CN111393720A - Nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and preparation method thereof - Google Patents
Nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and preparation method thereof Download PDFInfo
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- CN111393720A CN111393720A CN202010336795.9A CN202010336795A CN111393720A CN 111393720 A CN111393720 A CN 111393720A CN 202010336795 A CN202010336795 A CN 202010336795A CN 111393720 A CN111393720 A CN 111393720A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L7/00—Compositions of natural rubber
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention discloses a nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and a preparation method thereof. The nano zinc oxide modified nano crystal cellulose reinforced natural rubber is compounded by nano zinc oxide, nano crystal cellulose and natural rubber. Firstly, synthesizing nano zinc oxide/nanocrystalline cellulose by a hydrothermal method, and then preparing the modified nanocrystalline cellulose-reinforced natural rubber by a sol-gel method. The nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber prepared by the invention has good physical and mechanical properties, the tensile strength and the elongation at break are obviously improved, and the high temperature resistance, the ageing resistance and the friction performance are improved to a certain extent. The preparation process is simple, the reaction conditions are not harsh, and no harmful substances are generated.
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 nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and a preparation method thereof.
Background
Nanocrystalline cellulose (NCC) is obtained by degrading a cellulose raw material with mixed acid or sulfuric acid, and has some unique optical properties, rheological properties and mechanical properties due to its small particle size, large specific surface area and certain hydrophilicity. These properties make NCC have a wide range of applications: can be compounded with other materials to prepare degradable nano materials, and can also be used as a reinforcement to be doped into other materials to improve the mechanical property of the material.
Since the specific surface area of the NCC particles is extremely large and the surface hydroxyl groups are very abundant, the particles are easily agglomerated by hydrogen bonding during the drying process. The agglomerated NCC is difficult to redisperse by a physical method, and the application prospect is limited. How to improve the redispersibility of NCC by surface modification of NCC through some simple chemical modification methods is attracting more and more attention. Currently, the redispersibility of NCC is improved mainly by two methods, one by adding surfactants and the other by chemical grafting. The great advantage of the latter method is that the NCC suspension has good stability at high ionic concentrations.
Natural rubber has the characteristics of high elasticity and high elongation, but the elastic modulus and the shear modulus are low, and the heat resistance is poor, so that the application range of the natural rubber is limited. Chemical modification of natural rubber is the primary means to improve its properties. The current modification modes mainly comprise the following modes: (1) carrying out graft copolymerization on natural rubber, wherein polymerized monomers comprise acrylate, styrene, acrylonitrile and the like; (2) natural rubber is epoxidized, typically using peroxycarboxylic acids as the oxidizing agent; (3) clay particles are blended with natural rubber; (4) the natural rubber is chloridized.
The patent document CN101412825A discloses Japanese 2009.04.22 discloses a preparation method of a rubber/modified microcrystalline cellulose composite material, which comprises the following steps of (1) placing microcrystalline cellulose and a first monomer in a flask, introducing nitrogen for protection, preheating for 15-60 min at a reaction temperature of 25-100 ℃, adding an initiator at the temperature, stirring and mixing for 2-10 min, (3) adding an emulsified second monomer or a mixture of the second monomer and a third monomer, reacting for 20-180 min at the reaction temperature, obtaining modified microcrystalline cellulose, (4) mixing the modified microcrystalline cellulose and rubber according to a traditional rubber processing technology, obtaining the rubber/modified microcrystalline cellulose composite material, wherein the usage of the modified cellulose is 5-55% of the mass of the rubber, the first monomer is maleic anhydride or an ester thereof, fumaric anhydride or an ester thereof, acrylic acid, methacrylic acid, β -hydroxypropyl acrylate, β -hydroxyethyl methacrylate, acrylamide or vinyl acetate, the second monomer and the third monomer are styrene, methyl methacrylate, butyl acrylate, methyl acrylate, butyl acrylate, acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid, cellulose, acrylic acid, cellulose, acrylic acid, acrylic.
Patent document CN110317370A, published japanese patent No. 2019.10.11, discloses a cationic surfactant modified nanocellulose/natural rubber composite material and a preparation method thereof, comprising the following steps: (1) soaking the raw materials in 5-30% NaOH solution by mass for 5-30 min, stirring, filtering and washing to obtain slurry, adding 10-30% ammonium persulfate solution by mass into the slurry, stirring at 50-100 ℃, fully reacting for 1-5h, and centrifugally washing after the reaction is finished; adjusting pH to 9-11, adding H2O2 at 50-80 deg.C, and ultrasonic oxidizing for 10-30 min; dialyzing the product after centrifugation for 5-7d, then scattering the product after dialysis for 5-10min by a crusher, centrifuging and taking supernatant fluid, namely the prepared nano cellulose suspension; (2) placing the nano-cellulose suspension in a three-neck flask, adding a cationic surfactant under the water bath heating condition of 40-80 ℃, reacting for 2-4h, centrifuging at 3000-5000r/min for 3-5min after the reaction to remove the surfactant which is not adsorbed on the surface of the nano-cellulose, and finally obtaining the surface modified nano-cellulose; (3) adding 2-8g of surface-modified nano-cellulose into 15-30g of natural latex, stirring at room temperature for 10-30min to uniformly mix the two phases, then placing the mixture in a constant-temperature forced air drying oven at 40-60 ℃, and drying to constant weight to obtain a mixed rubber material; and then mixing the mixed rubber material on an open mill, standing for 24-36h, and vulcanizing at 140-145 ℃ to obtain the surface modified nano-cellulose/natural rubber composite material. The invention provides that the surface of the nano-cellulose prepared by an oxidation method is negatively charged because partial hydroxyl is oxidized into carboxyl, so that the surface of the nano-cellulose is modified by selecting a cationic surfactant. The modified nano-cellulose can be well dispersed in a natural rubber matrix, and the modified nano-cellulose has alkyl terminals, so that the interface combination of the nano-cellulose and the natural rubber is improved, and the outstanding reinforcing effect is shown.
The above patent documents modify nanocrystalline cellulose to increase dispersibility. However, the modification method of the nanocrystalline cellulose needs to be carried out for many 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 nanocrystalline cellulose reinforced rubber are available.
Disclosure of Invention
The invention aims to provide a nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and a preparation method thereof aiming at the defects in the prior art.
In order to achieve the aim, the invention provides a preparation method of nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber, which is characterized by comprising the following steps:
(1) NCC is made into NCC suspension with the mass fraction of 10-15 percent through magnetic stirring and ultrasonic dispersion;
(2) reduction of Zn (AcO)2·2H2Dispersing the O alcohol solution in the NCC suspension in the step (1), keeping the temperature at 70-90 ℃, stirring to form a uniform mixed solution, and adjusting the pH value of the mixed solution to 10 by using a sodium hydroxide solution with the concentration of 5 mol/L;
(3) continuously heating the suspension in the step (2) for 1-3h, and adding AgNO with the mass fraction of 10% -20%3Adding the aqueous solution into the suspension, stirring vigorously to mix uniformly, and reacting for 2-4 h;
(4) centrifuging the suspension obtained after the reaction in the step (3) to obtain a precipitate, carefully washing the precipitate with distilled water for three times, and drying the precipitate at 100-120 ℃ for 1-3h to obtain an NCC-ZnO compound;
(5) dissolving the NCC-ZnO compound prepared in the step (4) in a solvent to prepare NCC-ZnO sol with the mass concentration of 10-25%, wherein the solvent is one of dichloroethane, toluene, ethanol and isopropanol;
(6) uniformly mixing the NCC-ZnO sol in the step (5) with the natural rubber emulsion, and magnetically stirring for 20-28h to obtain NCC-ZnO rubber composite emulsion;
(7) and (4) transferring the composite emulsion obtained in the step (6) into a mould, and placing the mould in a drying oven to be dried for 36-60h at the temperature of 50-70 ℃ to obtain the nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber.
Preferably, Zn (AcO) in the step (2)2·2H2The mass ratio of O to NCC is 1 (2-4), and the reaction time is 4-7 h.
Preferably, Zn (AcO) in the step (2)2·2H2Zn (AcO) in O alcohol solution2·2H2The mass fraction of O is 40-60%.
The invention also provides the nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber prepared by the method.
The invention has the advantages that:
1. the invention adopts Zn (AcO)2·2H2The modified NCC-reinforced natural rubber has good physical and mechanical properties, remarkably improved tensile strength and elongation at break, good tensile property, and improved high temperature resistance, ageing resistance and friction performance to a certain extent. The composite material has wide application in the fields of aerospace sealing, insulation, heat preservation, heat insulation and the like.
2. The reaction conditions of the invention are not harsh and no harmful substances are generated.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a preparation method of a nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber composite material, which comprises the following specific steps:
(1) NCC is made into NCC suspension with the mass fraction of 10 percent through magnetic stirring and ultrasonic dispersion;
(2) reduction of Zn (AcO)2·2H2Dispersing the O alcohol solution in the NCC suspension in the step (1), keeping the temperature and stirring at 80 ℃ to form a uniform mixed solution, and then adjusting the pH value of the mixed solution to 10 by using a sodium hydroxide solution with the concentration of 5 mol/L;
(3) continuously heating the suspension in the step (2) for 2 hours, and adding AgNO with the mass fraction of 10%3Adding the aqueous solution into the suspension, stirring vigorously to mix uniformly, and reacting continuously for 3 hours;
(4) centrifuging the suspension obtained after the reaction in the step (3) to obtain a precipitate, carefully washing the precipitate with distilled water for three times, and drying the precipitate at 100 ℃ for 1 hour to obtain an NCC-ZnO compound;
(5) dissolving the NCC-ZnO compound prepared in the step (4) in an ethanol solvent to prepare NCC-ZnO sol with the mass concentration of 10%;
(6) uniformly mixing the NCC-ZnO sol in the step (5) with the natural rubber emulsion, and magnetically stirring for 20 hours to obtain NCC-ZnO rubber composite emulsion;
(7) and (4) transferring the composite emulsion obtained in the step (6) into a mold, and placing the mold in a drying oven to dry for 36 hours at 70 ℃ to obtain the nano zinc oxide modified nano crystal cellulose reinforced natural rubber.
Example 2
The embodiment provides a preparation method of a nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber composite material, which comprises the following specific steps:
(1) NCC is made into NCC suspension with the mass fraction of 15 percent through magnetic stirring and ultrasonic dispersion;
(2) reduction of Zn (AcO)2·2H2Dispersing the O alcohol solution in the NCC suspension in the step (1), keeping the temperature and stirring at 70 ℃ to form a uniform mixed solution, and then adjusting the pH value of the mixed solution to 10 by using a sodium hydroxide solution with the concentration of 5 mol/L;
(3) continuously heating the suspension in the step (2) for 3 hours, and adding AgNO with the mass fraction of 15%3Adding the aqueous solution into the suspension, stirring vigorously to mix uniformly, and reacting for 2 hours;
(4) centrifuging the suspension obtained after the reaction in the step (3) to obtain a precipitate, carefully washing the precipitate with distilled water for three times, and drying the precipitate at 120 ℃ for 2 hours to obtain an NCC-ZnO compound;
(5) dissolving the NCC-ZnO compound prepared in the step (4) in an ethanol solvent to prepare NCC-ZnO sol with the mass concentration of 15%;
(6) uniformly mixing the NCC-ZnO sol in the step (5) with the natural rubber emulsion, and magnetically stirring for 24 hours to obtain NCC-ZnO rubber composite emulsion;
(7) and (4) transferring the composite emulsion obtained in the step (6) into a mold, and placing the mold in a drying oven to dry for 48 hours at the temperature of 60 ℃ to obtain the nano zinc oxide modified nano crystal cellulose reinforced natural rubber.
Example 3
The embodiment provides a preparation method of a nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber composite material, which comprises the following specific steps:
(1) NCC is made into NCC suspension with the mass fraction of 10 percent through magnetic stirring and ultrasonic dispersion;
(2) reduction of Zn (AcO)2·2H2Dispersing the O alcohol solution in the NCC suspension in the step (1), keeping the temperature and stirring at 90 ℃ to form a uniform mixed solution, and then adjusting the pH value of the mixed solution to 10 by using a sodium hydroxide solution with the concentration of 5 mol/L;
(3) after the suspension in the step (2) is continuously heated for 3 hours, AgNO with the mass fraction of 20 percent is added3Adding the aqueous solution into the suspension, stirring vigorously to mix uniformly, and reacting for 4 hours;
(4) centrifuging the suspension obtained after the reaction in the step (3) to obtain a precipitate, carefully washing the precipitate with distilled water for three times, and drying the precipitate at 110 ℃ for 2 hours to obtain an NCC-ZnO compound;
(5) dissolving the NCC-ZnO compound prepared in the step (4) in an ethanol solvent to prepare NCC-ZnO sol with the mass concentration of 25%;
(6) uniformly mixing the NCC-ZnO sol in the step (5) with the natural rubber emulsion, and magnetically stirring for 28 hours to obtain NCC-ZnO rubber composite emulsion;
(7) and (4) transferring the composite emulsion obtained in the step (6) into a mold, and placing the mold in a drying oven to dry for 60 hours at 70 ℃ to obtain the nano zinc oxide modified nano crystal cellulose reinforced natural rubber.
Claims (4)
1. A preparation method of nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber is characterized by comprising the following steps:
(1) NCC is made into NCC suspension with the mass fraction of 10-15 percent through magnetic stirring and ultrasonic dispersion;
(2) reduction of Zn (AcO)2·2H2alcohol-O solutionDispersing the solution in the NCC suspension in the step (1), keeping the temperature at 70-90 ℃, stirring to form a uniform mixed solution, and adjusting the pH value of the mixed solution to 10 by using a sodium hydroxide solution with the concentration of 5 mol/L;
(3) continuously heating the suspension in the step (2) for 1-3h, and adding AgNO with the mass fraction of 10% -20%3Adding the aqueous solution into the suspension, stirring vigorously to mix uniformly, and reacting for 2-4 h;
(4) centrifuging the suspension obtained after the reaction in the step (3) to obtain a precipitate, carefully washing the precipitate with distilled water for three times, and drying the precipitate at 100-120 ℃ for 1-3h to obtain an NCC-ZnO compound;
(5) dissolving the NCC-ZnO compound prepared in the step (4) in a solvent to prepare NCC-ZnO sol with the mass concentration of 10-25%, wherein the solvent is one of dichloroethane, toluene, ethanol and isopropanol;
(6) uniformly mixing the NCC-ZnO sol in the step (5) with the natural rubber emulsion, and magnetically stirring for 20-28h to obtain NCC-ZnO rubber composite emulsion;
(7) and (4) transferring the composite emulsion obtained in the step (6) into a mould, and placing the mould in a drying oven to be dried for 36-60h at the temperature of 50-70 ℃ to obtain the nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber.
2. The method for preparing nano zinc oxide modified nano crystalline cellulose reinforced natural rubber as claimed in claim 1, wherein Zn (AcO) in the step (2)2·2H2The mass ratio of O to NCC is 1 (2-4), and the reaction time is 4-7 h.
3. The method for preparing nano zinc oxide modified nano crystalline cellulose reinforced natural rubber as claimed in claim 1, wherein Zn (AcO) in the step (2)2·2H2Zn (AcO) in O alcohol solution2·2H2The mass fraction of O is 40-60%.
4. The nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber prepared by the method of any one of claims 1 to 3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112791010A (en) * | 2020-12-31 | 2021-05-14 | 华南理工大学 | Chestnut shell aerogel and preparation method and application thereof |
| CN113999509A (en) * | 2021-12-09 | 2022-02-01 | 万华化学（宁波）有限公司 | Modified nano-cellulose and polylactic acid composite membrane and preparation method and application thereof |
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Application publication date: 20200710 |