CN111793258B - Corn byproduct based synthetic rubber environment-friendly material and preparation method thereof - Google Patents

Corn byproduct based synthetic rubber environment-friendly material and preparation method thereof Download PDF

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CN111793258B
CN111793258B CN202010722163.6A CN202010722163A CN111793258B CN 111793258 B CN111793258 B CN 111793258B CN 202010722163 A CN202010722163 A CN 202010722163A CN 111793258 B CN111793258 B CN 111793258B
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corn
carbon black
white carbon
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synthetic rubber
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CN111793258A (en
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张�浩
刘景圣
甄诺
王心雅
李响
薛瑾
李云琦
闵伟红
赵城彬
吴玉柱
许秀颖
曹勇
田林
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Jilin Agricultural University
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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

Abstract

An environment-friendly material of synthetic rubber based on corn byproducts and a preparation method thereof belong to the field of recycling of corn byproducts and rubber materials. The corn byproduct based synthetic rubber environment-friendly material comprises: 100 parts of rubber, 40-60 parts of corn byproduct modified white carbon black, 1-3 parts of stearic acid, 3-7 parts of zinc oxide, 0.8-1.2 parts of accelerator and 1-3 parts of vulcanizing agent; in the corn by-product modified white carbon black, the corn by-product is corn cellulose and/or alcohol soluble protein; the preparation method comprises 100 parts of precipitated white carbon black, 8-15 parts of corn by-products and 1-3 parts of polyhydric alcohol. The method realizes the full reutilization of the corn by-products, so that the white carbon black modified by the corn by-products and the rubber form a good coupling effect, the binding capacity of the white carbon black and the rubber is improved, and the efficiency of the damage and recombination of the white carbon black-rubber network structure is enhanced. The white carbon black modified by the corn by-product has smaller aggregate and better dispersity in the rubber matrix.

Description

Corn byproduct based synthetic rubber environment-friendly material and preparation method thereof
Technical Field
The invention relates to the technical field of recycling of corn byproducts and rubber materials, in particular to a corn byproduct based synthetic rubber environment-friendly material and a preparation method thereof.
Background
Corn is the first major grain crop in China, is an important grain resource and production raw material in China, more than 80% of starch is corn starch, and byproducts generated in the processing process are more than 1000 ten thousand tons every year. The processing by-products mainly comprise cellulose, alcohol soluble protein, glutelin, ash and the like, the components are almost insoluble in water, the bioavailability and the nutritive value are low, and the processing by-products are often used as feed in China or directly used as the discharge treatment of three wastes in industry, so that the comprehensive utilization added value of the corn by-products in China is low, and simultaneously, the waste and the environmental pollution are caused.
Although the corn processing byproducts (mainly cellulose and prolamin) are green renewable energy sources, the biomass corn byproduct-based functional material prepared and synthesized by the method has the advantages of biodegradability, no toxicity, no pollution, easiness in modification, good biocompatibility, renewability and the like compared with synthetic polymers. However, the mechanical properties of the natural biomass corn byproduct and the traditional fossil resource synthetic material are not good, which is the biggest bottleneck of the development of the field, so the research on the corn processing byproduct is urgently needed to provide a new material with improved mechanical properties.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a corn byproduct based synthetic rubber environment-friendly material and a preparation method thereof, which fully recycle corn byproducts, so that white carbon black modified by the corn byproducts and rubber form a good coupling effect, the binding capacity of the white carbon black and the rubber is improved, and the efficiency of breaking and recombining a white carbon black-rubber network structure is enhanced. In addition, the aggregate of the white carbon black modified by the corn by-product is smaller, and the dispersibility of the modified white carbon black in the rubber matrix is better.
The invention relates to a corn byproduct based synthetic rubber environment-friendly material, which comprises the following raw materials in parts by weight: 100 parts of rubber, 40-60 parts of corn byproduct modified white carbon black, 1-3 parts of stearic acid, 3-7 parts of zinc oxide, 0.8-1.2 parts of accelerator and 1-3 parts of vulcanizing agent;
in the corn by-product modified white carbon black, the corn by-product is corn cellulose and/or alcohol soluble protein; the composite material comprises 100 parts of precipitated white carbon black, 8-15 parts of corn cellulose and/or alcohol soluble protein and 1-3 parts of polyhydric alcohol.
The rubber is one or more of styrene butadiene rubber, butadiene rubber and isoprene rubber.
The polyalcohol is glycerol and/or ethylene glycol.
When the corn byproduct modified white carbon black is corn cellulose modified white carbon black, the adopted raw materials comprise precipitation-process white carbon black, corn cellulose and glycerol; the weight parts of all the raw materials are as follows: 100 parts of precipitated white carbon black; 8-15 parts of corn cellulose and 1-2 parts of glycerol.
When the corn byproduct modified white carbon black is prolamin modified white carbon black, the adopted raw materials comprise precipitation-method white carbon black, prolamin and glycol; the weight parts of all the raw materials are as follows: 100 parts of precipitated white carbon black; 8-15 parts of alcohol soluble protein and 2-3 parts of glycol.
Furthermore, the precipitated silica is preferably precipitated SI175 silica,measured by adopting a surfactant adsorption method (CTAB method), the specific surface area of the nano-particles is 170-175 m2/g。
Further, the corn cellulose is one or more of common cellulose, cellulose acetate, methyl cellulose, sodium carboxymethyl cellulose and cellulose triacetate, and is preferably common cellulose.
Further, the environment-friendly material of the corn byproduct based synthetic rubber further comprises 1-2 parts of an anti-aging agent, and the anti-aging agent RD and/or the anti-aging agent 4010NA, wherein the mass ratio of the anti-aging agent RD to the anti-aging agent 4010NA is preferably as follows: (0.5-1):(0.5-1).
Further, the vulcanizing agent is sulfur.
The invention relates to a preparation method of a corn byproduct based synthetic rubber environment-friendly material, which comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring and mixing the white carbon black obtained by the precipitation method, the corn by-product and the polyhydric alcohol according to the proportion to obtain the corn by-product modified white carbon black; wherein the corn by-product is corn cellulose and/or alcohol soluble protein;
in the step 1, the stirring speed is as follows: 800 to 1000 rpm.
Step 2:
according to the formula of the corn byproduct based synthetic rubber environment-friendly material, the raw materials are mixed and vulcanized to obtain the corn byproduct based synthetic rubber environment-friendly material; wherein, the vulcanization time is 0.18-0.57 min, the vulcanization speed is 4.25-6.58 ℃/min, and the positive vulcanization point is 15.27-23.46 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is prepared by using the prolamin modified white carbon black, and the tensile strength of the corn byproduct based synthetic rubber environment-friendly material is improved by 6.2-18.6%.
The corn byproduct based synthetic rubber environment-friendly material and the preparation method thereof have the beneficial effects that:
according to the invention, the corn by-product is fully recycled, so that the white carbon black modified by the corn by-product and rubber form a good coupling effect, the binding capacity of the white carbon black and the rubber is improved, and the efficiency of breaking and recombining a white carbon black-rubber network structure is enhanced. In addition, the aggregate of the white carbon black modified by the corn by-product is smaller, and the dispersibility of the modified white carbon black in the rubber matrix is better.
Drawings
FIG. 1 is a scanning electron microscope photograph showing the microdispersion and compatibility of ordinary cellulose particles and synthetic rubber in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the micro-dispersibility and compatibility of cellulose triacetate particles and synthetic rubber in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of the micro-dispersibility and compatibility of cellulose acetate particles and synthetic rubber in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image showing the micro-dispersibility and compatibility of methylcellulose particles and synthetic rubber in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of the micro-dispersibility and compatibility of sodium carboxymethylcellulose particles and synthetic rubber in example 5 of the present invention;
FIG. 6 is a stress-strain performance curve of a corn byproduct based synthetic rubber environment-friendly material prepared from cellulose modified white carbon black of different structures in examples 1-5 of the present invention;
FIG. 7 is a scanning electron microscope image of the microdispersion and compatibility of prolamin particles and synthetic rubber in example 6 of the present invention;
FIG. 8 is a graph of strain versus loss modulus for a corn by-product based synthetic rubber environmentally friendly material;
FIG. 9 is a graph of strain versus storage modulus for a corn by-product based synthetic rubber environmentally friendly material;
FIG. 10 is a graph of strain versus Tan δ for a corn by-product based synthetic rubber environmentally friendly material.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the following examples, the preparation method of the adopted corn cellulose is as follows: corn bran → drying → crushing → sieving → petroleum ether degreasing → alpha-amylase enzymolysis → alkaline hydrolysis (wherein, the liquid-material ratio is 16:1mL/g, the NaOH mass fraction is 7.4%, the extraction temperature is 70 ℃, the extraction time is 80min) → suction filtration → decolorization → centrifugation → precipitation → water washing → drying → corn cellulose; the prepared corn cellulose can be divided into one or more of common cellulose, cellulose acetate, methyl cellulose, sodium carboxymethyl cellulose and cellulose triacetate according to different structures, and the types of the cellulose are determined according to different production places of corn.
In the following examples, the method for preparing prolamin was: maize yellow powder (CGM) → drying → crushing → sieving → absolute ethyl alcohol decoloration (solid-to-liquid ratio is 1:10) → 55 ℃ thermostatic waterbath extraction for 30min → decoloration CGM → amylase enzymolysis → ultrasonic auxiliary ethanol extraction (wherein, ultrasonic power is 485W, ethanol volume concentration is 75%, extraction temperature is 60 ℃, extraction time is 60min) → centrifugation → supernatant → pH regulation 6 → standing → centrifugation → precipitation → water washing → freeze drying → prolamin (Zein), and the extraction rate of the prolamin is 89.86%.
Example 1
A preparation method of a corn byproduct based synthetic rubber environment-friendly material comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring 100g of precipitation method SI175 white carbon black, 10g of ordinary cellulose and 2g of glycerol by using a high-speed stirrer according to the proportion to obtain the corn cellulose modified white carbon black;
step 2:
taking 100g of styrene butadiene rubber (ESBR 1500E), 50g of corn cellulose modified white carbon black, 1g of stearic acid, 5g of zinc oxide, 0.9g of accelerator CZ, 1.8g of sulfur, 1.0g of antioxidant RD1.0g and 1.0g of antioxidant 4010NA, and mixing and vulcanizing the raw materials to obtain a corn byproduct based synthetic rubber environment-friendly material; wherein the vulcanization time is 0.21min, the vulcanization speed is 4.7 ℃/min, and the positive vulcanization point is 21.32 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, the maximum torque (MH) is 3.55N.m, the minimum torque (ML) is 1.44N.m, and the MH-ML is 2.11 N.m; the scanning electron micrograph of the micro-dispersion and the compatibility is shown in figure 1, which shows that the micro-dispersion is very good.
The physical and mechanical properties of the prepared corn by-product based synthetic rubber environment-friendly material are shown in table 1.
Example 2
A preparation method of a corn byproduct based synthetic rubber environment-friendly material comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring 100g of precipitation method SI175 white carbon black, 10g of cellulose triacetate and 2g of glycerol according to the proportion to obtain the corn cellulose modified white carbon black;
step 2:
taking 100g of styrene butadiene rubber (ESBR 1500E), 50g of corn cellulose modified white carbon black, 1g of stearic acid, 5g of zinc oxide, 0.9g of accelerator CZ, 1.8g of sulfur, 1.0g of antioxidant RD1.0g and 1.0g of antioxidant 4010NA, and mixing and vulcanizing the raw materials to obtain a corn byproduct based synthetic rubber environment-friendly material; wherein the vulcanization time is 0.32min, the vulcanization speed is 4.88 ℃/min, and the positive vulcanization point is 21.53 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, and the maximum torque (MH) is 3.89N.m, the minimum torque (ML) is 1.82N.m, and the MH-ML is 2.07 N.m; the scanning electron micrograph of the micro-dispersion and the compatibility is shown in figure 2, which illustrates that the micro-dispersion is poor
The physical and mechanical properties of the prepared corn by-product based synthetic rubber environment-friendly material are shown in table 1.
Example 3
A preparation method of a corn byproduct based synthetic rubber environment-friendly material comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring 100g of precipitation method SI175 white carbon black, 10g of cellulose acetate and 2g of glycerol according to the proportion to obtain the corn cellulose modified white carbon black;
step 2:
taking 100g of styrene butadiene rubber (ESBR 1500E), 50g of corn cellulose modified white carbon black, 1g of stearic acid, 5g of zinc oxide, 0.9g of accelerator CZ, 1.8g of sulfur, 1.0g of antioxidant RD1.0g and 1.0g of antioxidant 4010NA, and mixing and vulcanizing the raw materials to obtain a corn byproduct based synthetic rubber environment-friendly material; wherein the vulcanization time is 0.19min, the vulcanization speed is 4.25 ℃/min, and the positive vulcanization point is 23.46 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, the maximum torque (MH) is 2.55N.m, the minimum torque (ML) is 1.18N.m, and the MH-ML is 1.38 N.m; the scanning electron micrograph of the micro-dispersibility and the compatibility is shown in FIG. 3, which shows that the dispersibility is good.
The physical and mechanical properties of the prepared corn by-product based synthetic rubber environment-friendly material are shown in table 1.
Example 4
A preparation method of a corn byproduct based synthetic rubber environment-friendly material comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring 100g of precipitation method SI175 white carbon black, 10g of methyl cellulose and 2g of glycerol according to the proportion to obtain the corn cellulose modified white carbon black;
step 2:
taking 100g of styrene butadiene rubber (ESBR 1500E), 50g of corn cellulose modified white carbon black, 1g of stearic acid, 5g of zinc oxide, 0.9g of accelerator CZ, 1.8g of sulfur, 1.0g of antioxidant RD1.0g and 1.0g of antioxidant 4010NA, and mixing and vulcanizing the raw materials to obtain a corn byproduct based synthetic rubber environment-friendly material; wherein the vulcanization time is 0.18min, the vulcanization speed is 4.84 ℃/min, and the positive vulcanization point is 20.54 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, the maximum torque (MH) is 3.73N.m, the minimum torque (ML) is 1.45N.m, and the MH-ML is 2.28 N.m; the scanning electron micrograph of the micro-dispersibility and the compatibility is shown in FIG. 4, which shows that the dispersibility is good.
The physical and mechanical properties of the prepared corn by-product based synthetic rubber environment-friendly material are shown in table 1.
Example 5
A preparation method of a corn byproduct based synthetic rubber environment-friendly material comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring 100g of precipitation method SI175 white carbon black, 10g of carboxymethyl cellulose and 2g of glycerol according to the proportion to obtain the corn cellulose modified white carbon black;
step 2:
taking 100g of styrene butadiene rubber (ESBR 1500E), 50g of corn cellulose modified white carbon black, 1g of stearic acid, 5g of zinc oxide, 0.9g of accelerator CZ, 1.8g of sulfur, 1.0g of antioxidant RD1.0g and 1.0g of antioxidant 4010NA, and mixing and vulcanizing the raw materials to obtain a corn byproduct based synthetic rubber environment-friendly material; wherein the vulcanization time is 0.19min, the vulcanization speed is 4.8 ℃/min, and the positive vulcanization point is 21.04 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, the maximum torque (MH) is 3.49N.m, the minimum torque (ML) is 1.31N.m, and the MH-ML is 2.18 N.m; the scanning electron micrograph of the micro-dispersibility and the compatibility is shown in FIG. 5, which shows that the dispersibility is good.
The physical and mechanical properties of the prepared corn by-product based synthetic rubber environment-friendly material are shown in table 1.
TABLE 1 physical and mechanical properties of corn by-product-based synthetic rubber environment-friendly material prepared from cellulose modified white carbon black with different structures
Figure BDA0002600407950000061
The stress-strain performance curve of the corn byproduct based synthetic rubber environment-friendly material prepared from the cellulose modified white carbon black with different structures in examples 1-5 of the invention is shown in fig. 6, which illustrates that the corn byproduct based synthetic rubber environment-friendly material prepared from the methyl cellulose modified white carbon black has outstanding performance.
Example 6
A preparation method of a corn byproduct based synthetic rubber environment-friendly material comprises the following steps:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring 100g of precipitation method SI175 white carbon black, 10g of alcohol soluble protein and 3g of glycol according to the proportion to obtain alcohol soluble protein modified white carbon black;
step 2:
taking 100g of styrene butadiene rubber (ESBR 1500E), 50g of alcohol-soluble protein modified white carbon black, 1g of stearic acid, 5g of zinc oxide, 0.9g of accelerator CZ, 1.8g of sulfur, 1.0g of antioxidant RDI and 1.0g of antioxidant 4010NA, and mixing and vulcanizing the raw materials to obtain the corn byproduct based synthetic rubber environment-friendly material; wherein the vulcanization time is 0.57min, the vulcanization speed is 15.27 ℃/min, and the positive vulcanization point is 6.58 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, the maximum torque (MH) is 3.70N.m, the minimum torque (ML) is 1.30N.m, and the MH-ML is 2.39 N.m; the scanning electron micrograph of the microdispersion and the compatibility is shown in FIG. 7, which illustrates that the dispersibility is poor.
The physical and mechanical properties of the prepared corn by-product based synthetic rubber environment-friendly material are shown in table 2.
Example 7
The preparation method of the corn byproduct based synthetic rubber environment-friendly material is the same as that in example 6, except that the formula of the rubber is as follows:
100 parts of isoprene rubber, 60 parts of corn byproduct modified white carbon black, 3 parts of stearic acid, 7 parts of zinc oxide, 1.2 parts of an accelerator, 3 parts of a vulcanizing agent and 2.0 parts of an anti-aging agent 4010 NA;
in the corn by-product modified white carbon black, corn by-products are corn cellulose and alcohol soluble protein; the white carbon black preparation comprises 100 parts of precipitated white carbon black, 6 parts of corn cellulose and 12 parts of alcohol soluble protein respectively, and 3 parts of glycerol and ethylene glycol.
Example 8
The preparation method of the corn byproduct based synthetic rubber environment-friendly material is the same as that in example 6, except that the formula of the rubber is as follows:
the preparation method of the corn byproduct based synthetic rubber environment-friendly material is the same as that in example 6, except that the formula of the rubber is as follows:
100 parts of butadiene rubber, 50 parts of corn by-product modified white carbon black, 1 part of stearic acid, 3 parts of zinc oxide, 0.8 part of accelerator, 1 part of vulcanizing agent and 2.0 parts of anti-aging agent 4010 NA;
in the corn by-product modified white carbon black, the corn by-product is prolamin; the white carbon black comprises 100 parts of precipitated white carbon black, 8 parts of alcohol soluble protein and 1 part of glycerol.
Comparative example
The same as example 6, except that no prolamin was added, the vulcanization time was 1.25min, the vulcanization rate was 15.58 ℃/min, and the positive vulcanization point was 7.04 min.
The prepared corn byproduct based synthetic rubber environment-friendly material is tested, the maximum torque (MH) is 2.86N.m, the minimum torque (ML) is 0.63N.m, and the MH-ML is 2.23 N.m; the physical and mechanical properties of the synthetic rubbers prepared therefrom are shown in Table 2.
TABLE 2 stress-strain behavior of the corn by-product based synthetic rubber environmentally friendly material prepared from alcohol soluble egg modified white carbon black (170 ℃ X T90 min)
Figure BDA0002600407950000071
The dynamic mechanical properties of the synthetic rubbers prepared in examples 1 and 6 and comparative examples were measured and the relationship between strain and loss modulus is shown in FIG. 8 and the relationship between strain and storage modulus is shown in FIG. 9.
From fig. 8, it can be seen that the loss modulus and the storage modulus of the corn byproduct based synthetic rubber environment-friendly material decrease with the increase of strain, and the decrease range reflects the capability of breaking and recombining the network between the rubber and the white carbon black particles, and is generally used to characterize the binding capability of the white carbon black and the rubber. As can be seen from FIG. 8, the loss modulus and the storage modulus of both the alcohol-soluble protein-modified white carbon black and the cellulose-modified white carbon black are lower than those of the unmodified white carbon black sample, which indicates that the two modified compounds can form a good coupling effect with the white carbon black and the rubber, thereby improving the binding capacity of the white carbon black and the rubber and enhancing the efficiency of the destruction and recombination of the white carbon black-rubber network structure.
As can be seen from fig. 9 and 10, the payne effect refers to a phenomenon in which the dynamic modulus of the filled rubber is sharply decreased with an increase in strain, and the magnitude of the decrease reflects the size of the aggregate of the white carbon and the dispersibility of the carbon black in the rubber matrix. It can be seen from the figure that the payne effect of the alcohol soluble protein modified white carbon black (Z-white carbon black) and the cellulose modified white carbon black (C-white carbon black) is lower than that of the unmodified white carbon black sample, which indicates that the aggregates of the alcohol soluble protein and the cellulose modified white carbon black are smaller, and the modified white carbon black has better dispersibility in the SBR matrix and is consistent with the corresponding scanning electron microscope picture. Meanwhile, the hysteresis loss of the vulcanized rubber of the three materials is that the alcohol soluble protein modified white carbon black (Z-white carbon black) < the cellulose modified white carbon black (C-white carbon black) < the white carbon black according to the analysis of a strain-loss factor (tan delta) curve diagram.

Claims (10)

1. The corn byproduct based synthetic rubber environment-friendly material is characterized in that the formula of the corn byproduct based synthetic rubber environment-friendly material comprises the following raw materials in parts by weight: 100 parts of rubber, 40-60 parts of corn byproduct modified white carbon black, 1-3 parts of stearic acid, 3-7 parts of zinc oxide, 0.8-1.2 parts of accelerator and 1-3 parts of vulcanizing agent;
in the corn by-product modified white carbon black, the corn by-product is corn cellulose and/or alcohol soluble protein; the corn by-product modified white carbon black comprises 100 parts of precipitation-method white carbon black, 8-15 parts of corn cellulose and/or alcohol soluble protein and 1-3 parts of polyhydric alcohol.
2. The corn byproduct based synthetic rubber environment-friendly material as claimed in claim 1, wherein the rubber is one or more of styrene butadiene rubber, butadiene rubber and isoprene rubber; the polyalcohol is glycerol and/or ethylene glycol.
3. The corn by-product-based synthetic rubber environment-friendly material as claimed in claim 1, wherein when the corn by-product modified white carbon black is corn cellulose modified white carbon black, raw materials adopted by the corn by-product-based synthetic rubber environment-friendly material comprise precipitated white carbon black, corn cellulose and glycerol; the weight parts of all the raw materials are as follows: 100 parts of precipitated white carbon black; 8-15 parts of corn cellulose and 1-2 parts of glycerol.
4. The environment-friendly corn-byproduct-based synthetic rubber material as claimed in claim 1, wherein when the corn byproduct modified white carbon black is prolamin-modified white carbon black, the adopted raw materials comprise precipitation-process white carbon black, prolamin and glycol; the weight parts of all the raw materials are as follows: 100 parts of precipitated white carbon black; 8-15 parts of alcohol soluble protein and 2-3 parts of glycol.
5. The corn by-product-based synthetic rubber environment-friendly material as claimed in any one of claims 1 and 3 to 4, wherein the precipitated silica is precipitated SI175 silica, and the specific surface area of the precipitated silica is 170-175 m as measured by a surfactant adsorption method2/g。
6. The corn by-product-based synthetic rubber environment-friendly material as claimed in claim 1, wherein the corn cellulose is one or more of common cellulose, cellulose acetate, methyl cellulose, sodium carboxymethyl cellulose and cellulose triacetate.
7. The corn byproduct based synthetic rubber environment-friendly material as claimed in claim 1, wherein the formula of the corn byproduct based synthetic rubber environment-friendly material further comprises 1-2 parts of anti-aging agent, and anti-aging agent RD and/or anti-aging agent 4010 NA.
8. The corn by-product based synthetic rubber environment-friendly material as claimed in claim 7, wherein when the antioxidant is antioxidant RD and antioxidant 4010NA, the mass ratio is: (0.5-1):(0.5-1).
9. The method for preparing the corn by-product-based synthetic rubber environment-friendly material according to any one of claims 1 to 8, comprising the steps of:
step 1: preparation of cellulose modified white carbon black
Uniformly stirring and mixing the white carbon black obtained by the precipitation method, the corn by-product and the polyhydric alcohol according to the proportion to obtain the corn by-product modified white carbon black; wherein the corn by-product is corn cellulose and/or alcohol soluble protein;
step 2:
according to the formula of the corn byproduct based synthetic rubber environment-friendly material, the raw materials are mixed and vulcanized to obtain the corn byproduct based synthetic rubber environment-friendly material; wherein, the vulcanization time is 0.18-0.57 min, the vulcanization speed is 4.25-6.58 ℃/min, and the positive vulcanization point is 15.27-23.46 min.
10. The method for preparing the environment-friendly corn byproduct based synthetic rubber material according to claim 9, wherein the prepared environment-friendly corn byproduct based synthetic rubber material is prepared by using prolamin modified white carbon black, and the tensile strength of the environment-friendly corn byproduct based synthetic rubber material is improved by 6.2-18.6%.
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