CN107022121A - A kind of compounded rubber microsphere modified based on spitball shape graphene and preparation method thereof - Google Patents
A kind of compounded rubber microsphere modified based on spitball shape graphene and preparation method thereof Download PDFInfo
- Publication number
- CN107022121A CN107022121A CN201710302916.6A CN201710302916A CN107022121A CN 107022121 A CN107022121 A CN 107022121A CN 201710302916 A CN201710302916 A CN 201710302916A CN 107022121 A CN107022121 A CN 107022121A
- Authority
- CN
- China
- Prior art keywords
- graphene
- microballoon
- rubber
- parts
- spitball shape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of compounded rubber microsphere modified based on spitball shape graphene and preparation method thereof, the compounded rubber is formed by 100 parts of synthetic rubber, 0.1~10 part of spitball shape graphene microballoon, 0.5~5 part of vulcanizing agent, 3~10 parts of vulcanization accelerators and 5~20 parts of other auxiliary combinations.Spitball shape graphene microballoon has good mechanical property and elasticity, can effectively lift the mechanical strength of rubber, absorbs impact, improves material rebounds, improves thermal conductivity.On the one hand spitball shape structure reduces the stacking of graphene, added in rubber after on the other hand can cause graphene filler that there is impact resistance and elasticity with fine dispersion.The compounded rubber microsphere modified based on spitball shape graphene of the present invention has excellent mechanical strength, wearability, resilience, anti-flammability.
Description
Technical field
The invention belongs to rubber materials, it is related to a kind of compounded rubber microsphere modified based on spitball shape graphene and its preparation
Method.
Background technology
Rubber has unique high resiliency at room temperature, and light weight, application is wide, is used as a kind of important strategic goods and materials
It is widely used in the field such as national economy, new and high technology and defence and military however, simple rubbery intensity is low, modulus is low, resistance to
Poor, the antifatigue difference of mill, filler reinforcement is required for without practicality, therefore for most rubber.Carbon black (CB) and white carbon
(SiO2) it is the main reinforcing agent of traditional rubber, it is widely used in various rubbers, but while reinforcing rubber, by
The phase mutual friction between filler, macromolecular chain inside the intrinsic glutinous bullet hysteresis loss of elastomeric material and rubber, dynamic environment
The lower rubber used can produce substantial amounts of heat.And when the heat of generation can not be conducted in time, inside rubber
Meeting steep temperature rise, makes its performance degradation, and this needs to improve the thermal conductivity of rubber to improve its usability dynamically under
Energy and service life.There are many researchers to be combined Nano filling with rubber before this to obtain the compounded rubber of more preferable performance, such as
Fullerene, montmorillonite, expanded graphite, CNT etc. are added, but these materials are easy to reunite, it is difficult to it is this high viscous in rubber
Disperse in degree system, and balance can not be obtained in various performances, thus application is narrower.
Graphene is a kind of two-dimensional material of atomic thickness, and the specific surface area with superelevation, excellent mechanical property, height are led
Heating rate and self lubricity.These characteristics make it be widely studied in terms of composite so that the performance of high polymer material is obtained
To improvement.But graphene is easily reunited, graphite stacked structure can be re-formed, reducing it strengthens performance.Although can pass through
Add dispersant and carry out the method for surface modification to promote the dispersiveness of graphene and reduce the stacking of graphene, but these
Method improves the cost of graphene, and introduces new composition.Patent 201510208883.X《What a kind of graphene was modified
Abrasive rubber》Rubber is strengthened using multi-layer graphene, overall mechanical performance is improved.Patent 201610705206.3
《A kind of compounded rubber being modified based on three-dimensional grapheme and its preparation》With three-dimensional grapheme with it is rubber combined, utilize three-dimensional structure
Its thermal conductivity is improved while rubber mechanical property is lifted.
The content of the invention
The purpose of the present invention is to be answered for existing technical deficiency there is provided a kind of based on spitball shape graphene is microsphere modified
Close rubber and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：It is a kind of to answer based on spitball shape graphene is microsphere modified
Rubber is closed, in parts by mass including following component：100 parts of rubber, 0.1~10 part of spitball shape graphene microballoon, 0.5~5 part of sulphur
Agent, 3~10 parts of vulcanization accelerators and 5~20 parts of other auxiliary agents.The spitball shape graphene microballoon is wrinkled by single-layer graphene film
Pleat is formed, and microsphere diameter is 500nm~5 μm, and density is 0.2~0.4g/cm3, carbon-to-oxygen ratio is 20~60, and specific surface area is less than
200m2/g。
The spitball shape graphene microballoon is prepared by following steps：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere and is reduced, gone back
Former graphene oxide microballoon；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtained
Spitball shape graphene microballoon.
Further, in the single-layer graphene oxide dispersion liquid of the step (1), reducing agent can also be contained.In atomization
During, fold occurs for graphene oxide sheet, meanwhile, reducing agent is attached to sheet surfaces with molecular conformation.The reducing agent is
Hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride etc..Reducing agent and single-layer graphene oxide mass ratio be 0.1~
10.Atomization drying temperature in the step (1) is 100~200 DEG C so that be wrapped in the reducing agent in pleated structure to oxidation
Graphene is tentatively reduced.
Further, the reducing atmosphere described in step (2) is hydrazine hydrate steam, hydroiodic acid steam, hydrogen, hydrobromic acid
One or more in steam.Reducing condition is：30min~48h or so is reduced at 60~200 DEG C.
Further, the high-temperature process temperature described in step (3) be 2500~3000 DEG C, processing time be 30min~
48h, atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas.
Further, described rubber is natural rubber, nitrile rubber, silicon rubber, butadiene rubber, isoprene rubber, butylbenzene
One or more in rubber, EP rubbers, neoprene.
Further, other described auxiliary agents include：2~5 parts of stearic acid, 0.5~2 age resistor, 0.5~3 part of atoleine,
2~10 parts of zinc oxide.
Further, described vulcanizing agent is that sulphur, peroxide, metal oxide, resin curing agent, sulfur-bearing are organic
At least one of thing.
A kind of preparation method of the compounded rubber microsphere modified based on spitball shape graphene, comprises the following steps：
(1) will rubber, spitball shape graphene microballoon, vulcanization accelerator and other auxiliary agents add banbury in mixing 10~
30min, melting temperature is 40~90 DEG C, and 5~8h is stood afterwards；
(2) batch mixing and vulcanizing agent after standing are placed in 40~90 DEG C of mill and kneaded, be finally placed on flat board
Vulcanize on vulcanizer, vulcanize 10~40min at 150~180 DEG C.
The beneficial effects of the present invention are：The present invention prepares graphene oxide microballoon by atomization drying method first,
Reducing agent is added in graphene oxide dispersion before atomization drying, is well mixed, reducing agent is supported on molecular forms
Graphene oxide sheet surface.Afterwards during atomization drying, the oxygen-containing function of partial reduction agent and surface of graphene oxide
Group reacts, and product is deviate from the volatilization of solvent, and remaining reducing agent is then attached to graphene oxide sheet table with molecular forms
Face, and be wrapped with its gauffer.Second step uses electronation, under reducing atmosphere, inside graphene oxide microballoon
Fully reacted with reducing agent with the oxygen-containing functional group on surface, relatively low temperature make it that the generation and release of gas are slow, it is to avoid
Group fast eliminating produces gas, the phenomenon for causing volume drastically to expand in direct thermal reduction, thus maintain graphene still with
The form of fold piece is combined closely without separating.On the one hand 3rd step high temperature thermal reduction takes off remaining a small amount of oxygen-containing functional group
Remove, and repair the defect sturcture in graphene oxide sheet, on the other hand, make the moisture of residual in microballoon, reduzate and not anti-
The reducing agent removing answered.In addition, we have been surprisingly found that in an experiment, and at extreme temperatures under (2500~3000 DEG C), graphene
The diameter of microballoon is gradually reduced, density increase, specific surface area reduction.This be probably due under graphitization temperature, graphene film
Perfect structure so that graphene fold adhesion strengthens, the increase of graphene film intermolecular forces, Distance Shortened each other,
Progressively make the compact structure of graphene ball.Gained spitball shape graphene microballoon has good mechanical property and elasticity, can have
Effect absorbs impact, and stability is strong.In addition, spitball shape structure reduces the stacking of graphene, overall stability is improved.Spitball
Shape graphene ball can effectively lift the mechanical strength of rubber, absorb and impact and promote material rebounds.The addition of graphene is also improved
Material overall thermal conductivity and anti-flammability so that compounded rubber has higher service life.
Brief description of the drawings
Fig. 1 is the microscopic appearance of the spitball shape graphene microballoon prepared through the embodiment of the present invention 1.
Fig. 2 is the microscopic appearance of the expanded graphite alkene ball prepared through present invention contrast 2.
Embodiment
The method based on the microsphere modified compounded rubber of spitball shape graphene of preparation comprises the following steps：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon.The list
It can also contain reducing agent in layer graphene oxide dispersion.Reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, boron
Sodium hydride etc..Reducing agent is 0.1~10 with single-layer graphene oxide mass ratio.Atomization drying temperature is 100~200 DEG C；(2) will
The graphene oxide microballoon that step (1) is obtained, is placed in reducibility gas atmosphere, and 30min~48h is reduced at 60~200 DEG C
Obtain redox graphene microballoon；Described reducing atmosphere is in hydrazine hydrate steam, hydroiodic acid steam, hydrobromic acid steam
It is one or more；(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtained
To spitball shape graphene microballoon；Atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas, and processing time is
30min~48h.Further, the temperature treatment temperature is 2500~3000 DEG C.(4) the paper nodular graphite for obtaining step (3)
Kneaded in 0.1~10 part of alkene microballoon, 100 parts of rubber, 5~20 parts of addition banburies of 3~10 parts of vulcanization accelerator and other auxiliary agents
10~30min, melting temperature is 40~90 DEG C, and 5~8h is stood afterwards.Other auxiliary agents include：2~5 parts of stearic acid, 0.5~2 are prevented
Old agent, 0.5~3 part of atoleine, 2~10 parts of zinc oxide.(5) batch mixing and 0.5~5 part of vulcanizing agent obtained step (4) is put
Kneaded in 40~90 DEG C of mill, be finally placed on vulcanizing press vulcanize, at 150~180 DEG C vulcanize 10~
40min, is obtained based on the microsphere modified compounded rubber of spitball shape graphene.Sulphur, peroxide, metal oxide, resinae
Vulcanizing agent, sulfurous organic compound at least one of.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment belong to protection scope of the present invention.
Embodiment 1：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and 1h is reduced at 60 DEG C and is obtained
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 5
15min is kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 2 parts of atoleine, 4 parts of addition banburies of zinc oxide, melting temperature is
70 DEG C, 6h is stood afterwards；
(5) batch mixing and 4 parts of sulphur obtained step (4) is placed in 60 DEG C of mill and kneaded, and is finally placed on flat
Vulcanize on plate vulcanizer, vulcanize 30min at 160 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is fold microballoon of the diameter at 3~5 μm under microcosmic, as shown in Figure 1.Its density is 0.2g/cm3, carbon-to-oxygen ratio is 22.7, compares surface
Product is 190m2/g.The performance of gained rubber is as shown in table 2.
Embodiment 2：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and 1h is reduced at 90 DEG C and is obtained
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 6
15min is kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 2 parts of atoleine, 4 parts of addition banburies of zinc oxide, melting temperature is
70 DEG C, 6h is stood afterwards；
(5) batch mixing and 3.5 parts of sulphur obtained step (4) is placed in 60 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 30min at 160 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic lower for fold microballoon of the diameter at 3~5 μm.Its density is 0.23g/cm3, carbon-to-oxygen ratio is 23.1, and specific surface area is 181m2/
g.The performance of gained rubber is as shown in table 2.
Embodiment 3：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 8
15min, melting temperature are kneaded in part, 1.5 parts of stearic acid, 1 part of age resistor, 2 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 70 DEG C, 6h is stood afterwards；
(5) batch mixing and 4 parts of sulphur obtained step (4) is placed in 60 DEG C of mill and kneaded, and is finally placed on flat
Vulcanize on plate vulcanizer, vulcanize 30min at 160 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic lower for fold microballoon of the diameter at 3~5 μm.Its density is 0.25g/cm3, carbon-to-oxygen ratio is 22.9, and specific surface area is 166m2/
g.The performance of gained rubber is as shown in table 2.
By comparative example 1~3, final stone can be significantly reduced by improving second step reduction temperature and time
The specific surface area of black alkene microballoon, improves density, but influence little to carbon-to-oxygen ratio.This is due to that second step reduction mainly makes oxidation
The group of graphenic surface is slowly removed, reduction temperature is low or the time it is short can cause that reduction is insufficient, the group of residual exists
Removing is may proceed to during the 3rd high-temperature heat treatment, gas is produced and graphene film is outwards expanded.And spitball shape graphene is micro-
The specific surface area of ball is lower, and density is higher, and representative structure is more closely knit, and its resistance to pressure and elasticity more preferably, are integrated afterwards with rubber combined
Performance is more preferable, as shown in table 2.Therefore, to sum up consider, when second step reducing condition is preferably for high reduction temperature and long reduction
Between.
Embodiment 4：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 0.4, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.1 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 4
30min, melting temperature are kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 3 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 20min at 170 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic lower for fold microballoon of the diameter at 3~5 μm.Specific performance is as shown in table 1,2.
Embodiment 5：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.3 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 4
30min, melting temperature are kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 3 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 20min at 170 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic lower for fold microballoon of the diameter at 3~5 μm.Specific performance is as shown in table 1,2.
Embodiment 6：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 5, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.3 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 4
30min, melting temperature are kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 3 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 30min at 180 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic lower for fold microballoon of the diameter at 3~5 μm.Specific performance is as shown in table 1,2.
Embodiment 7：
1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 2000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 8
30min, melting temperature are kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 4 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 30min at 180 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic lower for fold microballoon of the diameter at 2~4 μm.Specific performance is as shown in table 1,2.
Embodiment 8：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 8
30min, melting temperature are kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 4 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 30min at 180 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is fold microballoon of the diameter in 500nm~3 μm under microcosmic.Specific performance is as shown in table 1,2.
Embodiment 9：
(1) dried by atomization drying method single-layer graphene oxide dispersion liquid, obtain graphene oxide microballoon, atomization temperature
For 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 7
30min, melting temperature are kneaded in part, 1 part of stearic acid, 1 part of age resistor, 2.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 4 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 15min at 160 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is fold microballoon of the diameter in 500nm~3 μm under microcosmic.Specific performance is as shown in table 1,2.
Comparative example 1：Method according to embodiment 1 prepares compounded rubber, unlike, without spitball shape in preparation process
Graphene microballoon.Performance is as shown in table 1,2.
Comparative example 2：Graphene oxide microballoon is without the direct thermal reduction of electronation：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1) is put into tube furnace, is continually fed into hydrogen-argon-mixed, temperature
3000 DEG C are risen to, programming rate is 5 DEG C/min, is incubated 1h；
(4) 0.2 part of graphene for obtaining step (3), 100 parts of butadiene rubber, 8 parts of vulcanization accelerator TMTD, stearic acid 2
30min is kneaded in part, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide, melting temperature is 80 DEG C, afterwards
Stand 5h；
(5) batch mixing and 4 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, 30min is vulcanized at 180 DEG C, obtain the compounded rubber of graphene modification.
Through above step, obtained graphene outward appearance is black fluffy powder, and microcosmic is hollow ball of the diameter at 1~10 μm
Shell, as shown in Figure 2.Performance is as shown in table 1,2.
The embodiment design parameter of table 1 and property
The frictional behaviour of table 2
Comparative example 3~6 is it can be found that the amount of the reducing agent added by improving before atomization drying can be effectively facilitated
Reducing degree of the graphene oxide microballoon before three step process, this is due to that reducing agent is dispersed in oxidation with molecular forms
Graphenic surface, can roll into a ball step-reaction, slow reduced graphene so that carbon-to-oxygen ratio is put forward in the first step and second step with ether ring
Rise, specific surface area reduction.And contrast knowable to before and after the reduction of the 3rd step, high-temperature heat treatment causes inside redox graphene microballoon
The group not removed departs from (carbon-to-oxygen ratio increase), and the swelling graphene interlayer structure of gas of generation causes specific surface area to rise.But
It is to be improved by adding reducing agent after reproducibility, the release gas that graphene microballoon can be less in the 3rd step high-temperature heat treatment,
Reduce volumetric expansion so that structure is more closely knit.Therefore, in order to obtain high density, low specific surface area graphene microballoon, plus
It is significant to enter reducing agent.
Comparative example 5,7 is it can be found that in the case where ensureing that first two steps reducing condition is consistent, improve the reduction of the 3rd step
Temperature causes specific surface area to increase, density reduction, and this is due to that the further release of gas causes lamellar structure further to strut.
However, surprisingly, after temperature rises to 3000 DEG C (embodiment 8), specific surface area is greatly lowered, it may be possible to which temperature is high
In after graphitization temperature, the big π structures of graphene are repaired, and the adhesion between lamella is greatly promoted, interlamellar spacing reduction, because
And cause graphene microballoon to center " aggregation ", more densification.
Comparative example 3,9 is understood, if being added without reducing agent, can significantly reduce graphite by 3000 DEG C of heat treatments merely
The specific surface area of alkene microballoon.But comparative example 8 is understood, add reducing agent and realize that most of functional group's removing can before heat treatment
To obtain the graphene microballoon of more consolidation.
Comparative example 8 and comparative example 1 are understood, graphene oxide microballoon directly is carried out into high-temperature heat treatment in comparative example,
A large amount of gas effusions cause volume rapid expanding during reduction, and specific surface area is high, and density is very low.Can be with one although being added into after rubber
Determine degree lifting mechanical property, but because the graphene film of expansion is present, enhanced amplitude is less than spitball shape graphene.
Graphene enhancing rubber performance and obturator performance it is closely related, the spitball shape graphene microballoon of filling it is close
Degree is higher, and specific surface area is bigger, represents that its structure is more closely knit, and space is fewer, and structure is more stable, is absorbing impact, resilience and resistance to
Performance in terms of mill is better.It is scattered more easily to reach stabilization also, particle is smaller.Thus, consider, it is necessary to obtain more
For closely knit graphene microballoon.The present invention realizes the densification of graphene microballoon, structure by controlling each step Reduction parameter
Completeization and performance optimization, so as to effectively improve the combination property of compounded rubber.
Embodiment 10：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.2 part of spitball shape graphene microballoon for obtaining step (3), 100 parts of butadiene rubber, vulcanization accelerator TMTD 8
30min, melting temperature are kneaded in part, 2 parts of stearic acid, 1 part of age resistor, 1.5 parts of atoleine, 4 parts of addition banburies of zinc oxide
For 80 DEG C, 5h is stood afterwards；
(5) batch mixing and 4 parts of vulcanizing agents obtained step (4) is placed in 80 DEG C of mill and kneaded, and is finally placed on
Vulcanize on vulcanizing press, vulcanize 30min at 180 DEG C, obtain based on the microsphere modified compounded rubber of spitball shape graphene.
Through above step, obtain based on the microsphere modified compounded rubber of spitball shape graphene.Spitball shape graphene microballoon exists
It is microcosmic it is lower be diameter in the fold microballoon of 500nm~3 μm, because step (1)~(3) are same as Example 8, therefore graphene is micro-
Carbon-to-oxygen ratio, density, the specific surface area of ball are same as Example 8.Specific nature is as shown in table 2.It can be found that improving graphene ball
Addition can further lift the properties of rubber.
Claims (10)
1. a kind of compounded rubber microsphere modified based on spitball shape graphene, it is characterised in that in parts by mass including such as the following group
Point：100 parts of rubber, 0.1~10 part of spitball shape graphene microballoon, 0.5~5 part of vulcanizing agent, 3~10 parts of vulcanization accelerators and 5~
20 parts of other auxiliary agents.The spitball shape graphene microballoon is formed by single-layer graphene film gauffer, and microsphere diameter is 500nm~5 μm,
Density is 0.2~0.4g/cm3, carbon-to-oxygen ratio is 20~60, and specific surface area is less than 200m2/g。
2. compounded rubber according to claim 1, it is characterised in that the spitball shape graphene microballoon is by following steps system
It is standby to obtain：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere and is reduced, obtain oxygen reduction
Graphite alkene microballoon；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtains spitball
Shape graphene microballoon.
3. compounded rubber according to claim 2, it is characterised in that the single-layer graphene oxide of the step (1) is disperseed
In liquid, reducing agent can also be contained.The reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride etc..Also
Former agent is 0.1~10 with single-layer graphene oxide mass ratio.
4. compounded rubber according to claim 2, it is characterised in that the atomization drying temperature in the step (1) is 100
~200 DEG C.
5. compounded rubber according to claim 2, it is characterised in that the reducing atmosphere in the step (2) is hydration
One or more in hydrazine steam, hydroiodic acid steam, hydrobromic acid steam.Reducing condition is：30min is reduced at 60~200 DEG C
~48h or so.
6. compounded rubber according to claim 2, it is characterised in that the high-temperature process temperature in the step (3) is
2500~3000 DEG C.High-temperature process atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas, and processing time is
30min~48h.
7. compounded rubber according to claim 1, it is characterised in that the rubber is natural rubber, nitrile rubber, silicon rubber
One or more in glue, butadiene rubber, isoprene rubber, butadiene-styrene rubber, EP rubbers, neoprene.
8. compounded rubber according to claim 1, it is characterised in that the vulcanizing agent is sulphur, peroxide, metal oxygen
At least one of compound, resin curing agent, sulfurous organic compound.
9. compounded rubber according to claim 1, it is characterised in that other described auxiliary agents include：2~5 parts of stearic acid,
0.5~2 age resistor, 0.5~3 part of atoleine, 2~10 parts of zinc oxide.
10. a kind of preparation method of the compounded rubber microsphere modified based on spitball shape graphene, it is characterised in that including following step
Suddenly：
(1) rubber, spitball shape graphene microballoon, vulcanization accelerator and other auxiliary agents are added and 10~30min are kneaded in banbury,
Melting temperature is 40~90 DEG C, and 5~8h is stood afterwards；
(2) batch mixing and vulcanizing agent after standing are placed in 40~90 DEG C of mill and kneaded, be finally placed on compression molding
Vulcanize on machine, vulcanize 10~40min at 150~180 DEG C.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710302916.6A CN107022121B (en) | 2017-05-03 | 2017-05-03 | A kind of compounded rubber and preparation method thereof microsphere modified based on spitball shape graphene |
| US16/622,953 US11225414B2 (en) | 2017-04-28 | 2018-02-26 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| RU2019138451A RU2734476C1 (en) | 2017-04-28 | 2018-02-26 | Graphene microspheres in form of paper lump, composite material of such microspheres and method of making such microspheres |
| KR1020197034665A KR102307001B1 (en) | 2017-04-28 | 2018-02-26 | Paperball-type graphene microspheres and their composite material and manufacturing method |
| PCT/CN2018/077221 WO2018196474A1 (en) | 2017-04-28 | 2018-02-26 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| EP18791151.6A EP3617141B1 (en) | 2017-04-28 | 2018-02-26 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710302916.6A CN107022121B (en) | 2017-05-03 | 2017-05-03 | A kind of compounded rubber and preparation method thereof microsphere modified based on spitball shape graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107022121A true CN107022121A (en) | 2017-08-08 |
| CN107022121B CN107022121B (en) | 2018-09-21 |
Family
ID=59528182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710302916.6A Active CN107022121B (en) | 2017-04-28 | 2017-05-03 | A kind of compounded rubber and preparation method thereof microsphere modified based on spitball shape graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107022121B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107651672A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of preparation method of Ultralight graphene microballoon for solar absorption |
| CN108584924A (en) * | 2018-05-15 | 2018-09-28 | 浙江大学 | A kind of preparation method of pressure-sensitive graphene film |
| WO2018196474A1 (en) * | 2017-04-28 | 2018-11-01 | 杭州高烯科技有限公司 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| CN109233014A (en) * | 2018-09-21 | 2019-01-18 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of butadiene rubber-graphene oxide composite material |
| WO2022037060A1 (en) * | 2020-08-19 | 2022-02-24 | 吴立中 | Preparation method for reduced graphene oxide nitrile rubber and for tooth block without tooth marks |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008255151A (en) * | 2007-04-02 | 2008-10-23 | Yokohama Rubber Co Ltd:The | Rubber composition and studless tire using the same |
| CN101993065A (en) * | 2010-12-17 | 2011-03-30 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene powder |
| CN105384164A (en) * | 2015-12-18 | 2016-03-09 | 上海理工大学 | Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof |
| CN106317505A (en) * | 2016-08-22 | 2017-01-11 | 广东纳路纳米科技有限公司 | Three-dimensional graphene modified rubber composite material and preparation method thereof |
-
2017
- 2017-05-03 CN CN201710302916.6A patent/CN107022121B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008255151A (en) * | 2007-04-02 | 2008-10-23 | Yokohama Rubber Co Ltd:The | Rubber composition and studless tire using the same |
| CN101993065A (en) * | 2010-12-17 | 2011-03-30 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene powder |
| CN105384164A (en) * | 2015-12-18 | 2016-03-09 | 上海理工大学 | Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof |
| CN106317505A (en) * | 2016-08-22 | 2017-01-11 | 广东纳路纳米科技有限公司 | Three-dimensional graphene modified rubber composite material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018196474A1 (en) * | 2017-04-28 | 2018-11-01 | 杭州高烯科技有限公司 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| CN107651672A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of preparation method of Ultralight graphene microballoon for solar absorption |
| CN108584924A (en) * | 2018-05-15 | 2018-09-28 | 浙江大学 | A kind of preparation method of pressure-sensitive graphene film |
| CN108584924B (en) * | 2018-05-15 | 2020-08-04 | 浙江大学 | Preparation method of pressure-sensitive graphene film |
| CN109233014A (en) * | 2018-09-21 | 2019-01-18 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of butadiene rubber-graphene oxide composite material |
| WO2022037060A1 (en) * | 2020-08-19 | 2022-02-24 | 吴立中 | Preparation method for reduced graphene oxide nitrile rubber and for tooth block without tooth marks |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107022121B (en) | 2018-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107022121B (en) | A kind of compounded rubber and preparation method thereof microsphere modified based on spitball shape graphene | |
| KR102307001B1 (en) | Paperball-type graphene microspheres and their composite material and manufacturing method | |
| CN106966383B (en) | A kind of spitball shape graphene microballoon and preparation method thereof | |
| CN104371153A (en) | Rubber composite modified by carbon nano tubes and graphene jointly | |
| CN105331112B (en) | A kind of graphene silicon rubber composite foam material and preparation method thereof | |
| Chen et al. | Cellulose nanocrystals reinforced foamed nitrile rubber nanocomposites | |
| Zhao et al. | In situ fabrication of molybdenum disulfide based nanohybrids for reducing fire hazards of epoxy | |
| CN102226016A (en) | Nano-mesoporous molecular sieve synergistic intumescent flame-retardant rubber and preparation method thereof | |
| CN107057058B (en) | A kind of graphene/cast nylon composite material and preparation method thereof | |
| CN106987188A (en) | A kind of graphene-based water-borne acrylic coatings and preparation method thereof | |
| CN107556627A (en) | Expandable graphite alkene/rubber composite and its preparation method and application | |
| CN105037830A (en) | High-strength low-heat-generation composite material and preparation method thereof | |
| CN111004434B (en) | High-wear-resistance anti-slip EVA (ethylene-vinyl acetate) composite foam material and preparation method thereof | |
| CN109942913A (en) | The preparation method of polymolecularity graphite oxide alkenyl rubber composite material | |
| CN105037823B (en) | Graphene oxide/Fe3O4 based composite conductive rubber and preparation method therefor | |
| Wang et al. | Good dispersion of hydrophilic nanoscale calcium carbonate particles in nitrile butadiene rubber matrix | |
| Watanabe et al. | Highly ductile polypropylene-based nanocomposites by dispersing monodisperse silica nanospheres in functionalized polypropylene containing hydroxyl groups | |
| Yan et al. | Probing the damping property of three‐dimensional graphene aerogels in carboxylated nitrile butadiene rubber/polyurethane blend | |
| CN107090324A (en) | A kind of complex lithium grease containing spitball shape graphene microballoon and preparation method thereof | |
| CN105111642A (en) | Tetrapropyl fluoro rubber with low-compression permanent deformation performance and preparation method for tetrapropyl fluoro rubber | |
| Cong et al. | Facile preparation of Cross-linked polyester composite rubber with excellent mechanical strength and high toughness by loading adjustable Low-cost clay | |
| CN107090325A (en) | A kind of graphene-based lubricating oil and preparation method thereof | |
| Boonmahitthisud et al. | Use of carbon nanotube and nanosilica as reinforcement nanofillers in NR/SBR blended latex | |
| CN107353439B (en) | A kind of PPR composite material and preparation method of graphene toughening | |
| CN106977768B (en) | A kind of method that spitball shape graphene improves 6 impact strength of nylon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |