placing the mixture in an oven for dehydration;
fourthly, the dry adhesive film prepared in the step three is processed at the temperature of 140-90Vulcanizing on a flat vulcanizing machine under the condition of (1) to obtain the dopamine modified microcrystalline cellulose/natural rubber composite material.
2. A preparation method of dopamine modified microcrystalline cellulose reinforced natural rubber is characterized by comprising the following steps:
preparing buffer solution with pH of 8.5 by taking tris (hydroxymethyl) aminomethane hydrochloride, then adding dopamine and microcrystalline cellulose, and stirring for reaction;
secondly, grinding the zinc oxide, the rubber additive and the sulfur to obtain uniform slurry-like mixed liquid;
thirdly, respectively adding the mixed liquid prepared in the first step and the second step into the natural latex, continuously stirring the mixture for curing, pouring the mixture on a smooth glass vessel, and placing the mixture in an oven for dehydration;
mixing the dry rubber film prepared in the step (c) to obtain a dopamine modified microcrystalline cellulose/natural rubber master batch;
fifthly, mixing the master batch with a certain amount of natural rubber at the temperature of 140-90Vulcanizing the mixture on a flat vulcanizing machine under the condition of (1) to obtain the dopamine modified microcrystalline cellulose/natural rubber composite materialAnd (4) feeding.
3. The preparation method of dopamine-modified microcrystalline cellulose-reinforced natural rubber as described in claim 1 or 2, wherein in step (r), the mass ratio of dopamine to microcrystalline cellulose is (0.1-2):1, the stirring reaction time is 3-7h, and the stirring reaction temperature is 20-30 ℃.
4. The preparation method of dopamine modified microcrystalline cellulose reinforced natural rubber as described in claim 1 or 2, wherein the rubber auxiliary in step (ii) is 1-5 parts of dispersion stabilizer, 0.5-3 parts of accelerator, 1-3 parts of sulfur, 2-5 parts of zinc oxide, and the grinding time is 1-3 hours.
5. The method for preparing dopamine modified microcrystalline cellulose reinforced natural rubber as described in claim 1 or 2, wherein in the third step, the weight ratio of the mixed solution prepared in the first step to the mixed solution prepared in the second step is 1:2-1:8, the weight ratio of the two mixed solutions to natural latex is 1:1-1:10, and the natural latex is natural rubber emulsion with 60% solid content.
6. The method for preparing dopamine modified microcrystalline cellulose reinforced natural rubber according to claim 1 or 2, wherein the stirring reaction condition in the third step is that the stirring time is 3-6h at 60 ℃ and the dehydration temperature is 80-90 ℃.
7. The preparation method of the dopamine modified microcrystalline cellulose reinforced natural rubber as described in claim 2, wherein the mixing temperature in the step (iv) is 80 ℃ and the mixing time is 20 min.
8. The dopamine-modified microcrystalline cellulose-reinforced natural rubber prepared by the preparation method of dopamine-modified microcrystalline cellulose-reinforced natural rubber according to any one of claims 1 to 7.
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| CN102002173A (en) * | 2010-10-26 | 2011-04-06 | 华南理工大学 | Preparation method for nanocrystals cellulose/white carbon black/rubber composite material |
| CN111001314A (en) * | 2019-12-13 | 2020-04-14 | 安徽勉以信网络科技有限公司 | Preparation method and application of nanocrystalline cellulose/dopamine composite membrane |
| CN112375369A (en) * | 2020-11-27 | 2021-02-19 | 四川大学 | Interface supermolecule reinforced nano composite material and preparation method thereof |
-
2022
- 2022-03-24 CN CN202210295696.XA patent/CN114539639A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002173A (en) * | 2010-10-26 | 2011-04-06 | 华南理工大学 | Preparation method for nanocrystals cellulose/white carbon black/rubber composite material |
| CN111001314A (en) * | 2019-12-13 | 2020-04-14 | 安徽勉以信网络科技有限公司 | Preparation method and application of nanocrystalline cellulose/dopamine composite membrane |
| CN112375369A (en) * | 2020-11-27 | 2021-02-19 | 四川大学 | Interface supermolecule reinforced nano composite material and preparation method thereof |
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| Title |
|---|
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