阅读说明：本技术 一种改性纳米纤维素/聚吡咯复合材料及制备方法、抗静电橡胶组合物及制备方法 (Modified nano-cellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof ) 是由 汤晶 云霄 王伟 任衍峰 周天明 于 2021-05-14 设计创作，主要内容包括：本发明公开了一种改性纳米纤维素/聚吡咯复合材料及制备方法、抗静电橡胶组合物及制备方法,所述改性纳米纤维素/聚吡咯复合材料,按重量份计,包括纳米纤维素90-110份,苯乙烯15-25份,丙烯酸30-50份,吡咯50-70份,引发剂0.4-0.6份；将改性纳米纤维素/聚吡咯复合材料加入橡胶组合物中制备得到抗静电橡胶组合物；苯乙烯和丙烯酸对纳米纤维素进行改性,使其在橡胶基体中均匀分散；聚吡咯与纳米纤维素间形成氢键,随纳米纤维素在橡胶基体形成多层次交联的网络结构,形成导电通路,提高橡胶组合物的导电性能；由该橡胶组合物生产的轮胎可以很好的将轮胎行驶过程中产生的静电导出,从而提高橡胶轮胎的抗静电性能。(The invention discloses a modified nano-cellulose/polypyrrole composite material and a preparation method thereof, and an antistatic rubber composition and a preparation method thereof, wherein the modified nano-cellulose/polypyrrole composite material comprises, by weight, 90-110 parts of nano-cellulose, 15-25 parts of styrene, 30-50 parts of acrylic acid, 50-70 parts of pyrrole, and 0.4-0.6 part of an initiator; adding the modified nano-cellulose/polypyrrole composite material into a rubber composition to prepare an antistatic rubber composition; styrene and acrylic acid modify the nano-cellulose to uniformly disperse the nano-cellulose in a rubber matrix; hydrogen bonds are formed between the polypyrrole and the nano-cellulose, and a multi-layer cross-linked network structure is formed in the rubber matrix along with the nano-cellulose to form a conductive path, so that the conductive performance of the rubber composition is improved; the tire produced by the rubber composition can well lead out static electricity generated in the running process of the tire, thereby improving the antistatic performance of the rubber tire.)

1. The modified nano-cellulose/polypyrrole composite material is characterized by comprising, by weight, 90-110 parts of nano-cellulose, 15-25 parts of styrene, 30-50 parts of acrylic acid, 50-70 parts of pyrrole and 0.4-0.6 part of an initiator.

2. The modified nanocellulose/polypyrrole composite material according to claim 1, wherein the modification mode of nanocellulose is polymer graft modification, and the adopted modification monomers are styrene and acrylic acid.

3. The preparation method of the modified nano-cellulose/polypyrrole composite material according to claim 2, characterized in that the nano-cellulose, the initiator and the styrene are mixed uniformly, acrylic acid is added for reaction to obtain the modified nano-cellulose suspension, 15-25 parts of pyrrole and toluene-4-sulfonic acid are added for mixing uniformly, and 0.1mol/L FeCl is added₃And (4) reacting 17-22 parts of aqueous solution to obtain the modified nano-cellulose/polypyrrole composite material.

4. The preparation method of the modified nanocellulose/polypyrrole composite material according to claim 3, characterized by comprising the following steps:

s1, preparing modified nano cellulose: preparing the nano-cellulose into 2g/L nano-cellulose aqueous solution, placing the nano-cellulose aqueous solution, an initiator and styrene into a flask, stirring for 15-20min at the temperature of 60-85 ℃, dropwise adding acrylic acid, and reacting for 60-180min at the reaction temperature to obtain modified nano-cellulose suspension;

s2, adding pyrrole and toluene-4-sulfonic acid into the modified nano cellulose suspension, magnetically stirring for 1-2h under the condition of ice-water bath, and dropwise adding FeCl₃Reacting for 8-10 hours under the condition of ice-water bath, and obtaining the modified nano-cellulose/polypyrrole composite material after suction filtration.

5. The antistatic rubber composition is characterized by comprising the following components in parts by weight:

50-70 parts of solution polymerized styrene-butadiene rubber;

30-50 parts of butadiene rubber;

60-80 parts of white carbon black;

9.6-12.8 parts of a silane coupling agent;

3-5 parts of an anti-aging agent;

3-5 parts of zinc oxide;

1-3 parts of stearic acid;

20-30 parts of operating oil;

1-2 parts of sulfur;

2.0-3.3 parts of an accelerator;

10-18 parts of antistatic agent.

The antistatic agent is the modified nanocellulose/polypyrrole composite material according to any one of claims 1-2.

6. The antistatic rubber composition as claimed in claim 5, wherein the solution polymerized styrene-butadiene rubber is a terminal modified solution polymerized styrene-butadiene rubber with styrene content of 21 wt% and vinyl content of 63 wt%.

7. The antistatic rubber composition according to claim 5, wherein the butadiene rubber is neodymium-based butadiene rubber; the white carbon black is high-dispersion white carbon black; the silane coupling agent is Si 69; the operating oil is environment-friendly aromatic oil TDAE; the anti-aging agent is p-phenylenediamine anti-aging agent 4020; the sulfur is insoluble sulfur; the accelerator is accelerator DPG and accelerator NS.

8. The method for preparing an antistatic rubber composition according to claim 5, comprising the steps of:

first-stage mixing: adding solution polymerized styrene-butadiene rubber, white carbon black, operating oil, a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid into an internal mixer for mixing to obtain a section of masterbatch;

and (3) second-stage mixing: adding the first-stage masterbatch, an antistatic agent and zinc oxide into an internal mixer for mixing to obtain second-stage masterbatch;

and (3) final refining: and adding the two-stage masterbatch, the accelerator NS and the sulfur into an internal mixer for mixing to obtain final rubber.

9. The method for preparing the antistatic rubber composition according to claim 8, which is characterized by comprising the following steps:

first-stage mixing: setting the rotating speed of an internal mixer to be 30-50rpm, adding solution polymerized styrene butadiene rubber and butadiene rubber, lifting lump, adding white carbon black and operating oil, lifting lump, adding a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid, pressing a top bolt for 60-100s, discharging rubber when the temperature of a rubber material is raised to 150 ℃, discharging the rubber, discharging sheets, cooling, and building a stack to obtain a section of masterbatch;

and (3) second-stage mixing: setting the rotating speed of an internal mixer to be 30-50rpm, adding a first-stage masterbatch and an antistatic agent, pressing a top bolt for 50-100s, lifting a lump, adding zinc oxide, pressing the top bolt for 30-60s, heating the rubber material to 140 ℃, discharging the rubber, discharging sheets, cooling, and building stacks to obtain a second-stage masterbatch;

and (3) final refining: setting the rotating speed of an internal mixer to be 30-50rpm, adding two-stage masterbatch, an accelerator and sulfur, pressing a top bolt for 50-100s, lifting a lump, pressing the top bolt for 20-100s, lifting the lump, pressing the top bolt, discharging rubber, discharging pieces, cooling, stacking when the temperature of a rubber material is raised to 95 ℃, and obtaining the final rubber.

Technical Field

The invention relates to the technical field of tire rubber formulas, in particular to a modified nano-cellulose/polypyrrole composite material and a preparation method thereof, and an antistatic rubber composition and a preparation method thereof.

Background

With the development of the tire industry and the increase of consumer demand, the development trend of tires is more focused on quality and performance, including safety, fuel economy, wear resistance and the like. The concept of 'green tire' is provided in the last 90 years, and the tread rubber formula is optimized by using high-part white carbon black in the tread formula, so that the effects of low rolling resistance, improved wet skid resistance and improved wear resistance are achieved. However, static electricity accumulation is easily formed in the running process of the tire, and the rubber and the white carbon black are non-conductive materials, so that the charge cannot be led out, and the antistatic performance of the tire is poor.

The nano cellulose (CNC) has the characteristics of high strength and low density, is a renewable and degradable green nano material, can be used as a reinforcing system to replace fillers when being applied to tires, but has hydrogen bonds inside and outside molecules, so that the nano cellulose is difficult to disperse, and the use of the nano cellulose in non-polar rubber is limited. Polypyrrole (PPy) is a high-conductivity polymer material, can be connected with cellulose through hydrogen bonds, and the CNC/PPy conductive material formed by compounding the polypyrrole (PPy) and the cellulose has good environmental protection performance and high stability. From the perspective of formula design, the nano-cellulose and the polypyrrole are compounded and used in a rubber formula as an antistatic agent, so that the antistatic performance of the tire can be effectively improved; however, a large amount of hydroxyl exists on the surface and inside of the nano-cellulose, the hydrophobicity is poor, the compatibility and the dispersibility of the nano-cellulose in non-polar rubber are influenced, and the compatibility of the nano-cellulose and polypyrrole in an elastomer is poor due to a special pi-bond macromolecular chain structure in the polypyrrole, so that the compatibility of the nano-cellulose and polypyrrole composite material and a rubber system is difficult, and therefore, how to solve the problem of the dispersibility of the nano-cellulose and polypyrrole composite material in the rubber system, the nano-cellulose and polypyrrole composite material is uniformly dispersed in the rubber system, and the antistatic performance of the rubber material is improved is a difficult point.

Disclosure of Invention

In order to solve the problems, the invention provides a modified nano-cellulose/polypyrrole composite material and a preparation method thereof, and an antistatic rubber composition and a preparation method thereof.

The technical scheme adopted by the invention is as follows:

the modified nano-cellulose/polypyrrole composite material comprises, by weight, 90-110 parts of nano-cellulose, 15-25 parts of styrene, 30-50 parts of acrylic acid, 50-70 parts of pyrrole and 0.4-0.6 part of an initiator.

Preferably, the modification mode of the nanocellulose is polymer grafting modification, and the adopted modification monomers are styrene and acrylic acid.

The nano-cellulose is a high-strength biomass filler, can be regenerated and has wide sources, but a large amount of hydroxyl groups exist on the surface and inside of the nano-cellulose, so that the nano-cellulose has poor hydrophobicity and the compatibility and the dispersibility of the nano-cellulose in non-polar rubber are influenced. Styrene and acrylic acid are adopted to modify the nano-cellulose, carboxyl at the end of the acrylic acid chain permeates into the nano-cellulose and is subjected to polycondensation with hydroxyl of the nano-cellulose to perform grafting reaction, so that the strong acting force in the nano-cellulose is destroyed, and the bonding effect between the nano-cellulose and rubber is increased; hydrophobic styrene reacts with acrylic double bonds through free radical polymerization, so that the surface polarity of the nano-cellulose is reduced, the compatibility of the nano-cellulose in non-polar rubber is improved, and the modified nano-cellulose has better compatibility with solution polymerized styrene-butadiene rubber due to the existence of a benzene ring structure in the styrene, so that the modified nano-cellulose can be well dispersed in a rubber matrix.

The invention also aims to provide a preparation method of the modified nano-cellulose/polypyrrole composite material, which comprises the steps of uniformly mixing the nano-cellulose, the initiator and the styrene, adding the acrylic acid for reaction to obtain a modified nano-cellulose suspension, adding 15-25 parts of pyrrole and toluene-4-sulfonic acid for uniform mixing, and adding 0.1mol/L FeCl₃And (4) reacting 17-22 parts of aqueous solution to obtain the modified nano-cellulose/polypyrrole composite material.

Preferably, the method specifically comprises the following steps:

s1, preparing modified nano cellulose: preparing the nano-cellulose into 2g/L nano-cellulose aqueous solution, placing the nano-cellulose aqueous solution, an initiator and styrene into a flask, stirring for 15-20min at the temperature of 60-85 ℃, dropwise adding acrylic acid, and reacting for 60-180min at the reaction temperature to obtain modified nano-cellulose suspension;

s2, adding pyrrole and toluene-4-sulfonic acid into the modified nano cellulose suspension, magnetically stirring for 1-2h under the condition of ice-water bath, and dropwise adding FeCl₃Reacting for 8-10 hours under the condition of ice-water bath, and obtaining the modified nano-cellulose/polypyrrole composite material after suction filtration.

In FeCl₃Middle Fe³⁺Under the catalytic oxidation action of the organic acid, pyrrole is polymerized to form polypyrrole which is a conductive polymer, so that the organic acid is low in cost and is environment-friendly. The special pi-bond macromolecular chain structure in polypyrrole makes the polypyrrole have poor compatibility in an elastomer, but the polypyrrole can form a hydrogen bond with nanocellulose, the hydrogen bond is uniformly loaded on the nanocellulose, the modified nanocellulose/polypyrrole composite material is added into a rubber formula, and the polypyrrole is uniformly dispersed in a rubber matrix along with the nanocellulose to form polypyrroleThe composite material realizes the conduction of current in the rubber matrix through the conductive path formed by the polypyrrole, thereby leading out the static electricity generated in the rubber and improving the conductive performance of the rubber.

The invention also provides an antistatic rubber composition, which comprises the following components in parts by weight:

50-70 parts of solution polymerized styrene-butadiene rubber;

30-50 parts of butadiene rubber;

60-80 parts of white carbon black;

9.6-12.8 parts of a silane coupling agent;

3-5 parts of an anti-aging agent;

3-5 parts of zinc oxide;

1-3 parts of stearic acid;

20-30 parts of operating oil;

1-2 parts of sulfur;

2.0-3.3 parts of an accelerator;

10-18 parts of antistatic agent.

The antistatic agent is the modified nano-cellulose/polypyrrole composite material.

Preferably, the solution-polymerized styrene-butadiene rubber is a terminal-modified solution-polymerized styrene-butadiene rubber having a styrene content of 21 wt% and a vinyl content of 63 wt%.

Preferably, the butadiene rubber is neodymium butadiene rubber; the white carbon black is high-dispersion white carbon black; the silane coupling agent is Si 69; the operating oil is environment-friendly aromatic oil TDAE; the anti-aging agent is p-phenylenediamine anti-aging agent 4020; the sulfur is insoluble sulfur; the accelerator is accelerator DPG and accelerator NS.

The modified nano-cellulose/polypyrrole composite material is added into the rubber composition as an antistatic agent, the styrene and acrylic acid modified nano-cellulose has good compatibility with a rubber matrix and forms a hydrogen bond with polypyrrole, so that the styrene and acrylic acid modified nano-cellulose is uniformly dispersed in the rubber matrix to form a multi-layer cross-linked network structure, a conductive path is formed in the rubber composition, the conductivity of the rubber composition is effectively improved, the tire produced by the rubber composition can well lead out static electricity generated in the running process of the tire, and the antistatic performance of the rubber tire is improved.

The last object of the present invention is to provide a process for the preparation of an antistatic rubber composition comprising the steps of:

first-stage mixing: adding solution polymerized styrene-butadiene rubber, white carbon black, operating oil, a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid into an internal mixer for mixing by using a shearing internal mixer to obtain a section of master batch;

and (3) second-stage mixing: adding the first-stage masterbatch, an antistatic agent and zinc oxide into an internal mixer for mixing to obtain second-stage masterbatch;

and (3) final refining: and adding the two-stage masterbatch, the accelerator NS and the sulfur into an internal mixer for mixing to obtain final rubber.

Preferably, the method specifically comprises the following steps:

first-stage mixing: setting the rotating speed of an internal mixer to be 30-50rpm, adding solution polymerized styrene butadiene rubber and butadiene rubber, lifting lump, adding white carbon black and operating oil, lifting lump, adding a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid, pressing a top bolt for 60-100s, discharging rubber when the temperature of a rubber material is raised to 150 ℃, discharging the rubber, discharging sheets, cooling, and building a stack to obtain a section of masterbatch;

and (3) second-stage mixing: setting the rotating speed of an internal mixer to be 30-50rpm, adding a first-stage masterbatch and an antistatic agent, pressing a top bolt for 50-100s, lifting a lump, adding zinc oxide, pressing the top bolt for 30-60s, heating the rubber material to 140 ℃, discharging the rubber, discharging sheets, cooling, and building stacks to obtain a second-stage masterbatch;

and (3) final refining: setting the rotating speed of an internal mixer to be 30-50rpm, adding two-stage masterbatch, an accelerator and sulfur, pressing a top bolt for 50-100s, lifting a lump, pressing the top bolt for 20-100s, lifting the lump, pressing the top bolt, discharging rubber, discharging pieces, cooling, stacking when the temperature of a rubber material is raised to 95 ℃, and obtaining the final rubber.

Compared with the prior art, the invention provides a modified nano-cellulose/polypyrrole composite material and a preparation method thereof, an antistatic rubber composition and a preparation method thereof,

1. styrene and acrylic acid are adopted to modify the nano-cellulose, and the acrylic acid and the nano-cellulose are subjected to grafting reaction to destroy the strong acting force in the nano-cellulose and increase the bonding effect between the nano-cellulose and rubber; hydrophobic styrene reacts with acrylic acid double bonds to reduce the surface polarity of the nano-cellulose; meanwhile, the benzene ring structure in the styrene ensures that the modified nano-cellulose has better compatibility with the solution polymerized styrene-butadiene rubber, so that the modified nano-cellulose is well dispersed in a rubber matrix;

2. pyrrole is polymerized to form polypyrrole in the reaction process, hydrogen bonds are formed between the polypyrrole and the nanocellulose, the polypyrrole and the nanocellulose are uniformly loaded on the nanocellulose, and a multi-level cross-linked network structure is formed along with the uniform dispersion of the nanocellulose in a rubber matrix, so that a conductive path is formed in the rubber composition, and the conductive performance of the rubber composition is improved;

3. the modified nano-cellulose/polypyrrole composite material is added into the rubber composition as the antistatic agent, and is uniformly dispersed in the rubber composition, so that the problem of dispersion of the antistatic agent in a rubber matrix is solved, and the tire produced by the rubber composition can well lead out static generated in the running process of the tire, so that the antistatic performance of the rubber tire is improved.

Detailed Description

The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.

Example 1

A preparation method of a modified nano-cellulose/polypyrrole composite material A specifically comprises the following steps:

s1, preparing modified nano cellulose: preparing 2g/L nano-cellulose aqueous solution from 100 parts by weight of nano-cellulose, placing the nano-cellulose aqueous solution, 0.5 part by weight of initiator and 20 parts by weight of styrene into a flask, stirring for 17min at 70 ℃, dropwise adding 40 parts by weight of acrylic acid, and reacting for 120min at a reaction temperature to obtain a modified nano-cellulose suspension;

s2, adding 60 parts by weight of pyrrole and 22 parts by weight of toluene-4-sulfonic acid into the modified nano-cellulose suspension, and dissolving the mixture in iceMagnetically stirring for 1.5h under the condition of water bath, and dropwise adding 19 parts by weight of 0.1mol/L FeCl₃And reacting for 9 hours under the condition of ice-water bath, and performing suction filtration to obtain the modified nano-cellulose/polypyrrole composite material A.

Example 2

A preparation method of a modified nano-cellulose/polypyrrole composite material B specifically comprises the following steps:

s1, preparing modified nano cellulose: preparing 90 parts by weight of nano-cellulose into 2g/L nano-cellulose aqueous solution, placing the nano-cellulose aqueous solution, 0.4 part by weight of initiator and 15 parts by weight of styrene into a flask, stirring for 15min at 60 ℃, dropwise adding 30 parts by weight of acrylic acid, and reacting for 60min at reaction temperature to obtain modified nano-cellulose suspension;

s2, adding 50 parts by weight of pyrrole and 15 parts by weight of toluene-4-sulfonic acid into the modified nano-cellulose suspension, magnetically stirring for 1 hour under the condition of ice-water bath, and dropwise adding 17 parts by weight of 0.1mol/L FeCl₃And reacting for 8 hours under the condition of ice-water bath, and performing suction filtration to obtain the modified nano-cellulose/polypyrrole composite material B.

Example 3

A preparation method of a modified nano-cellulose/polypyrrole composite material C specifically comprises the following steps:

s1, preparing modified nano cellulose: preparing 110 parts by weight of nano-cellulose into 2g/L nano-cellulose aqueous solution, placing the nano-cellulose aqueous solution, 0.6 part by weight of initiator and 25 parts by weight of styrene into a flask, stirring for 20min at 85 ℃, dropwise adding 50 parts by weight of acrylic acid, and reacting for 180min at a reaction temperature to obtain a modified nano-cellulose suspension;

s2, adding 70 parts by weight of pyrrole and 25 parts by weight of toluene-4-sulfonic acid into the modified nano-cellulose suspension, magnetically stirring for 2 hours under the condition of ice-water bath, and dropwise adding 22 parts by weight of 0.1mol/L FeCl₃And reacting for 10 hours under the condition of ice-water bath, and performing suction filtration to obtain the modified nano-cellulose/polypyrrole composite material C.

Examples 4 to 8, comparative examples 1 to 3

The specific formulations of the antistatic rubber compositions provided in examples 4-8 and the rubber compositions provided in comparative examples 1-3 are shown in Table 1.

TABLE 1 formulation tables of antistatic rubber compositions provided in examples 4 to 8 and rubber compositions provided in comparative examples 1 to 3

Wherein, the parts are all parts by weight in Table 1.

The antistatic rubber compositions provided in examples 4 to 6 and the rubber compositions provided in comparative examples 1 to 3 were subjected to property tests, and the test results are shown in Table 2.

TABLE 2 comparison of the properties of the antistatic rubber compositions provided in examples 4 to 6 and the rubber compositions provided in comparative examples 1 to 3

Detecting items	Example 4	Example 5	Example 6	Comparative example 1	Comparative example 2	Comparative example 3
							300% stress at definite elongation (MPa)	9.3	9.0	8.7	10.1	9.2	9.6
Tensile Strength (MPa)	16.8	17.2	16.3	18.1	17.3	17.5
							Elongation at Break (%)	550	496	520	488	522	536
Tear Strength (KN/m)	37	39	35	38	37	38
							Volume resistivity (omega cm)	7.71×1010	3.26×109	1.14×109	1.85×1015	3.76×1013	8.87×1012

As shown in Table 2, in examples 4 to 6, as the addition amount of the antistatic agent modified nanocellulose/polypyrrole composite material A increases, the volume resistivity of the rubber composition gradually decreases, and in example 6, 18 parts by weight of the modified nanocellulose/polypyrrole composite material A is added, the volume resistivity is the lowest, and the antistatic effect is the best; the antistatic agent is not added in the comparative example 1, the volume resistivity is highest, and the antistatic effect is worst;

in the comparative example 2, only 5 parts by weight of the antistatic agent modified nano-cellulose/polypyrrole composite material A is added, so that the addition amount is small, the volume resistivity is reduced to some extent, but the volume resistivity is not obvious, and the antistatic effect is poor;

in comparative example 3, the conventional unmodified nanocellulose/polypyrrole composite material was used as an antistatic agent and added to the rubber composition, and the volume resistivity thereof was not significantly decreased, the antistatic effect was poor, and the antistatic performance requirement of the tire could not be satisfied, because the unmodified nanocellulose/polypyrrole composite material had poor compatibility with the rubber composition and poor dispersion effect in the rubber composition, and thus the antistatic effect was poor.

Furthermore, the elongation at break of examples 4-6 are all greater than that of comparative example 1, indicating that the elongation at break increases after the addition of the antistatic agent to the rubber composition because the addition of the antistatic agent provides additional double bonds that react with the rubber macromolecular chains during vulcanization, increasing the molecular weight and crosslink density of the rubber composition.

In conclusion, the modified nano-cellulose/polypyrrole composite material provided by the invention is added into an antistatic rubber composition as an antistatic agent, so that the problem of dispersion of the antistatic agent in a rubber matrix is solved, the antistatic effect of the rubber composition is effectively improved, the modified nano-cellulose/polypyrrole composite material can be directly applied to a rubber formula filled with all-white carbon black, the tread rubber processing technology is met, the operation is simple, and the basic physical properties meet the performance requirements.

Example 9

The preparation method of the antistatic rubber composition provided in example 6 specifically includes the following steps:

first-stage mixing: setting the rotating speed of an internal mixer to be 30rpm, adding solution polymerized styrene butadiene rubber and butadiene rubber, lifting lumps, adding white carbon black and operating oil, lifting lumps, adding a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid, pressing a top bolt for 60s, discharging rubber when the temperature of a rubber material is raised to 150 ℃, discharging sheets, cooling, and building stacks to obtain a section of master batch;

and (3) second-stage mixing: setting the rotating speed of an internal mixer to be 30rpm, adding a section of masterbatch and an antistatic agent, pressing a top bolt for 50s, lifting lumps, adding zinc oxide, pressing the top bolt for 30s, discharging rubber when the temperature of rubber materials is raised to 140 ℃, discharging sheets, cooling, and building stacks to obtain a second section of masterbatch;

and (3) final refining: setting the rotating speed of an internal mixer to be 30rpm, adding two-stage masterbatch, an accelerator and sulfur, pressing a top bolt for 50s, lifting a lump, pressing a top bolt for 20s, lifting the lump, pressing the top bolt, heating the rubber material to 95 ℃, discharging the rubber, discharging the sheet, cooling, and stacking to obtain the final rubber.

Example 10

The preparation method of the antistatic rubber composition provided in example 7 specifically includes the following steps:

first-stage mixing: setting the rotating speed of an internal mixer at 50rpm, adding solution polymerized styrene butadiene rubber and butadiene rubber, lifting lumps, adding white carbon black and operating oil, lifting lumps, adding a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid, pressing a top bolt for 100s, discharging rubber when the temperature of a rubber material is raised to 150 ℃, discharging sheets, cooling, and building stacks to obtain a section of master batch;

and (3) second-stage mixing: setting the rotating speed of an internal mixer to be 50rpm, adding a section of masterbatch and an antistatic agent, pressing a top bolt for 100s, lifting lumps, adding zinc oxide, pressing the top bolt for 60s, discharging rubber when the temperature of rubber materials is raised to 140 ℃, discharging sheets, cooling, and building stacks to obtain a second section of masterbatch;

and (3) final refining: setting the rotating speed of an internal mixer to be 50rpm, adding two-stage masterbatch, an accelerator and sulfur, pressing a top bolt for 100s, lifting a lump, pressing a top bolt, heating a rubber material to 95 ℃, discharging the rubber, discharging sheets, cooling, and building stacks to obtain the final rubber.

Example 11

The preparation method of the antistatic rubber composition provided in example 8 specifically includes the following steps:

first-stage mixing: setting the rotating speed of an internal mixer to be 40rpm, adding solution polymerized styrene butadiene rubber and butadiene rubber, lifting lumps, adding white carbon black and operating oil, lifting lumps, adding a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid, pressing a top bolt for 80s, discharging rubber when the temperature of a rubber material is raised to 150 ℃, discharging sheets, cooling, and building stacks to obtain a section of master batch;

and (3) second-stage mixing: setting the rotating speed of an internal mixer to be 40rpm, adding a section of masterbatch and an antistatic agent, pressing a top bolt for 75s, lifting lumps, adding zinc oxide, pressing the top bolt for 45s, discharging rubber when the temperature of rubber materials is raised to 140 ℃, discharging sheets, cooling, and building stacks to obtain a second section of masterbatch;

and (3) final refining: setting the rotating speed of an internal mixer to be 40rpm, adding two-stage masterbatch, an accelerator and sulfur, pressing a top bolt for 75s, lifting a lump, pressing a top bolt for 60s, lifting the lump, pressing the top bolt, heating the rubber material to 95 ℃, discharging the rubber, discharging the sheet, cooling, and stacking to obtain the final rubber.

The modified nano-cellulose/polypyrrole composite material and the preparation method thereof, the antistatic rubber composition and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and central concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.