CN109943004A - A kind of preparation method of butadiene rubber composite material - Google Patents
A kind of preparation method of butadiene rubber composite material Download PDFInfo
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Abstract
The invention belongs to technical field of rubber material, and in particular to a kind of preparation method of butadiene rubber composite material.The present invention is using butadiene as raw material, polymerization, which is carried out, by the effect of catalyst forms butadiene rubber base-material, 1- butylene is added in synthesis process again simultaneously, inside the rubber for forming insertion, gaseous mixture will be used to replace again, in the mixed solvent is soluble in using the ethylene in gaseous mixture, utilize the ethylene of solvent, under the action of catalyst and cocatalyst, it is reacted with 1- butylene, it forms it into butene-ethylene polymer and is wrapped up with to being combined property of butadiene rubber raw material, it is effective improve can butadiene rubber performance, then reuse dibutyl maleate, graft modification is carried out to it, it can be very good to be combined with increase particle, avoid falling off for particle, and while graft modification, realize between polymer using particle and metal ion as the crosslinking of core, by being crosslinked, further increase can The mechanical property of butadiene rubber.
Description
Technical field
The invention belongs to technical field of rubber material, and in particular to a kind of preparation method of butadiene rubber composite material.
Background technique
Butadiene rubber is cis--Isosorbide-5-Nitrae-polybutadiene rubber abbreviation, is to be only second to the second-biggest-in-the-world of butadiene-styrene rubber to lead to
With synthetic rubber, have that elasticity is good, resistance to low temperature is good, heat is low, hysteresis loss is small, resistance to immunity in the wrong, crack resistance and dynamic
The advantages that state property can be good.Butadiene rubber yield is only second to butadiene-styrene rubber, and second is occupied in synthetic rubber.Butadiene rubber is bullet
Property and the best synthetic rubber of cold resistance, particularly suitable for automobile tire processed and cold-resistant product, can also manufacture padded coaming and
Various rubber overshoes, adhesive plaster, adhesive tape and sandwich rubber etc. can be also used in combination with natural rubber, neoprene and nitrile rubber etc., take turns
It is widely used in the production of the rubber products such as tire, impact modification, adhesive tape, sebific duct and rubber overshoes.
The epoxidation modification research of butadiene rubber is concentrated mainly on the butadiene rubber of low molecular weight, Makowsik,
Zuchowska et al. has carried out epoxidation research to high-cis polybutadiene, low-cis-polybutadiene and 1,2- polybutadiene,
Its oil resistivity, air-tightness and resistance to wet skidding performance can preferably be improved.For the hydrogenation modification of butadiene rubber, patent US5399632 is public
One kind has been opened to use without using hydrogen hydrogenation medium (one kind is to hydrogen compound), it is right under the action of palladium catalyst such as formic acid
Butadiene rubber adds the method for hydrogen.The resistance to ag(e)ing of butadiene rubber and hydraulic pressure resistant performance obtain biggish improvement after hydrogenation, and hydrogenate
Product is with higher to use temperature, and creep and compressive deformation all reduce.It is chain end modified for butadiene rubber, patent
US5844050 is disclosed with stannic chloride or organic polyfunctional compound methyl diphenylene diisocyanate, chloro triazine
With the modified REs butadiene rubber such as phenyl acyl chlorides, not only wearability significantly improves modified butadiene rubber.Using compound 4,
Bis- diethylamino Benzophenone (TEAB) the modified RE butadiene rubbers of 4-, can be improved the resilience performance of polymer.With esters chemical combination
Object is modified butadiene rubber, can improve the blended and processing performance of butadiene rubber Yu other rubber.Chlorination for butadiene rubber
Modified, Xia Yuzheng, Tang Yukuan et al. discovery not only reduce double bond content, improve its resistance to ag(e)ing after butadiene rubber chlorination,
And due to the introducing of chlorine atom, mixing Characteristics are improved, vulcanizate tensile strength, oil resistivity, anti-flammability and cohesive force
Deng all having obtained significantly improving, it can be used as anticorrosive paint, ink, printing coloring agent and adhesive etc..
Although many to the method for modifying of butadiene rubber at present, i.e., the enabled physical chemistry etc. for preferably improving butadiene rubber
Performance, but modified butadiene rubber tearing toughness is low, is not able to satisfy market demands.
Summary of the invention
The technical problems to be solved by the invention: low for the modified butadiene rubber tearing toughness of current conventional method
Problem, the present invention provides a kind of preparation methods of butadiene rubber composite material.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of preparation method of butadiene rubber composite material, the preparation method include the following steps:
(1) it by mixed solvent, catalyst and butadiene cyclohexane solution 10~13:1:6~8 in mass ratio, is put into reaction kettle,
It is protected using argon gas, is warming up to 90~95 DEG C, is stirred to react；
(2) after the completion of reaction, argon gas is displaced using gaseous mixture, adds butadiene cyclohexane solution volume 30~40%
1- butylene ethanol solution and butadiene cyclohexane solution quality 2~4% cocatalyst, and boost to 1.3~1.9MPa,
110~115 DEG C are warming up to, heat preservation；
(3) cooling after wait keep the temperature, discharging collects out material, material out is evaporated, and removes solvent, collects remaining
Toluene, residue, dibutyl maleate 10~16:5 in mass ratio~7:3 are put into reactor and mix preheating by object；
(4) after preheating, the enhancing particle of 1~2% initiator of residue quality and residue quality 6~9% is added,
Stirring, cooling, evaporative removal toluene is spray-dried, washing, dry to get butadiene rubber composite material.
Mixed solvent is ethyl alcohol, carbon tetrachloride 4~9:3 by volume in the step (1)
In the step (1) catalyst the preparation method comprises the following steps: by alkyl aluminum, mixed solution 1:10 in mass ratio~16 carry out ultrasound
Concussion, adds 1~2 times of alkyl aluminum quality of neodymium iso-octanate, the sodium chloride of alkyl aluminum quality 40~50%, at 50~55 DEG C
It is stirred mixing, is stood, is freeze-dried to get catalyst.
The mixed solution be hexane, hexamethylene, toluene, in acetone any one or it is any two kinds by any than mixed
It closes.
Gaseous mixture is ethylene in the step (2), 4~6:2 is mixed nitrogen in molar ratio.
In the step (2) cocatalyst the preparation method comprises the following steps: by magnesium chloride, titanium chloride and water in mass ratio 4~6:
3:20 is mixed, and is added the polyacrylamide of magnesium chloride quality 2~5%, is stirred, and is stood at 5~8 DEG C,
Spray drying collects dried object to get cocatalyst.
Initiator is di-t-butyl peroxide, any one in peroxidized t-butyl perbenzoate in the step (4).
Enhancing particle is modified graphene, mica and complexed surfactant 2:4~6 in mass ratio in the step (4):
0.3, which mills, mixes.
The modified graphene the preparation method comprises the following steps:
A. graphite, sodium nitrate 4~7:2 in mass ratio are uniformly mixed, are put into reactor, add 2~4 times of graphite quality
The concentrated sulfuric acid is stirred, and 1~4 times of graphite quality of potassium permanganate is added, and is stirred at 12~16 DEG C, is being warming up to 30~33 DEG C,
40~50min to be stirred, 1~2 times of graphite quality of water is added dropwise, stirring adds the hydrogen peroxide of potassium permanganate quality 30~40%,
Mixing is stood, and is filtered, and is washed, dry, obtains graphite oxide；
B. according to parts by weight, 100~120 parts of N, N- methylene formamide, 30~35 parts of graphene oxides, 13~15 parts are taken
C16/C18Alkylamide propyl dimethyl tertiary amine, 10~12 parts of methanol, 4~6 parts of maleic anhydrides, are put into reaction kettle, and boosting rises
Temperature is stirred to react, cooling, adjusts pH to 8.5~9.0, is stood, is added 3~5 times of graphene oxide quality of hydrazine hydrate, stir
It mixes, discharges, filter, washing is dry to get modified graphene.
The complexed surfactant is by neopelex, dioctyl succinate disulfonate acid 1:1 in mass ratio
~3 mix.
The present invention is compared with other methods, and advantageous effects are:
(1) of the invention by, to metal ion progress flocculation, metal ion being made to be adsorbed flocculation using polyacrylamide, from
And mix metal ion therein uniformly, the effect of auxiliary catalysis is improved, and polyacrylamide is added can be with
Certain facilitation is played to butadiene rubber well, secondly the present invention passes through oxidation by being used as raw material with graphite
Processing obtains graphene oxide, then passes through utilization and C16/C18Alkylamide propyl dimethyl tertiary amine etc. is reacted, and is formed
Alkyls quaternary surfactant, and it is incorporated in surface of graphene oxide, its dispersion performance and absorption property are improved, is added simultaneously
Enter maleic anhydride to be modified, further enhance the binding performance of graphene and particle and substrate, can effectively and mica into
Row, which combines, improves enhancing dispersion performance of the particle in rubber and the associativity with rubber, effectively enhances the mechanical property of rubber
Energy；
(2) present invention is carried out polymerization by the effect of catalyst and is formed butadiene rubber base-material using butadiene as raw material, while again
1- butylene is added in synthesis process, inside the rubber for forming insertion, then gaseous mixture will be used to replace, using in gaseous mixture
Ethylene be soluble in the mixed solvent, using the ethylene of solvent, under the action of catalyst and cocatalyst, with 1- fourth
Alkene is reacted, and is formed it into butene-ethylene polymer and is wrapped up with to being combined property of butadiene rubber raw material, effectively changes
It is kind can butadiene rubber performance, improve tearing toughness, then reuse dibutyl maleate, it is right in the effect of initiator
It carries out graft modification, by modified effect, can be very good to be combined with increase particle, avoids falling off for particle, and
And while graft modification, realize between polymer using particle and metal ion as the crosslinking of core, by being crosslinked into one
Step increase can butadiene rubber mechanical property.
Specific embodiment
Mixed solvent is ethyl alcohol, carbon tetrachloride 4~9:3 by volume
Catalyst the preparation method comprises the following steps: by alkyl aluminum, mixed solvent 1:10 in mass ratio~16 carry out ultrasonic vibration 10min, then
1~2 times of alkyl aluminum quality of neodymium iso-octanate, the sodium chloride of alkyl aluminum quality 40~50% is added, is stirred at 50~55 DEG C
Mixing 20min is mixed, 2h is stood, is freeze-dried to get catalyst.
Mixed solution be hexane, hexamethylene, toluene, in acetone any one or it is any two kinds be mixed by any ratio and
At.
Gaseous mixture is ethylene, 4~6:2 is mixed nitrogen in molar ratio.
Cocatalyst the preparation method comprises the following steps: magnesium chloride, titanium chloride and water 4~6:3:20 in mass ratio are mixed,
The polyacrylamide for adding magnesium chloride quality 2~5% is stirred 1h, and carries out standing 4h at 5~8 DEG C, spray drying,
Dried object is collected to get cocatalyst.
Initiator is di-t-butyl peroxide, any one in peroxidized t-butyl perbenzoate.
Complexed surfactant is to mix neopelex, dioctyl succinate disulfonate acid 1:1~3 in mass ratio
It closes.
Modified graphene the preparation method comprises the following steps:
A. graphite, sodium nitrate 4~7:2 in mass ratio are uniformly mixed, are put into reactor, add 2~4 times of graphite quality
The concentrated sulfuric acid is stirred, and 1~4 times of graphite quality of potassium permanganate is added, and is stirred at 12~16 DEG C, is being warming up to 30~33 DEG C,
40~50min to be stirred, 1~2 times of graphite quality of water is added dropwise, stirring adds the hydrogen peroxide of potassium permanganate quality 30~40%,
Mixing is stood, and is filtered, and is washed, dry, obtains graphite oxide；
B. according to parts by weight, 100~120 parts of N, N- methylene formamide, 30~35 parts of graphene oxides, 13~15 parts are taken
C16/C18Alkylamide propyl dimethyl tertiary amine, 10~12 parts of methanol, 4~6 parts of maleic anhydrides, are put into reaction kettle, and boosting rises
Temperature is stirred to react, cooling, adjusts pH to 8.5~9.0, is stood, is added 3~5 times of graphene oxide quality of hydrazine hydrate, stir
It mixes, discharges, filter, washing is dry to get modified graphene.
Enhancing particle be modified graphene, mica and complexed surfactant 2:4~6:0.3 in mass ratio mill mixing and
At.
A kind of preparation method of butadiene rubber composite material, the preparation method include the following steps:
(1) it by mixed solvent, catalyst and butadiene cyclohexane solution 10~13:1:6~8 in mass ratio, is put into reaction kettle,
It is protected using argon gas, is warming up to 90~95 DEG C, is stirred to react 8~12h；
(2) after the completion of reaction, argon gas is displaced using gaseous mixture, adds butadiene cyclohexane solution volume 30~40%
Mass fraction be the cocatalyst of 30%1- butylene ethanol solution and butadiene cyclohexane solution quality 2~4%, and boost
To 1.3~1.9MPa, 110~115 DEG C are warming up to, keeps the temperature 4~7h；
(3) it after wait keep the temperature, is cooled to room temperature, discharges, collect out material, material out is evaporated, remove solvent, collect
Toluene, residue, dibutyl maleate 10~16:5 in mass ratio~7:3 are put into reactor and mixed by residue, pre- at 50 DEG C
Hot 25min；
(4) after preheating, the enhancing particle of 1~2% initiator of residue quality and residue quality 6~9% is added,
60~70 DEG C are warming up to, 10h is stirred, is cooled to room temperature, then carries out rotary evaporation removal toluene, spray drying uses second respectively
Alcohol, water are washed, dry to get butadiene rubber composite material.
Embodiment 1
Mixed solvent is ethyl alcohol, carbon tetrachloride 9:3 by volume
Catalyst the preparation method comprises the following steps: by alkyl aluminum, mixed solvent 1:16 in mass ratio carry out ultrasonic vibration 10min, add
The sodium chloride of the neodymium iso-octanate, alkyl aluminum quality 50% that 2 times of alkyl aluminum quality is stirred mixing 20min at 55 DEG C, stands
2h is freeze-dried to get catalyst.
Mixed solution is toluene.
Gaseous mixture is ethylene, 6:2 is mixed nitrogen in molar ratio.
Cocatalyst the preparation method comprises the following steps: magnesium chloride, titanium chloride and water 6:3:20 in mass ratio are mixed, then plus
The polyacrylamide for entering magnesium chloride quality 5% is stirred 1h, and carries out standing 4h at 8 DEG C, and dried object is collected in spray drying,
Up to cocatalyst.
Initiator is di-t-butyl peroxide.
Complexed surfactant is to mix neopelex, dioctyl succinate disulfonate acid 1:3 in mass ratio
It forms.
Modified graphene the preparation method comprises the following steps:
A. graphite, sodium nitrate 7:2 in mass ratio are uniformly mixed, are put into reactor, add 4 times of graphite quality of dense sulphur
Acid is stirred, and 4 times of graphite quality of potassium permanganate is added, and is stirred at 16 DEG C, is being warming up to 33 DEG C, is being stirred 50min, is being added dropwise
The water that 2 times of graphite quality, stirring, adds the hydrogen peroxide of potassium permanganate quality 40%, mixes, and stands, and filters, and washs, dry,
Obtain graphite oxide；
B. according to parts by weight, 120 parts of N, N- methylene formamide, 35 parts of graphene oxides, 15 parts of C are taken16/C18Alkylamide
Propyl-dimethyl tertiary amine, 12 parts of methanol, 6 parts of maleic anhydrides, are put into reaction kettle, and boosting heating is stirred to react, cooling, adjust
PH to 9.0 stands, adds 3~5 times of graphene oxide quality of hydrazine hydrate, stirs, and discharges, and filters, washing, it is dry to get
Modified graphene.
Enhancing particle is milled for modified graphene, mica and complexed surfactant 2:6:0.3 in mass ratio and is mixed.
A kind of preparation method of butadiene rubber composite material, the preparation method include the following steps:
(1) it by mixed solvent, catalyst and butadiene cyclohexane solution 13:1:8 in mass ratio, is put into reaction kettle, uses argon
Gas shielded is warming up to 95 DEG C, is stirred to react 12h；
(2) after the completion of reaction, argon gas is displaced using gaseous mixture, adds the matter of butadiene cyclohexane solution volume 40%
It measures score and is the cocatalyst of 30%1- butylene ethanol solution and butadiene cyclohexane solution quality 4%, and boost to
1.9MPa is warming up to 115 DEG C, keeps the temperature 7h；
(3) it after wait keep the temperature, is cooled to room temperature, discharges, collect out material, material out is evaporated, remove solvent, collect
Toluene, residue, dibutyl maleate 16:7:3 in mass ratio are put into reactor and mixed, preheated at 50 DEG C by residue
25min；
(4) after preheating, the enhancing particle of 2% initiator of residue quality and residue quality 9% is added, is warming up to
70 DEG C, 10h is stirred, is cooled to room temperature, then carry out rotary evaporation removal toluene, spray drying is washed using ethyl alcohol, water respectively
It washs, it is dry to get butadiene rubber composite material.
Embodiment 2
Mixed solvent is ethyl alcohol, carbon tetrachloride 6:3 by volume
Catalyst the preparation method comprises the following steps: by alkyl aluminum, mixed solvent 1:14 in mass ratio carry out ultrasonic vibration 10min, add
The sodium chloride of the neodymium iso-octanate, alkyl aluminum quality 45% that 1.5 times of alkyl aluminum quality is stirred mixing 20min at 53 DEG C, quiet
2h is set, is freeze-dried to get catalyst.
Mixed solution is hexane, 4:3 is mixed hexamethylene by volume.
Gaseous mixture is ethylene, 5:2 is mixed nitrogen in molar ratio.
Cocatalyst the preparation method comprises the following steps: magnesium chloride, titanium chloride and water 5:3:20 in mass ratio are mixed, then plus
The polyacrylamide for entering magnesium chloride quality 3% is stirred 1h, and carries out standing 4h at 6 DEG C, and dried object is collected in spray drying,
Up to cocatalyst.
Initiator is peroxidized t-butyl perbenzoate.
Complexed surfactant is to mix neopelex, dioctyl succinate disulfonate acid 1:2 in mass ratio
It forms.
Modified graphene the preparation method comprises the following steps:
A. graphite, sodium nitrate 5:2 in mass ratio are uniformly mixed, are put into reactor, add 3 times of graphite quality of dense sulphur
Acid is stirred, and 3 times of graphite quality of potassium permanganate is added, and is stirred at 14 DEG C, is being warming up to 32 DEG C, is being stirred 45min, is being added dropwise
The water that 2 times of graphite quality, stirring, adds the hydrogen peroxide of potassium permanganate quality 35%, mixes, and stands, and filters, and washs, dry,
Obtain graphite oxide；
B. according to parts by weight, 110 parts of N, N- methylene formamide, 33 parts of graphene oxides, 14 parts of C are taken16/C18Alkylamide
Propyl-dimethyl tertiary amine, 11 parts of methanol, 5 parts of maleic anhydrides, are put into reaction kettle, and boosting heating is stirred to react, cooling, adjust
PH to 9.0 stands, adds 4 times of graphene oxide quality of hydrazine hydrate, stirs, and discharges, and filters, washing, dry to get changing
Property graphene.
Enhancing particle is milled for modified graphene, mica and complexed surfactant 2:5:0.3 in mass ratio and is mixed.
A kind of preparation method of butadiene rubber composite material, the preparation method include the following steps:
(1) it by mixed solvent, catalyst and butadiene cyclohexane solution 11:1:7 in mass ratio, is put into reaction kettle, uses argon
Gas shielded is warming up to 93 DEG C, is stirred to react 10h；
(2) after the completion of reaction, argon gas is displaced using gaseous mixture, adds the matter of butadiene cyclohexane solution volume 35%
It measures score and is the cocatalyst of 30%1- butylene ethanol solution and butadiene cyclohexane solution quality 3%, and boost to
1.7MPa is warming up to 113 DEG C, keeps the temperature 5h；
(3) it after wait keep the temperature, is cooled to room temperature, discharges, collect out material, material out is evaporated, remove solvent, collect
Toluene, residue, dibutyl maleate 13:6:3 in mass ratio are put into reactor and mixed, preheated at 50 DEG C by residue
25min；
(4) after preheating, the enhancing particle of 1.5% initiator of residue quality and residue quality 8% is added, is heated up
To 65 DEG C, 10h is stirred, is cooled to room temperature, then carry out rotary evaporation removal toluene, spray drying is carried out using ethyl alcohol, water respectively
Washing, it is dry to get butadiene rubber composite material.
Embodiment 3
Mixed solvent is ethyl alcohol, carbon tetrachloride 4:3 by volume
Catalyst the preparation method comprises the following steps: by alkyl aluminum, mixed solvent 1:10 in mass ratio carry out ultrasonic vibration 10min, add
The sodium chloride of the neodymium iso-octanate, alkyl aluminum quality 40% that 1 times of alkyl aluminum quality is stirred mixing 20min at 50 DEG C, stands
2h is freeze-dried to get catalyst.
Mixed solution is hexane.
Gaseous mixture is ethylene, 4:2 is mixed nitrogen in molar ratio.
Cocatalyst the preparation method comprises the following steps: magnesium chloride, titanium chloride and water 4:3:20 in mass ratio are mixed, then plus
The polyacrylamide for entering magnesium chloride quality 2% is stirred 1h, and carries out standing 4h at 5 DEG C, and dried object is collected in spray drying,
Up to cocatalyst.
Initiator is di-t-butyl peroxide.
Complexed surfactant is to mix neopelex, dioctyl succinate disulfonate acid 1:1 in mass ratio
It forms.
Modified graphene the preparation method comprises the following steps:
A. graphite, sodium nitrate 4:2 in mass ratio are uniformly mixed, are put into reactor, add 2 times of graphite quality of dense sulphur
Acid is stirred, and 1 times of graphite quality of potassium permanganate is added, and is stirred at 12 DEG C, is being warming up to 30 DEG C, is being stirred 40min, is being added dropwise
The water that 1 times of graphite quality, stirring, adds the hydrogen peroxide of potassium permanganate quality 30%, mixes, and stands, and filters, and washs, dry,
Obtain graphite oxide；
B. according to parts by weight, 100 parts of N, N- methylene formamide, 30 parts of graphene oxides, 13 parts of C are taken16/C18Alkylamide
Propyl-dimethyl tertiary amine, 10 parts of methanol, 4 parts of maleic anhydrides, are put into reaction kettle, and boosting heating is stirred to react, cooling, adjust
PH to 8.5 stands, adds 3 times of graphene oxide quality of hydrazine hydrate, stirs, and discharges, and filters, washing, dry to get changing
Property graphene.
Enhancing particle is milled for modified graphene, mica and complexed surfactant 2:4:0.3 in mass ratio and is mixed.
A kind of preparation method of butadiene rubber composite material, the preparation method include the following steps:
(1) it by mixed solvent, catalyst and butadiene cyclohexane solution 10:1:6 in mass ratio, is put into reaction kettle, uses argon
Gas shielded is warming up to 90 DEG C, is stirred to react 8h；
(2) after the completion of reaction, argon gas is displaced using gaseous mixture, adds the matter of butadiene cyclohexane solution volume 30%
It measures score and is the cocatalyst of 30%1- butylene ethanol solution and butadiene cyclohexane solution quality 2%, and boost to
1.3MPa is warming up to 110 DEG C, keeps the temperature 4h；
(3) it after wait keep the temperature, is cooled to room temperature, discharges, collect out material, material out is evaporated, remove solvent, collect
Toluene, residue, dibutyl maleate 10:5:3 in mass ratio are put into reactor and mixed, preheated at 50 DEG C by residue
25min；
(4) after preheating, the enhancing particle of 1% initiator of residue quality and residue quality 6% is added, is warming up to
60 DEG C, 10h is stirred, is cooled to room temperature, then carry out rotary evaporation removal toluene, spray drying is washed using ethyl alcohol, water respectively
It washs, it is dry to get butadiene rubber composite material.
Comparative example 1
It is substantially the same manner as Example 2, only the difference is that lacking enhancing particle in step (4).
Comparative example 1
It is substantially the same manner as Example 2, only unlike lack modified graphene in enhancing particle in step (4).
Comparative example 2
Commercially available butadiene rubber.
The butadiene rubber of butadiene rubber composite material and comparative example 2 prepared by Examples 1 to 3 and comparative example 1 is put into punching
Sample preparation on piece machine, and detected, detection is executed according to according to national standard G/T528-1998 and GB 530-81.Pulling experiment is used
6.18mm wide cut-off knife dumbbell plate.The tensile speed of puller system is 500 ± 50 mm/s, and laboratory temperature is 25 DEG C, relative humidity
It is 80%., testing result is as follows:
It can to sum up obtain, butadiene rubber composite material prepared by the present invention is had excellent performance.
Claims (10)
1. a kind of preparation method of butadiene rubber composite material, which is characterized in that the preparation method includes the following steps:
(1) it by mixed solvent, catalyst and butadiene cyclohexane solution 10~13:1:6~8 in mass ratio, is put into reaction kettle,
It is protected using argon gas, is warming up to 90~95 DEG C, is stirred to react；
(2) after the completion of reaction, argon gas is displaced using gaseous mixture, adds butadiene cyclohexane solution volume 30~40%
1- butylene ethanol solution and butadiene cyclohexane solution quality 2~4% cocatalyst, and boost to 1.3~1.9MPa,
110~115 DEG C are warming up to, heat preservation；
(3) cooling after wait keep the temperature, discharging collects out material, material out is evaporated, and removes solvent, collects remaining
Toluene, residue, dibutyl maleate 10~16:5 in mass ratio~7:3 are put into reactor and mix preheating by object；
(4) after preheating, the enhancing particle of 1~2% initiator of residue quality and residue quality 6~9% is added,
Stirring, cooling, evaporative removal toluene is spray-dried, washing, dry to get butadiene rubber composite material.
2. the preparation method of butadiene rubber composite material according to claim 1, which is characterized in that mixed in the step (1)
Bonding solvent is ethyl alcohol, carbon tetrachloride 4~9:3 by volume.
3. the preparation method of butadiene rubber composite material according to claim 1, which is characterized in that urged in the step (1)
Agent the preparation method comprises the following steps: by alkyl aluminum, mixed solution 1:10 in mass ratio~16 carry out ultrasonic vibration, add alkyl aluminum
1~2 times of neodymium iso-octanate, the sodium chloride of alkyl aluminum quality 40~50% are measured, mixing is stirred at 50~55 DEG C, is stood,
Freeze-drying is to get catalyst.
4. the preparation method of butadiene rubber composite material according to claim 3, which is characterized in that the mixed solution is for oneself
Alkane, hexamethylene, toluene, any one or any two kinds in acetone are mixed by any ratio.
5. the preparation method of butadiene rubber composite material according to claim 1, which is characterized in that mixed in the step (2)
Conjunction gas is ethylene, 4~6:2 is mixed nitrogen in molar ratio.
6. the preparation method of butadiene rubber composite material according to claim 1, which is characterized in that auxiliary in the step (2)
Co-catalyst the preparation method comprises the following steps: magnesium chloride, titanium chloride and water 4~6:3:20 in mass ratio are mixed, add chlorination
The polyacrylamide of magnesia amount 2~5%, is stirred, and is stood at 5~8 DEG C, spray drying, collect dried object to get
Cocatalyst.
7. the preparation method of butadiene rubber composite material according to claim 1, which is characterized in that draw in the step (4)
Hair agent is di-t-butyl peroxide, any one in peroxidized t-butyl perbenzoate.
8. the preparation method of butadiene rubber composite material according to claim 1, which is characterized in that increase in the step (4)
Strong particle is milled for modified graphene, mica and complexed surfactant 2:4~6:0.3 in mass ratio to be mixed.
9. the preparation method of butadiene rubber composite material according to claim 8, which is characterized in that the modified graphene
The preparation method comprises the following steps:
A. graphite, sodium nitrate 4~7:2 in mass ratio are uniformly mixed, are put into reactor, add 2~4 times of graphite quality
The concentrated sulfuric acid is stirred, and 1~4 times of graphite quality of potassium permanganate is added, and is stirred at 12~16 DEG C, is being warming up to 30~33 DEG C,
40~50min to be stirred, 1~2 times of graphite quality of water is added dropwise, stirring adds the hydrogen peroxide of potassium permanganate quality 30~40%,
Mixing is stood, and is filtered, and is washed, dry, obtains graphite oxide；
B. according to parts by weight, 100~120 parts of N, N- methylene formamide, 30~35 parts of graphene oxides, 13~15 parts are taken
C16/C18Alkylamide propyl dimethyl tertiary amine, 10~12 parts of methanol, 4~6 parts of maleic anhydrides, are put into reaction kettle, and boosting rises
Temperature is stirred to react, cooling, adjusts pH to 8.5~9.0, is stood, is added 3~5 times of graphene oxide quality of hydrazine hydrate, stir
It mixes, discharges, filter, washing is dry to get modified graphene.
10. the preparation method of butadiene rubber composite material according to claim 8, which is characterized in that the composite surface is living
Property agent be neopelex, dioctyl succinate disulfonate acid 1:1~3 in mass ratio are mixed.
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| CN201910135546.0A CN109943004A (en) | 2019-02-25 | 2019-02-25 | A kind of preparation method of butadiene rubber composite material |
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Application publication date: 20190628 |