CN117304586A - Biological base rubber nano composite material and preparation method and application thereof - Google Patents

Biological base rubber nano composite material and preparation method and application thereof Download PDF

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Publication number
CN117304586A
CN117304586A CN202311140477.5A CN202311140477A CN117304586A CN 117304586 A CN117304586 A CN 117304586A CN 202311140477 A CN202311140477 A CN 202311140477A CN 117304586 A CN117304586 A CN 117304586A
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itaconate
bio
rubber
nanocomposite
carbon black
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郭平云
张晓岭
王欣
侯红霞
郑红兵
王衍金
栾波
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Shandong Jingbo Zhongju New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/02—Elements
    • C08K3/06—Sulfur
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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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

The invention discloses a bio-based rubber nanocomposite and a preparation method and application thereof, belonging to the technical field of bioengineering rubber. The bio-based rubber nanocomposite is prepared by coupling reaction of modified bio-based itaconate raw rubber and nano white carbon black. The bio-based rubber nanocomposite has Si-Si bonds formed by bonding the silane groups of the modified bio-based itaconate raw rubber and the silicon hydroxyl groups in the nano white carbon black, and can remarkably improve the dispersibility of the nano white carbon black in the modified bio-based itaconate raw rubber. The bio-based itaconate crude rubber and the nano white carbon black are not simply and physically mixed any more, but are connected together through chemical bonds. And the bio-based rubber nanocomposite can be applied to tire treads to prepare green tires with low rolling resistance, good wet skid resistance and low oil consumption.

Description

Biological base rubber nano composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of bioengineering rubber, in particular to a bio-based rubber nanocomposite and a preparation method and application thereof.
Background
In recent years, with the increasing awareness of environmental protection, efforts have been made to prepare green tires having low rolling resistance, good wet skid resistance, and low oil consumption. White carbon black (SiO) is used in tire tread rubber 2 ) Is one of effective methods for reducing the rolling resistance of tires and improving the wet skid resistance. SiO (SiO) 2 The excellent performance of the polymer is used in the rubber industry more and more widely, but the white carbon black has small particles and large specific surface area, contains a large amount of hydroxyl groups on the surface, is easy to agglomerate, has poor compatibility with rubber, is difficult to disperse uniformly in dry mixing, and leads to the performance reduction of rubber products. Meanwhile, the dry mixing method has the problems of large dust pollution, high energy consumption and the like.
The Chinese patent publication No. CN 115627044A discloses a bio-based itaconate rubber white carbon black composite material and a preparation method thereof, wherein the surface of the white carbon black is modified by a silane coupling agent, then slurry is prepared, and the bio-based itaconate rubber white carbon black composite material is obtained by wet-process compounding. However, the silane coupling agent surface modification of the white carbon black is time-consuming and labor-consuming, and in the wet process compounding process, the bio-based rubber emulsion is extremely easy to break, so that the white carbon black is difficult to disperse uniformly.
How to improve the dispersibility of white carbon black in a rubber matrix, so that the white carbon black can be better combined with bio-based itaconate rubber to obtain a rubber material with better performance, and the white carbon black becomes one of the problems to be solved urgently by the technicians in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a bio-based rubber nanocomposite, and a preparation method and application thereof. The silicon hydroxyl of the nanometer white carbon black in the bio-based rubber nanocomposite is bonded with the silane group of the modified bio-based itaconate raw rubber to form Si-Si bond, so that the dispersing effect of the nanometer white carbon black is better.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a bio-based rubber nanocomposite which is prepared by coupling reaction of modified bio-based itaconate raw rubber and nano white carbon black.
The bio-based rubber nanocomposite is provided with Si-Si bonds formed by bonding the silane groups of the modified bio-based itaconate raw rubber and the silicon hydroxyl groups in the nano white carbon black.
The modified bio-based itaconate raw rubber is prepared by emulsion polymerization of a modifier, an itaconate monomer, a conjugated diene monomer and an oxidation-reduction initiator.
The modifier is selected from vinyl-containing silanes.
The vinyl structure in the modifier opens double bonds under the action of an oxidation-reduction initiator, and the double bonds on the macromolecule chain of the bio-based itaconate raw rubber obtained by polymerizing the itaconate monomer and the conjugated diene monomer undergo an addition reaction to prepare the modified bio-based itaconate raw rubber.
The connection position of the vinyl structure in the modifier is on the side chain or the main chain of the bio-based itaconate raw rubber macromolecule. Then, through the mixing process, the silane structure on the macromolecule chain of the modified bio-based itaconate rubber and the silicon hydroxyl of the nano white carbon black are dehydrated to form Si-Si bond, so that the dispersion performance of the nano white carbon black in the modified bio-based itaconate rubber is remarkably improved.
And finally, carrying out mould pressing vulcanization on the prepared material at a certain temperature to obtain the bio-based rubber nanocomposite.
In some embodiments of the present invention, the temperature of the press-molding cure is preferably 160 ℃, and the curing agent used for the cure is preferably sulfur. And (3) generating crosslinking reaction to generate vulcanized rubber when the rubber compound is vulcanized.
Preferably, the mass ratio of the modified bio-based itaconate raw rubber to the nano white carbon black is 5: (1-4). More preferably 5: (2-3); further preferably 5:3.
Preferably, the mass ratio of the modifier to the itaconate monomer is (2-15): (5-95); more preferably (2 to 10): (15-80). In some embodiments of the invention, the mass ratio of the vinyl-containing silane modifier to the itaconate ester monomer is preferably 3:20 or 1:12 or 1:20.
Preferably, the mass ratio of the itaconate ester monomer to the conjugated diene monomer is (5-95): (5-95); more preferably (20 to 80): (20-80); further preferably 3:2.
Preferably, the mass ratio of the redox initiator to the modifier is (0.01-5): (2-15). More preferably (0.1 to 3): (3 to 12), more preferably 0.1:12 or 0.3:10 or 1:3.
Preferably, the modifier is selected from one or more of vinyl silane, dimethyl dimethylamino vinyl silane, divinyl dimethyl silane, tetravinyl silane, vinyl triethoxy silane, trivinyl silane, vinyl trimethyl silane, dimethyl vinyl ethoxy silane, methyl vinyl dimethoxy silane, vinyl triacetoxy silane, triisoallyloxy vinyl silane, vinyl tri (beta-methoxyethoxy) silane, vinyl trichloro silane and dichloro methyl vinyl silane; more preferably one or more of vinylsilane, dimethylvinylsilane, dimethyldimethylaminovinylsilane, divinyldimethylsilane, tetravinylsilane, vinyltriethoxysilane, trivinylsilane, vinyltrimethylsilane; further preferred are one or more of vinylsilane, dimethylvinylsilane, vinyltrimethylsilane.
Preferably, the redox initiator is selected from one or more of p-menthane hydroperoxide, tert-butyl hydroperoxide and cumene hydroperoxide; more preferably one or more of p-menthane hydroperoxide and t-butyl hydroperoxide.
Preferably, the itaconate ester monomer is selected from one or more of diethyl itaconate, dibutyl itaconate, dipentyl itaconate, dihexyl itaconate, diheptyl itaconate, dioctyl itaconate, dinonyl itaconate and didecyl itaconate. More preferably one or more of diethyl itaconate, dibutyl itaconate and dipentyl itaconate. In some embodiments of the invention, the itaconate ester monomer is selected from diethyl itaconate or dibutyl itaconate.
Preferably, the conjugated diene is selected from butadiene and/or isoprene. In some embodiments of the invention, the conjugated diene is selected from butadiene or isoprene.
Preferably, the bio-based rubber nanocomposite further comprises stearic acid, zinc oxide, an anti-aging agent 4020, an anti-aging agent RD, an accelerator NS and an accelerator CZ.
The invention also provides a preparation method of the bio-based rubber nanocomposite, which comprises the following steps:
1) In inert atmosphere, mixing a silane modifier containing vinyl, deionized water, an itaconate monomer, conjugated diene and an redox initiator, and performing emulsion polymerization reaction to prepare modified bio-based itaconate raw rubber;
2) And mixing and vulcanizing the prepared modified bio-based itaconate crude rubber and nano white carbon black to obtain the bio-based rubber nanocomposite.
The mass ratio of the deionized water to the itaconic acid ester monomer is preferably (100-300): (5-95).
In the preparation method of the invention, the step 1) can be added with the following emulsifying agent, electrolyte, activating agent, deoxidizer, molecular weight regulator, terminator and flocculating agent as reaction additives.
The emulsifier is preferably one or more of oleate, linoleate, abietate, laurate and fatty acid salt; more preferably oleate or abietate. In some embodiments of the invention, the emulsifier is preferably potassium oleate or potassium disproportionated rosin acid.
The electrolyte is preferably one or more of sodium bicarbonate, potassium chloride, sodium hydrogen phosphate, sodium phosphate and sodium acetate; more preferably one or more of sodium bicarbonate, potassium chloride, sodium hydrogen phosphate.
The activator is preferably one or more of sodium formaldehyde sulfoxylate, ferrous sulfate, ferric sodium ethylenediamine tetraacetate and tetrasodium ethylenediamine tetraacetate; sodium formaldehyde sulfoxylate is more preferred.
The oxygen scavenger is preferably sodium dithionite.
The molecular weight regulator is preferably alkyl mercaptan and/or multi-mercapto mercaptan compound; more preferably an alkyl mercaptan; more preferably n-dodecyl mercaptan or t-dodecyl mercaptan.
The terminator is preferably one or more of sodium polysulfide, hydroxylamine compound and dimethyl sodium dithiocarbamate; more preferably sodium polysulfide or isopropyl hydroxylamine.
The flocculant is preferably dicyandiamide formaldehyde condensate or epoxy amine copolymer.
Preferably, the mass ratio of the emulsifier to the itaconate monomer is (1-10): (5-95).
Preferably, the mass ratio of the electrolyte to the itaconate monomer is (0.1-4): (5-95).
Preferably, the mass ratio of the activator to the itaconate monomer is (0.01-0.4): (5-95).
Preferably, the mass ratio of the deoxidizer to the itaconate monomer is (0.01-0.06): (5-95).
Preferably, the mass ratio of the molecular weight regulator to the itaconate monomer is (0.01-0.5): (5-95).
Preferably, the mass ratio of the terminator to the itaconate monomer is (0.2-3): (5-95).
Preferably, the mass ratio of the flocculant to the itaconate monomer is (0.1-1): (5-95). More preferably (0.1 to 1): (10-60). In some embodiments of the invention, the mass ratio of flocculant to itaconate ester monomer is preferably 0.1:20 or 0.8:60 or 0.1:12. Other conventional substances can be added as reaction raw materials in the mixing and vulcanizing process in the step 2) for preparing the bio-based rubber nanocomposite.
The other conventional materials used as the reaction raw materials are preferably stearic acid, zinc oxide, an anti-aging agent 4020 (N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine), an anti-aging agent RD (2, 4-trimethyl-1, 2-dihydroquinoline polymer), an accelerator NS (N-t-butyl-2-benzothiazole hypo-yellow amide), and an accelerator CZ (N-cyclohexyl-2-benzothiazole sulfenamide).
The invention also provides application of the bio-based rubber nanocomposite or the bio-based rubber nanocomposite prepared by the preparation method in rubber products.
The bio-based rubber nanocomposite can effectively weaken the Paen effect, and has lower rolling resistance when applied to tires.
The invention also provides a green tire, which contains the bio-based rubber nanocomposite or the bio-based rubber nanocomposite prepared by the preparation method.
Preferably, the content of the bio-based rubber nanocomposite in the green tire is 30-60 wt%.
Compared with the prior art, the bio-based rubber nanocomposite is prepared by coupling reaction of modified bio-based itaconate raw rubber and nano white carbon black. The bio-based rubber nanocomposite has Si-Si bonds formed by bonding the silane groups of the modified bio-based itaconate raw rubber and the silicon hydroxyl groups in the nano white carbon black, and can remarkably improve the dispersibility of the nano white carbon black in the modified bio-based itaconate raw rubber. The bio-based itaconate crude rubber and the nano white carbon black are not simply and physically mixed any more, but are connected together through chemical bonds. And the bio-based rubber nanocomposite can be applied to tire treads to prepare green tires with low rolling resistance, good wet skid resistance and low oil consumption.
Drawings
FIG. 1 is an electron microscope scan of the bio-based rubber nanocomposite prepared in example 1;
FIG. 2 is an electron microscope scan of the bio-based rubber nanocomposite prepared in comparative example 1.
Detailed Description
In order to further illustrate the present invention, the bio-based rubber nanocomposite provided by the present invention, and a method for preparing the same and applications thereof will be described in detail with reference to examples.
Example 1
Adding 600g of deionized water, 12g of potassium oleate, 3.6g of potassium chloride, 0.1g of ferrous sulfate, 0.35g of formaldehyde sodium bisulfate, 0.5g of ethylene diamine tetraacetic acid disodium salt, 0.12g of sodium dithionite, 240g of diethyl itaconate, 0.4g of n-dodecyl mercaptan and 36g of modifier vinylsilane into a polymerization reaction device, sealing the polymerization device, vacuumizing and then filling nitrogen gas, and performing the operation for 4 times; then 160g of butadiene and 0.3g of p-menthane hydroperoxide are added, and the mixture is reacted for 10 hours under the conditions of 8 ℃ and 0.4 MPa; then adding 5.2g of terminator sodium polysulfide to terminate reaction to obtain bio-based rubber emulsion, and then demulsifying and drying 6000g of aqueous solution containing flocculant dicyandiamide formaldehyde condensate (containing flocculant 1.2 g) to obtain modified bio-based itaconic acid ester crude rubber.
100g of the modified bio-based itaconate crude rubber, 60g of nano white carbon black (7000 GR), 2g of Stearic Acid (SA), 5g of zinc oxide, 1g of age resistor 4020, 1g of age resistor RD, 1g of accelerator NS, 1g of accelerator CZ and 1.5g of sulfur are taken, mixed on a two-roll mill, and then subjected to mold pressing vulcanization at 160 ℃ to obtain the bio-based rubber nanocomposite.
FIG. 1 is an electron microscope scan of the bio-based rubber nanocomposite prepared in example 1.
Example 2
600g of deionized water, 11.2g of disproportionated potassium abietate, 3.6g of sodium bicarbonate, 0.16g of ferrous sulfate, 0.56g of formaldehyde sodium bisulfate, 0.6g of ethylene diamine tetraacetic acid disodium salt, 0.08g of sodium dithionite, 240g of dibutyl itaconate, 0.92g of tertiary dodecyl mercaptan and 20g of modifier dimethyl vinylsilane are added into a polymerization reaction device, then the polymerization device is closed, and the operation is carried out for 3 times after vacuumizing and nitrogen charging are carried out; then 160g of isoprene and 0.6g of tert-butyl hydroperoxide are added, and the mixture is reacted for 10 hours under the conditions of 5 ℃ and 0.8 MPa; then adding 4.8g of terminator isopropyl hydroxylamine to terminate reaction to obtain bio-based rubber emulsion, and then demulsifying and drying 6000g of aqueous solution of flocculant-containing epoxy amine copolymer (3.2 g of flocculant-containing itaconic acid ester crude rubber).
100g of the modified bio-based itaconate crude rubber, 60g of white carbon black, 2g of stearic acid, 5g of zinc oxide, 1g of an anti-aging agent 4020, 1g of an anti-aging agent RD, 1.2g of an accelerator NS, 1g of an accelerator CZ and 1.5g of sulfur are taken, mixed on a two-roll mill, and then subjected to compression molding vulcanization at 150 ℃ to obtain the bio-based rubber nanocomposite.
Example 3
Adding 600g of deionized water, 11.2g of disproportionated potassium abietate, 8.4g of sodium hydrogen phosphate, 0.12g of ferrous sulfate, 0.42g of formaldehyde sodium bisulfate, 0.6g of ethylene diamine tetraacetic acid disodium salt, 0.16g of sodium dithionite, 240g of dibutyl itaconate, 0.2g of tertiary dodecyl mercaptan and 12g of modifier vinyl trimethylsilane into a polymerization reaction device, sealing the polymerization device, vacuumizing and then filling nitrogen for 3 times; then 160g of butadiene and 4g of p-menthane hydroperoxide are added and reacted for 8 hours under the conditions of 12 ℃ and 0.7 MPa; then adding 5g of terminator sodium polysulfide to terminate the reaction to obtain bio-based rubber emulsion, and then demulsifying and drying 6000g of aqueous solution (containing 2g of flocculant) of epoxy amine copolymer containing flocculant to obtain the modified bio-based itaconate rubber.
100g of the modified bio-based itaconate crude rubber, 60g of white carbon black, 2g of stearic acid, 5g of zinc oxide, 1g of an anti-aging agent 4020, 1g of an anti-aging agent RD, 1.2g of an accelerator NS, 1g of an accelerator CZ and 1.5g of sulfur are taken, mixed on a two-roll mill, and then subjected to compression molding vulcanization at 160 ℃ to obtain the bio-based rubber nanocomposite.
Comparative example 1
Corresponding to example 1, the modifier vinylsilane in the polymerization formulation was removed.
Adding 600g of deionized water, 12g of potassium oleate, 3.6g of potassium chloride, 0.1g of ferrous sulfate, 0.35g of formaldehyde sodium bisulfate, 0.5g of ethylene diamine tetraacetic acid disodium salt, 0.12g of sodium dithionite, 240g of diethyl itaconate and 0.4g of n-dodecyl mercaptan into a polymerization reaction device, sealing the polymerization device, vacuumizing and then filling nitrogen gas, and performing the operation for 4 times; then 160g of butadiene and 0.3g of p-menthane hydroperoxide are added, and the mixture is reacted for 10 hours under the conditions of 8 ℃ and 0.4 MPa; then adding 5.2g of terminator sodium polysulfide to terminate reaction to obtain bio-based rubber emulsion, and then demulsifying and drying 6000g of aqueous solution containing flocculant dicyandiamide formaldehyde condensate (containing flocculant 1.2 g) to obtain bio-based itaconic acid ester crude rubber.
100g of the bio-based itaconate crude rubber, 60g of nano white carbon black, 2g of stearic acid, 5g of zinc oxide, 1g of an anti-aging agent 4020, 1g of an anti-aging agent RD, 1g of an accelerator NS, 1g of an accelerator CZ and 1.5g of sulfur are taken, mixed on a two-roll mill, and then subjected to compression molding vulcanization at 160 ℃ to obtain the bio-based rubber nanocomposite.
FIG. 2 is an electron microscope scan of the bio-based rubber nanocomposite prepared in comparative example 1. By comparing fig. 1 and fig. 2, it is apparent that the dispersibility of the filler in the bio-based rubber nanocomposite prepared in fig. 1, i.e., example 1, is superior to that of fig. 2, and aggregation and agglomeration of the filler do not occur. The bio-based rubber nanocomposite prepared by adopting the modifier vinyl silane can reduce internal friction between fillers and improve the compatibility of the fillers and rubber.
Comparative example 2
100g of bio-based itaconate crude rubber, 60g of Si-69 g of nano white carbon black, 2g of stearic acid, 5g of zinc oxide, 1g of anti-aging agent 4020, 1g of anti-aging agent RD, 1g of accelerator NS, 1g of accelerator CZ and 1.5g of sulfur are taken, mixed on a two-roll mill, and then subjected to mold pressing vulcanization at 160 ℃ to obtain the bio-based rubber nanocomposite.
The biobased itaconate raw rubber and biobased rubber nanocomposite materials obtained in the above examples 1 to 3 and comparative examples 1 to 2 were tested according to the following test methods, and the test results are shown in table 1;
(1) Rubber raw mooney viscosity (ml1+4, 100 ℃) test: testing according to GB/T1232-2000, wherein the testing temperature is 100 ℃;
(2) Dynamic mechanical property test: testing was performed according to GB/T13937-1992, test temperature: -70-80 ℃, heating rate of 3 ℃/min, -70 ℃ for 15min, dynamic strain of 0.25%, static strain of 2.5%;
(3) Tensile strength test: testing according to GB/T528-92, wherein the stretching speed is 500+/-50 mm/min;
(4) Abrasion resistance performance test: the test was performed according to GB/T9867-2008. Table 1 table of performance data for raw rubber and biobased rubber nanocomposite in examples 1 to 3 and comparative examples 1 to 2
Note that: the wet skid resistance of the bio-based rubber nanocomposite can be generally expressed by dynamic viscoelasticity tan delta at 0 ℃, and the greater the numerical value, the better the wet skid resistance; the heat buildup can be expressed in terms of dynamic viscoelasticity tan delta @60 ℃, with lower values and lower heat buildup.
The data show that the molecular weight and the Mooney viscosity of the modified bio-based itaconate raw rubber prepared by the invention are higher. The tearing strength, the tensile strength and the wear resistance of the bio-based rubber nanocomposite prepared by the invention are all improved. In addition, the anti-wet skid property of the bio-based rubber nanocomposite is obviously improved, the heat generation is obviously reduced, and the rolling resistance of the tire can be reduced when the bio-based rubber nanocomposite is applied to the tire.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (10)

1. The bio-based rubber nanocomposite is characterized by being prepared by performing a coupling reaction on modified bio-based itaconate raw rubber and nano white carbon black;
the modified bio-based itaconate raw rubber is prepared by emulsion polymerization of a modifier, an itaconate monomer, a conjugated diene monomer and an oxidation-reduction initiator;
the modifier is selected from vinyl-containing silanes.
2. The bio-based rubber nanocomposite according to claim 1, wherein the mass ratio of the modified bio-based itaconate raw rubber to the nano white carbon black is 5: (1-4);
the mass ratio of the modifier to the itaconate monomer is (2-15): (5-95);
the mass ratio of the itaconate ester monomer to the conjugated diene monomer is (5-95): (5-95);
the mass ratio of the redox initiator to the modifier is (0.01-5): (2-15).
3. The bio-based rubber nanocomposite according to claim 1, wherein the modifier is selected from one or more of vinylsilane, dimethylvinylsilane, dimethyldimethylaminovinylsilane, divinyldimethylsilane, tetravinylsilane, vinyltriethoxysilane, trivinylsilane, vinyltrimethylsilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, vinyltriacetoxysilane, triisoallyloxyvinylsilane, vinyltris (β -methoxyethoxy) silane, vinyltrichlorosilane, dichloromethylvinylsilane.
4. The biobased rubber nanocomposite according to claim 1, wherein the redox initiator is selected from one or more of p-menthane hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide.
5. The biobased rubber nanocomposite of claim 1, wherein said itaconate ester monomer is selected from one or more of diethyl itaconate, dibutyl itaconate, dipentyl itaconate, dihexyl itaconate, diheptyl itaconate, dioctyl itaconate, dinonyl itaconate, didecyl itaconate;
the conjugated diene is selected from butadiene and/or isoprene.
6. The bio-based rubber nanocomposite according to claim 1, further comprising stearic acid, zinc oxide, an anti-aging agent 4020, an anti-aging agent RD, an accelerator NS, and an accelerator CZ.
7. The preparation method of the bio-based rubber nanocomposite is characterized by comprising the following steps of:
1) In inert atmosphere, mixing a silane modifier containing vinyl, deionized water, an itaconate monomer, conjugated diene and an redox initiator, and performing emulsion polymerization reaction to prepare modified bio-based itaconate raw rubber;
2) And mixing and vulcanizing the prepared modified bio-based itaconate crude rubber and nano white carbon black to obtain the bio-based rubber nanocomposite.
8. Use of the biobased rubber nanocomposite of any one of claims 1 to 6 or the biobased rubber nanocomposite prepared by the preparation method of claim 7 in rubber products.
9. A green tire comprising the bio-based rubber nanocomposite according to any one of claims 1 to 6 or the bio-based rubber nanocomposite produced by the production method according to claim 7.
10. The green tire of claim 9 wherein the biobased rubber nanocomposite in the green tire is present in an amount of 30wt% to 60wt%.
CN202311140477.5A 2023-09-05 2023-09-05 Biological base rubber nano composite material and preparation method and application thereof Pending CN117304586A (en)

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