CN113667257B - Modified nanocellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof - Google Patents
Modified nanocellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof Download PDFInfo
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- CN113667257B CN113667257B CN202110527861.5A CN202110527861A CN113667257B CN 113667257 B CN113667257 B CN 113667257B CN 202110527861 A CN202110527861 A CN 202110527861A CN 113667257 B CN113667257 B CN 113667257B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7466—Combinations of similar mixers
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- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- 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
Abstract
The invention discloses a modified nano-cellulose/polypyrrole composite material, a preparation method, an antistatic rubber composition and a preparation method, 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 nano cellulose to make it uniformly disperse in rubber matrix; the polypyrrole and the nanocellulose form a hydrogen bond, and form a multi-level cross-linked network structure along with the nanocellulose in the rubber matrix to form a conductive path, so that the conductivity of the rubber composition is improved; the tyre produced by the rubber composition can well lead out static electricity generated in the tyre running process, thereby improving the antistatic performance of the rubber tyre.
Description
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, an antistatic rubber composition and a preparation method thereof.
Background
With the development of the tire industry and the improvement of consumer demands, 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 put forward in the 90 th century, and the tread rubber formula is optimized by using high-fraction 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 easy to form in the running process of the tire, rubber and white carbon black are non-conductive materials, and charges cannot be led out, so that the antistatic performance of the tire is poor.
The nanocellulose (cellulose nanocrystal, CNC) has the characteristics of high strength and low density, is a renewable and degradable green nanomaterial, can be used as a reinforcing system instead of a filler in a tire, but has hydrogen bonds inside and outside the molecule, so that the nanocellulose is difficult to disperse, and the use of the nanocellulose in nonpolar rubber is limited. Polypyrrole (PPy) is a high-conductivity polymer material, can be connected with cellulose by hydrogen bonds, and is a CNC/PPy conductive material formed by compounding the high-conductivity polymer material and the cellulose by hydrogen bonds, and has good environmental protection and high stability. From the aspect of formulation design, the nano cellulose and polypyrrole are compounded and used in a rubber formulation as an antistatic agent, so that the antistatic performance of the tire can be effectively improved; however, the surface and the inside of the nanocellulose have a large number of hydroxyl groups, the hydrophobicity is poor, the compatibility and the dispersibility of the nanocellulose in nonpolar rubber are affected, and the special pi-bond macromolecular chain structure in the polypyrrole leads to the poor compatibility of the nanocellulose and the polypyrrole in an elastomer, so that the nanocellulose and the polypyrrole composite material are difficult to be compatible with a rubber system, and therefore, how to solve the dispersibility of the nanocellulose and the polypyrrole composite material in the rubber system, so that the nanocellulose and the polypyrrole composite material are uniformly dispersed in the rubber system, and the antistatic performance of the rubber material is improved.
Disclosure of Invention
In order to solve the problems, the invention provides a modified nanocellulose/polypyrrole composite material, a preparation method, an antistatic rubber composition and a preparation method, wherein the nanocellulose is modified, the combination effect between the nanocellulose and rubber is increased, the nanocellulose and the rubber are uniformly dispersed in a rubber system, the nanocellulose and the polypyrrole are compounded in a rubber formula, the polypyrrole and the modified nanocellulose form hydrogen bonds, the nanocellulose is uniformly dispersed in a rubber matrix along with the nanocellulose, a multi-layer crosslinked network structure is formed, and a conductive path is formed in the rubber composition, so that the antistatic performance of a tire is effectively improved.
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 nanocellulose is modified by polymer grafting, and the adopted modified monomers are styrene and acrylic acid.
Nanocellulose is a high-strength biomass filler, renewable and widely available, but the presence of a large number of hydroxyl groups on the surface and inside of nanocellulose results in poor hydrophobicity, affecting its compatibility and dispersibility in nonpolar rubber. Styrene and acrylic acid are adopted to modify the nano cellulose, and carboxyl groups at the end of the acrylic acid penetrate into the nano cellulose and are condensed with hydroxyl groups of the nano cellulose to carry out grafting reaction, so that the strong action force in the nano cellulose is destroyed, and the bonding action between the nano cellulose and rubber is increased; the hydrophobic styrene reacts with acrylic double bonds through free radical polymerization, so that the surface polarity of the nanocellulose is reduced, the compatibility of the nanocellulose in nonpolar rubber is improved, and the existence of benzene ring structures in the styrene enables the modified nanocellulose to have better compatibility with solution polymerized styrene-butadiene rubber, so that the modified nanocellulose can be well dispersed in a rubber matrix.
The invention further aims to provide a preparation method of the modified nanocellulose/polypyrrole composite material, wherein the nanocellulose, the initiator and the styrene are uniformly mixed, acrylic acid is added for reaction to obtain a modified nanocellulose suspension, pyrrole and 15-25 parts of toluene-4-sulfonic acid are added for uniform mixing, and 0.1mol/L FeCl is added 3 17-22 parts of aqueous solution, and reacting to obtain the modified nano-cellulose/polypyrrole composite material.
Preferably, the method specifically comprises the following steps:
s1, preparing modified nanocellulose: preparing the nanocellulose into 2g/L nanocellulose aqueous solution, placing the nanocellulose aqueous solution, an initiator and styrene into a flask, stirring for 15-20min at 60-85 ℃, dropwise adding acrylic acid, and reacting for 60-180min at the reaction temperature to obtain modified nanocellulose suspension;
s2, adding pyrrole and toluene-4-sulfonic acid into the modified nanocellulose suspension, magnetically stirring for 1-2h under the ice water bath condition, and dropwise adding FeCl 3 And (3) reacting for 8-10 hours under the ice water bath condition, and carrying out suction filtration to obtain the modified nano cellulose/polypyrrole composite material.
In FeCl 3 Fe of (B) 3+ Under the catalytic oxidation action, pyrrole is polymerized to form polypyrrole, and the polypyrrole is a conductive polymer, has low cost and is environment-friendly. The special pi-bond macromolecular chain structure in the polypyrrole leads the polypyrrole to have poor compatibility in the elastomer, but the polypyrrole can form hydrogen bonds with the nanocellulose, and 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 a multi-layer crosslinked network structure, thereby forming a conductive path in the rubber composition,the composite material realizes the conduction of current in the rubber matrix through a conductive path formed by polypyrrole, thereby leading out static electricity generated in the rubber and improving the conductivity 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 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 promoter;
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, wherein the styrene content is 21wt% and the vinyl content is 63wt%.
Preferably, the butadiene rubber is neodymium butadiene rubber; the white carbon black is high-dispersion white carbon black; the silane coupling agent is Si69; the operation oil is environment-friendly aromatic hydrocarbon 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 nanocellulose/polypyrrole composite material is used as an antistatic agent to be added into a rubber composition, styrene and acrylic acid modified nanocellulose have good compatibility with a rubber matrix and form hydrogen bonds with polypyrrole, so that the modified nanocellulose/polypyrrole composite material is uniformly dispersed in the rubber matrix to form a multi-layer crosslinked network structure, a conductive path is formed in the rubber composition, the conductivity of the rubber composition is effectively improved, static generated in the running process of the tire can be well led out, and the antistatic performance of the rubber tire is improved.
The final object of the present invention is to provide a process for preparing an antistatic rubber composition comprising the steps of:
and (3) 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 master batch;
two-stage mixing: adding the primary masterbatch, an antistatic agent and zinc oxide into an internal mixer for mixing to obtain a secondary masterbatch;
and (3) final refining: adding the two-stage masterbatch, an accelerator NS and sulfur into an internal mixer for mixing to obtain final rubber.
Preferably, the method specifically comprises the following steps:
and (3) mixing: setting the rotation speed of an internal mixer to be 30-50rpm, adding solution polymerized styrene-butadiene rubber and butadiene rubber, extracting lump, adding white carbon black and operating oil, extracting 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 the rubber is raised to 150 ℃, discharging the rubber, discharging sheets, cooling and building a stack to obtain a section of master batch;
two-stage mixing: setting the rotation speed of an internal mixer to be 30-50rpm, adding a section of 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, discharging the masterbatch when the temperature of the masterbatch is raised to 140 ℃, discharging the masterbatch, cooling, and building a stack to obtain a second section of masterbatch;
and (3) final refining: setting the rotation speed of an internal mixer to be 30-50rpm, adding two sections of masterbatch, an accelerant and sulfur, pressing a top plug for 50-100s, lifting the lump, pressing the top plug for 20-100s, lifting the lump, pressing the top plug, discharging rubber when the temperature of the rubber material is raised to 95 ℃, discharging the rubber, cooling and building up the rubber to obtain the final rubber.
Compared with the prior art, the modified nano-cellulose/polypyrrole composite material and the preparation method, the antistatic rubber composition and the preparation method thereof,
1. styrene and acrylic acid are adopted to modify the nano cellulose, the acrylic acid and the nano cellulose are subjected to grafting reaction, so that the strong action force in the nano cellulose is destroyed, and the bonding action between the nano cellulose and rubber is increased; hydrophobic styrene reacts with acrylic double bonds to reduce the polarity of the surface of the nanocellulose; meanwhile, the benzene ring structure in the styrene enables the modified nanocellulose to have better compatibility with the solution polymerized styrene-butadiene rubber, so that the modified nanocellulose 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 uniform dispersion of the nanocellulose in a rubber matrix, so that a conductive path is formed in the rubber composition, and the conductivity of the rubber composition is improved;
3. the modified nanocellulose/polypyrrole composite material is added into the rubber composition as an 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 conduct out static electricity generated in the running process of the tire, thereby improving the antistatic performance of the rubber tire.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof so that those skilled in the art can better understand the present invention.
Example 1
The preparation method of the modified nanocellulose/polypyrrole composite material A specifically comprises the following steps:
s1, preparing modified nanocellulose: preparing 100 parts by weight of nanocellulose into 2g/L nanocellulose aqueous solution, placing the nanocellulose aqueous solution, 0.5 part by weight of initiator and 20 parts by weight of styrene into a flask, stirring at 70 ℃ for 17min, dropwise adding 40 parts by weight of acrylic acid, and reacting at the reaction temperature for 120min to obtain modified nanocellulose suspension;
s2, adding 60 parts by weight of pyrrole and 22 parts by weight of toluene-4-sulfonic acid into the modified nanocellulose suspension, magnetically stirring for 1.5h under the ice water bath condition, and dropwise adding 19 parts by weight of FeCl of 0.1mol/L 3 And (3) reacting for 9 hours under the ice water bath condition, and filtering to obtain the modified nano cellulose/polypyrrole composite material A.
Example 2
The preparation method of the modified nanocellulose/polypyrrole composite material B specifically comprises the following steps:
s1, preparing modified nanocellulose: preparing 90 parts by weight of nanocellulose into 2g/L nanocellulose aqueous solution, placing the nanocellulose aqueous solution, 0.4 part by weight of initiator and 15 parts by weight of styrene into a flask, stirring at 60 ℃ for 15min, dropwise adding 30 parts by weight of acrylic acid, and reacting at the reaction temperature for 60min to obtain modified nanocellulose suspension;
s2, adding 50 parts by weight of pyrrole and 15 parts by weight of toluene-4-sulfonic acid into the modified nanocellulose suspension, magnetically stirring for 1h under the ice water bath condition, and dropwise adding 17 parts by weight of FeCl with the concentration of 0.1mol/L 3 And (3) reacting for 8 hours under the ice water bath condition, and filtering to obtain the modified nano cellulose/polypyrrole composite material B.
Example 3
The preparation method of the modified nanocellulose/polypyrrole composite material C specifically comprises the following steps:
s1, preparing modified nanocellulose: preparing 110 parts by weight of nanocellulose into 2g/L nanocellulose aqueous solution, placing the nanocellulose aqueous solution, 0.6 part by weight of initiator and 25 parts by weight of styrene into a flask, stirring at 85 ℃ for 20min, dropwise adding 50 parts by weight of acrylic acid, and reacting at the reaction temperature for 180min to obtain modified nanocellulose suspension;
s2, adding 70 parts by weight of pyrrole and 25 parts by weight of toluene-4-sulfonic acid into the modified nanocellulose suspension, magnetically stirring for 2 hours under the ice water bath condition, and dropwise adding 22 parts by weight of FeCl with the concentration of 0.1mol/L 3 And (3) reacting for 10 hours under the ice water bath condition, and filtering 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 to 8 and the rubber compositions provided in comparative examples 1 to 3 are shown in Table 1.
TABLE 1 antistatic rubber compositions provided in examples 4-8 and rubber composition formulation tables provided in comparative examples 1-3
Wherein, the parts in Table 1 are parts by weight.
The antistatic rubber compositions provided in examples 4 to 6 and the rubber compositions provided in comparative examples 1 to 3 were subjected to performance test, and the test results are shown in Table 2.
TABLE 2 antistatic rubber compositions provided in examples 4-6 and comparative tables of the properties of the rubber compositions provided in comparative examples 1-3
| 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 (Ω cm) | 7.71×10 10 | 3.26×10 9 | 1.14×10 9 | 1.85×10 15 | 3.76×10 13 | 8.87×10 12 |
As is clear from Table 2, examples 4 to 6, in which the volume resistivity of the rubber composition gradually decreased as the amount of the antistatic agent-modified nanocellulose/polypyrrole composite A added was increased, and 18 parts by weight of the modified nanocellulose/polypyrrole composite A was added in example 6, the volume resistivity was the lowest and the antistatic effect was the best; comparative example 1, in which no antistatic agent was added, had the highest volume resistivity and the worst antistatic effect;
in comparative example 2, only 5 parts by weight of antistatic agent modified nanocellulose/polypyrrole composite material A is added, the addition amount is small, the volume resistivity is reduced to some extent, but the antistatic effect is not obvious, and the antistatic effect is poor;
in comparative example 3, the conventional non-modified nanocellulose/polypyrrole composite material is used as an antistatic agent and added into a rubber composition, the volume resistivity of the composite material is not obviously reduced, the antistatic effect is poor, and the antistatic performance requirement of a tire cannot be met, because the compatibility of the non-modified nanocellulose/polypyrrole composite material and the rubber composition is poor, the dispersion effect in the rubber composition is poor, and the antistatic effect is poor.
In addition, examples 4-6 all have greater elongation at break than 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 upon vulcanization, increasing the molecular weight and crosslink density of the rubber composition.
In conclusion, the modified nanocellulose/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 nanocellulose/polypyrrole composite material can be directly applied to a rubber formula filled with full white carbon black, the processing technology of tread rubber 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 the embodiment 6 specifically comprises the following steps:
and (3) mixing: setting the rotation speed of an internal mixer to be 30rpm, adding solution polymerized styrene-butadiene rubber and butadiene rubber, extracting lump, adding white carbon black and operating oil, extracting lump, 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 the rubber is raised to 150 ℃, discharging, cooling, and building a pile to obtain a section of masterbatch;
two-stage mixing: setting the rotation speed of an internal mixer to be 30rpm, adding a section of masterbatch and an antistatic agent, pressing a top bolt for 50s, lifting a lump, adding zinc oxide, pressing the top bolt for 30s, discharging the masterbatch when the temperature of the masterbatch is raised to 140 ℃, discharging the masterbatch, cooling, and building a stack to obtain a second section of masterbatch;
and (3) final refining: setting the rotation speed of an internal mixer to be 30rpm, adding two sections of masterbatch, an accelerant and sulfur, pressing a top bolt for 50s, lifting a lump, pressing the top bolt for 20s, lifting the lump, pressing the top bolt, discharging rubber when the temperature of the rubber is raised to 95 ℃, discharging the rubber, cooling, and building a stack to obtain the final rubber.
Example 10
The preparation method of the antistatic rubber composition provided in the embodiment 7 specifically comprises the following steps:
and (3) mixing: setting the rotation speed of an internal mixer to be 50rpm, adding solution polymerized styrene-butadiene rubber and butadiene rubber, extracting lump, adding white carbon black and operating oil, extracting lump, 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 the rubber is raised to 150 ℃, discharging, cooling, and building a pile to obtain a section of masterbatch;
two-stage mixing: setting the rotation speed of an internal mixer to be 50rpm, adding a section of masterbatch and an antistatic agent, pressing a top bolt for 100s, lifting a lump, adding zinc oxide, pressing the top bolt for 60s, discharging the masterbatch when the temperature of the masterbatch is raised to 140 ℃, discharging the masterbatch, cooling, and building a stack to obtain a second section of masterbatch;
and (3) final refining: setting the rotation speed of an internal mixer to be 50rpm, adding two sections of masterbatch, an accelerant and sulfur, pressing a top bolt for 100s, lifting a lump, pressing the top bolt for 100s, lifting the lump, pressing the top bolt, discharging rubber when the temperature of the rubber is raised to 95 ℃, discharging the rubber, cooling, and building a stack to obtain the final rubber.
Example 11
The preparation method of the antistatic rubber composition provided in the embodiment 8 specifically comprises the following steps:
and (3) mixing: setting the rotation speed of an internal mixer to be 40rpm, adding solution polymerized styrene-butadiene rubber and butadiene rubber, extracting lump, adding white carbon black and operating oil, extracting lump, adding a silane coupling agent, an anti-aging agent, an accelerator DPG and stearic acid, pressing a top bolt for 80 seconds, discharging rubber when the temperature of the rubber is raised to 150 ℃, discharging, cooling, and building a pile to obtain a section of masterbatch;
two-stage mixing: setting the rotation speed of an internal mixer to 40rpm, adding a section of masterbatch and an antistatic agent, pressing a top bolt for 75s, lifting a lump, adding zinc oxide, pressing the top bolt for 45s, discharging the masterbatch when the temperature of the masterbatch is raised to 140 ℃, discharging the masterbatch, cooling, and building a stack to obtain a second section of masterbatch;
and (3) final refining: setting the rotation speed of an internal mixer to be 40rpm, adding two sections of masterbatch, an accelerant and sulfur, pressing a top bolt for 75s, lifting a lump, pressing the top bolt for 60s, lifting the lump, pressing the top bolt, discharging rubber when the temperature of the rubber is raised to 95 ℃, discharging the rubber, cooling, and building a stack to obtain the final rubber.
The modified nano cellulose/polypyrrole composite material, the preparation method, the antistatic rubber composition and the preparation method provided by the invention are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in the understanding of the methods and central concepts of the present invention. 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 (7)
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;
the modification mode of the nanocellulose is polymer grafting modification, and the adopted modified monomers are styrene and acrylic acid; the saidUniformly mixing nanocellulose, an initiator and styrene, adding acrylic acid for reaction to obtain modified nanocellulose suspension, adding 15-25 parts of pyrrole and toluene-4-sulfonic acid, uniformly mixing, and adding 0.1mol/L FeCl 3 17-22 parts of aqueous solution, and reacting to obtain the modified nano-cellulose/polypyrrole composite material.
2. The method for preparing the modified nanocellulose/polypyrrole composite material as claimed in claim 1, wherein the method specifically comprises the following steps:
s1, preparing modified nanocellulose: preparing the nanocellulose into 2g/L nanocellulose aqueous solution, placing the nanocellulose aqueous solution, an initiator and styrene into a flask, stirring for 15-20min at 60-85 ℃, dropwise adding acrylic acid, and reacting for 60-180min at the reaction temperature to obtain modified nanocellulose suspension;
s2, adding pyrrole and toluene-4-sulfonic acid into the modified nanocellulose suspension, magnetically stirring for 1-2h under the ice water bath condition, and dropwise adding FeCl 3 And (3) reacting for 8-10 hours under the ice water bath condition, and carrying out suction filtration to obtain the modified nano cellulose/polypyrrole composite material.
3. An 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 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 promoter;
10-18 parts of antistatic agent;
the antistatic agent is the modified nanocellulose/polypyrrole composite material of claim 1.
4. An antistatic rubber composition according to claim 3, wherein said solution polymerized styrene-butadiene rubber is a terminal modified solution polymerized styrene-butadiene rubber having a styrene content of 21wt% and a vinyl content of 63wt%.
5. An antistatic rubber composition according to claim 3, wherein said butadiene rubber is neodymium-based butadiene rubber; the white carbon black is high-dispersion white carbon black; the silane coupling agent is Si69; the operation oil is environment-friendly aromatic hydrocarbon 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.
6. A method for preparing an antistatic rubber composition according to claim 3, comprising the steps of:
and (3) 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 master batch;
two-stage mixing: adding the primary masterbatch, an antistatic agent and zinc oxide into an internal mixer for mixing to obtain a secondary masterbatch;
and (3) final refining: adding the two-stage masterbatch, an accelerator NS and sulfur into an internal mixer for mixing to obtain final rubber.
7. The method for preparing an antistatic rubber composition according to claim 6, comprising the steps of:
and (3) mixing: setting the rotation speed of an internal mixer to be 30-50rpm, adding solution polymerized styrene-butadiene rubber and butadiene rubber, extracting lump, adding white carbon black and operating oil, extracting 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 the rubber is raised to 150 ℃, discharging the rubber, discharging sheets, cooling and building a stack to obtain a section of master batch;
two-stage mixing: setting the rotation speed of an internal mixer to be 30-50rpm, adding a section of 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, discharging the masterbatch when the temperature of the masterbatch is raised to 140 ℃, discharging the masterbatch, cooling, and building a stack to obtain a second section of masterbatch;
and (3) final refining: setting the rotation speed of an internal mixer to be 30-50rpm, adding two sections of masterbatch, an accelerant and sulfur, pressing a top plug for 50-100s, lifting the lump, pressing the top plug for 20-100s, lifting the lump, pressing the top plug, discharging rubber when the temperature of the rubber material is raised to 95 ℃, discharging the rubber, cooling and building up the rubber to obtain the final rubber.
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