CN106243250B - The control method of solwution method butyl rubber bromo structure - Google Patents
The control method of solwution method butyl rubber bromo structure Download PDFInfo
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Abstract
The invention discloses a kind of methods that effective control solwution method butyl rubber bromination replaces position, this method removes unreacted monomer in solwution method synthesis butyl rubber glue first, the cosolvent being made of alkane and electrophilicity reagent centainly matched is added, butyl rubber glue is diluted to a certain concentration, strong oxidizing property reagent solution is added to be uniformly mixed, the alkane solution of bromine is added in reaction kettle by multiple spot injection method later and carries out bromination reaction, lye is added after reaction to terminate, is washed to neutrality；Bromo structure regulator is added, carries out three kinds of microstructure adjustment；It is eventually adding the auxiliary agents such as structural stabilizing agent, antioxidant and deacidification agent, it is post-treated, the relative amount of the secondary position allylic structure of bromo is greater than 70% in obtained product, for the content of bromo uncle position allylic structure less than 20%, the properties such as bromine content, degree of unsaturation and Mooney viscosity meet the requirement of automobile tire inner tube of a tyre inner liner and Medical rubber plug etc..
Description
Technical field
The present invention relates to the control method that a kind of solwution method brombutyl replaces position, this method can be effectively controlled bromination
The relative scale of three kinds of microstructures in butyl rubber.
Background technique
With domestic tire meridian, tubeless and the butylated fast development of medical rubber stopper, China is to brominated butyl
The demand sustainable growth of rubber.The Apparent con- sumption of China's brombutyl in 2007 only has 12.50 ten thousand t, increases within 2011
17.51 ten thousand t are added to, further increase respectively to 18.82 ten thousand t and 20.15 ten thousand t within 2012 and 2013.Chinese bromination in 2013
Butyl rubber import volume increased by 59% or so compared with 2007, and average annual amplification is 8% or so.The corresponding product degree of self-sufficiency was by 2007
7% or so for being completely dependent on import and developing to 2013, the product degree of self-sufficiency is lower.
China's brombutyl in 2013 is in the Supply Structure of low and middle-end field and high-end field, Yanshan Petrochemical and Zhejiang
River mail transfer company occupies the supply ratio in low and middle-end field 47%, and substantially external in the high-end application field such as curing bag
Bright Sheng and Exxon Corporation occupied by.Therefore, novel brombutyl production technology is developed, high-quality bromination fourth is produced
Base rubber fills up domestic market blank, reduces the dependence to external imported product, the popularization to domestic brombutyl future
Using having important practical significance.
The bromination reaction of butyl rubber mainly presses the progress of ionic substitution reaction course, and molecular bromine is by alkene first
Double bond polarizes to form positive and negative ion, and the double bond of the butyl rubber of Bromonium ion attack later forms transition state bromide ion.Due to side
The steric hindrance of methyl makes bromine anion stalled offence on chain, and transition state is caused to lose H+It generates, forms the secondary position allyl of bromo
Based structures, while generating small molecule hydrogen bromide.Since the secondary position allylic structure of bromo is unstable, it is prone to rearrangement reaction transformation
At bromo uncle position allylic structure.There is non-bromination, bromo uncle position allyl and the secondary position allyl of bromo in brombutyl
Three kinds of microstructures.Since allylic structure relative amount high brombutyl in bromo uncle position has faster vulcanization reaction
Rate, but also reduce the mooney scorch safety of rubber simultaneously, and the secondary position allylic structure of bromo is just in contrast.Cause
This, needs the relative scale of three kinds of microstructures in strict control brombutyl in industrial production, to prepare high-performance
Brombutyl product.
Summary of the invention
In order to develop novel brombutyl production technology, production high-quality brombutyl, to fill up domestic
The dependence of the market vacancy, reduction to external imported product, the invention proposes a kind of effective solwution method butyl rubber bromo knots
The control method of structure is, it can be achieved that continuous, efficient and stable prepares the qualified butyl rubber bromide of three kinds of microstructure ratios
Glue product.
The present invention provides a kind of control method of solwution method butyl rubber bromo structure, comprising the following steps:
(a) butyl rubber glue is synthesized by solwution method, 0.5~6h of heating stirring in 40~80 DEG C of waters bath with thermostatic control takes off
Unreacted monomer in removing glue liquid；
(b) electrophilicity reagent is added into the synthesis butyl rubber glue for removed unreacted monomer, adds later strong
Oxidative reagent；
(c) alkane solution that bromine is added into reaction kettle carries out bromination reaction；
(d) after bromination reaction, the NaOH solution that 1.0~20wt% of mass fraction is added terminates reaction, neutralization reaction 5
Stop stirring after~30min, glue is washed with distilled water to pH value close to neutrality；
(e) structure regulator is added into the glue that step (d) obtains；
(f) bromo structural stabilizing agent, antioxidant and deacidification agent are added into the glue that step (e) obtains；
(g) boiling water is added into the glue that step (f) obtains, then solvent is flashed and is removed, products therefrom is post-treated
Dehydration, it is dry and squeeze it is blocking after obtain product.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein mixed solvent is used in step (b)
It is preferably 10~40wt% that the concentration of butyl rubber glue is synthesized after dilution.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (b), mixed solvent
The ratio that contained electrophilicity reagent accounts for total solvent volume is preferably not greater than 50% and is not 0.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (b), electrophilicity examination
Agent is preferably methylene chloride, dichloroethanes, ethylene oxide, pyridine or N,N-dimethylformamide.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (b), synthesize butyl
The strong oxidizing property reagent being added in rubber glue, dosage are preferably 0.1~5 times of bromine molal quantity.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (b), strong oxidizing property
Reagent is preferably potassium bichromate, sodium metaperiodate, potassium permanganate or hydrogen peroxide.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (c), the alkane of bromine
Hydrocarbon solution is preferably the bromine hexane solution of 0.1~3mol/L.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (c), bromine solution
It is preferred that being added under the conditions of normal pressure is protected from light by multiple spot injection method.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (e), structure is adjusted
The dosage of agent is preferably to account for the mass percent 0.5~3% of brombutyl, it is stirred to react at 10~90 DEG C 5 after addition~
30min。
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (e), structure is adjusted
Agent is preferably tetrabutylammonium bromide, tetraethylammonium bromide, benzyl triethyl ammonium bromide or triphenylphosphine.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (f), bromo structure
Stabilizer is added in the glue that step (e) is obtained after being dissolved in mineral oil, and the dosage of bromo structural stabilizing agent preferably accounts for bromination
The mass percent 0.1~3.0% of butyl rubber.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein in step (f), bromo structure
Stabilizer is preferably dibutyl tin dilaurate, zinc stearate, magnesium stearate, iron naphthenate or epoxidized soybean oil.
The invention has the following beneficial effects:
(1) the present invention relates to a kind of by solwution method synthesis butyl rubber glue and directly bromination prepares brombutyl
Method, avoid the solvent needed for slurry processes technology prepares brombutyl switching and sizing material dissolution process, simplify
Bromination reaction technique reduces production cost；
(2) a certain amount of electrophilicity reagent is added in reaction dissolvent according to the present invention, accelerates bromination reaction rate,
The bromination reaction time is shortened, production efficiency is improved；
(3) the invention discloses a kind of methods that effectively control solwution method butyl rubber bromination replaces position, to inhibit bromo
Structure has secondary position to the transformation of uncle position, efficiently, continuously and stably prepares the brombutyl of high-quality.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The concentration of butyl rubber glue is synthesized after dilution:
In the present invention, the concentration that butyl rubber glue is synthesized after dilution is not particularly limited, usually uses mixed solvent
By the concentration dilution for synthesizing butyl rubber glue to 10~40wt%: if the synthesis butyl rubber gelatin concentration after dilution is lower than
10wt% be easy to cause brombutyl Mooney viscosity after leading to reaction to reduce since gelatin concentration is too low；If after dilution
Synthesis butyl rubber gelatin concentration be higher than 40wt%, since gelatin concentration is excessively high, viscosity is excessive, bromine and glue is caused to react
Mixing is uneven in the process, and the bromine content of brominated butyl rubber of synthesis is relatively low, and structure proportion is unqualified.
Electrophilicity reagent accounts for the ratio of mixed solvent total volume:
In the present invention, the ratio for accounting for mixed solvent total volume to electrophilicity reagent used is not particularly limited, usually parent
The ratio that electrical reagent accounts for mixed solvent total volume is 0~50%: if electrophilicity reagent accounts for the ratio of mixed solvent total volume
It is 0, due to not having the presence of electrophilicity reagent, the secondary position allylic structure content of bromo is be easy to cause to reduce；If electrophilicity is tried
The ratio that agent accounts for mixed solvent total volume is greater than 50%, since electrophilicity ratio of reagents is excessively high in solvent, causes bromobutyl rubber
Plastic structure ratio is unqualified.
The dosage of strong oxidizing property reagent:
In the present invention, the dosage of strong oxidizing property reagent used is not particularly limited, the use of usual strong oxidizing property reagent
Amount is 0.1~5 times of bromine molal quantity: if the dosage of strong oxidizing property reagent is lower than 0.1 times of bromine molal quantity, due to strong oxygen
The dosage of the property changed reagent is very few, and the degree of unsaturation of brombutyl is be easy to cause to reduce always as the reaction time increases；
If the dosage of strong oxidizing property reagent is higher than 5 times of bromine molal quantity, since the dosage of strong oxidizing property reagent is excessive, cause to react
Strong oxidizer residual is more in glue afterwards is difficult to remove.
The concentration of bromine hexane solution:
In the present invention, the concentration of bromine hexane solution used is not particularly limited, usual bromine hexane solution
Concentration be 0.1~3mol/L: if the concentration of bromine hexane solution is easy to make lower than 0.1mol/L since concentration is too low
It is relatively low at bromine content of brominated butyl rubber after bromination；If the concentration of bromine hexane solution is higher than 3mol/L, due to concentration mistake
Height, causes the reduction of brombutyl degree of unsaturation, and structure proportion is unqualified.
The dosage of structure regulator:
In the present invention, the dosage of structure regulator used is not particularly limited, the dosage of usual structure regulator accounts for
The mass percent of brombutyl is 0.5~3%: if the dosage of structure regulator accounts for the quality hundred of brombutyl
Score is lower than 0.5%, since the dosage of structure regulator is very few, be easy to cause adjustment structure reaction insufficient, is not achieved effectively
The purpose of adjustment structure；If the mass percent that the dosage of structure regulator accounts for brombutyl is higher than 3%, due to structure
The dosage of regulator is excessive, causes the raising of production cost, and easily influences the performance of final products.
Temperature when structure regulator adds:
In the present invention, temperature when adding to structure regulator is not particularly limited, when usual structure regulator adds
Temperature be 10~90 DEG C: if temperature be lower than 10 DEG C, since reaction temperature is lower, be easy to cause adjustment structure reaction rate compared with
It is low, increase the time cost of reaction；If temperature is higher than 90 DEG C, since reaction temperature is excessively high, cause by the secondary position allyl of bromo
Transformation of the based structures to bromo uncle position allylic structure.
The reaction time of adjustment structure:
In the present invention, the reaction time of adjustment structure is not particularly limited, the reaction time of usual adjustment structure is 5
~30min: if the reaction time of adjustment structure be easy to cause adjustment structure to react less than 5min since the reaction time is too short
It is insufficient, the purpose of effective adjustment structure is not achieved；If the reaction time of adjustment structure is more than 30min, due to the reaction time
It is too long, the raising of time cost is caused, and have no other beneficial effects.
The dosage of bromo structural stabilizing agent:
In the present invention, the dosage of bromo structural stabilizing agent used is not particularly limited, usual bromo structural stabilizing agent
Dosage account for brombutyl mass percent be 0.1~3%: if the dosage of bromo structural stabilizing agent accounts for brominated butyl
The mass percent of rubber is less than 0.1%, and since the dosage of structure regulator is very few, the bromine of substantially stabilized final products is not achieved
For the purpose of structure；If the dosage of bromo structural stabilizing agent accounts for the mass percent of brombutyl more than 3%, due to bromine
It is excessive for the dosage of structural stabilizing agent, the raising of production cost is caused, and easily influence the performance of final products.
7 embodiments are set forth below, the present invention is further illustrated, the present invention is not limited solely to these embodiments.
Embodiment 1:
The butyl rubber glue 2000mL of solwution method synthesis is added in reaction kettle, n-hexane and dichloroethanes group are added
At mixed solvent, gelatin concentration is diluted to 15%, wherein dichloroethanes accounts for the 30% of overall solution volume, is added later
The potassium dichromate aqueous solution 100mL of 27.59g/L, the degree of unsaturation of butyl rubber are 1.9%；By the hexane solution of bromine
20mL (volume ratio of n-hexane and bromine is 25:1) is added in storage tank；Temperature of charge in reaction kettle is heated to 45 DEG C, to
The hexane solution of bromine in storage tank is added in reaction kettle by multiple spot injection method, after bromination reaction 2min, 400mL mass is added
The NaOH solution of score 1.5wt% terminates, and stops stirring after neutralization reaction 15min；Glue is washed with distilled water to pH value to connect
Weakly acidic pH is added the tetrabutylammonium bromide solution aqueous solution 100mL of mass fraction 0.5%, is stirred to react 10min at 30 DEG C, most
Dibutyl tin dilaurate (2.0wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%) are added afterwards
The auxiliary agents such as equal auxiliary agents are added boiling water and flash off solvent, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, obtained bromine
The relative amount for changing the secondary position allylic structure of bromo in butyl rubber product is 72%, opposite the containing of bromo uncle position allylic configuration
Amount is 16%, bromine content 2.1wt%, degree of unsaturation 1.5%.
Embodiment 2:
The butyl rubber glue 3000mL of solwution method synthesis is added in reaction kettle, n-hexane and methylene chloride group are added
At mixed solvent, gelatin concentration is diluted to 10%, wherein methylene chloride accounts for the 50% of overall solution volume, is added later
The potassium permanganate solution 150mL of 41.39g/L, the degree of unsaturation of butyl rubber are 2.0%；By the hexane solution of bromine
30mL (volume ratio of n-hexane and bromine is 20:1) is added in storage tank；Temperature of charge in reaction kettle is heated to 50 DEG C, to
The hexane solution of bromine in storage tank is added in reaction kettle by multiple spot injection method, after bromination reaction 2.5min, 400mL matter is added
The NaOH solution for measuring score 2.0wt% terminates, and stops stirring after neutralization reaction 20min；Glue is washed with distilled water to pH value
Close to neutrality, the benzyl triethyl ammonium bromide aqueous solution 150mL of mass fraction 1.0% is added, is stirred to react 15min at 50 DEG C,
The auxiliary agents such as iron naphthenate (1.5wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%) are eventually adding,
Boiling water is added and flashes off solvent, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, obtained brombutyl product
The relative amount of the middle secondary position allylic structure of bromo is 74%, and the relative amount of bromo uncle position allylic configuration is 15%, and bromine contains
Amount is 2.2wt%, degree of unsaturation 1.6%.
Embodiment 3:
The butyl rubber glue 5000mL of solwution method synthesis is added in reaction kettle, n-hexane and methylene chloride group are added
At mixed solvent, gelatin concentration is diluted to 13%, wherein methylene chloride accounts for the 40% of overall solution volume, is added later
The sodium metaperiodate aqueous solution 200mL of 38.79g/L, the degree of unsaturation of butyl rubber are 1.8%；By the hexane solution of bromine
40mL (volume ratio of n-hexane and bromine is 19:1) is added in storage tank；Temperature of charge in reaction kettle is heated to 40 DEG C, to
The alkane solution of bromine in storage tank is added in reaction kettle by multiple spot injection method, after bromination reaction 1.5min, 400mL mass is added
The NaOH solution of score 2.5wt% terminates, and stops stirring after neutralization reaction 10min；Glue is washed with distilled water to pH value to connect
Weakly acidic pH is added the hexane solution 200mL of the triphenylphosphine of mass fraction 2.0%, is stirred to react 5min at 40 DEG C, is eventually adding
Boiling water is added in the auxiliary agents such as magnesium stearate (2.0wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%)
Solvent is flashed off, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, bromo is secondary in obtained brombutyl product
The relative amount of position allylic structure is 71%, and the relative amount of bromo uncle position allylic configuration is 14%, and bromine content is
2.0wt%, degree of unsaturation 1.7%.
Embodiment 4:
The butyl rubber glue 5000mL of solwution method synthesis is added in reaction kettle, n-hexane and methylene chloride group are added
At mixed solvent, gelatin concentration is diluted to 17%, wherein methylene chloride accounts for the 40% of overall solution volume, and concentration is added later
30% hydrogen peroxide 20mL, the degree of unsaturation of butyl rubber are 1.8%；By the hexane solution 40mL of bromine (n-hexane with
The volume ratio of bromine is 19:1) it is added in storage tank；Temperature of charge in reaction kettle is heated to 40 DEG C, into reaction kettle by more
The alkane solution of bromine in storage tank is added in point injection method, after bromination reaction 1.5min, is added 400mL mass fraction 2.5wt%'s
NaOH solution (asking supplemental amount) terminates, and stops stirring after neutralization reaction 10min；Glue is washed with distilled water to pH value to approach
Neutrality is added the tetraethylammonium bromide aqueous solution 400mL of mass fraction 3.0%, is stirred to react 25min at 50 DEG C, is eventually adding
Boiling water is added in the auxiliary agents such as zinc stearate (2.0wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%)
Solvent is flashed off, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, bromo is secondary in obtained brombutyl product
The relative amount of position allylic structure is 71%, and the relative amount of bromo uncle position allylic configuration is 14%, and bromine content is
1.9wt%, degree of unsaturation 1.65%.
Embodiment 5:
The butyl rubber glue 3000mL of solwution method synthesis is added in reaction kettle, n-hexane and ethylene oxide group are added
At mixed solvent, gelatin concentration is diluted to 20%, ethylene oxide accounts for the 30% of overall solution volume, is added later
The sodium metaperiodate aqueous solution 100mL of 21.39g/L, the degree of unsaturation of butyl rubber are 2.0%；By the hexane solution of bromine
100mL (volume ratio of n-hexane and bromine is 20:1) is added in storage tank；Temperature of charge in reaction kettle is heated to 50 DEG C, to
The hexane solution of bromine in storage tank is added in reaction kettle by multiple spot injection method, after bromination reaction 2.5min, 200mL matter is added
The NaOH solution for measuring score 2.0wt% terminates, and stops stirring after neutralization reaction 20min；Glue is washed with distilled water to pH value
Close to neutrality, the benzyl triethyl ammonium bromide aqueous solution 150mL of mass fraction 1.0% is added, is stirred to react 15min at 10 DEG C,
Epoxidized soybean oil (3.0wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%) etc. is eventually adding to help
Agent is added boiling water and flashes off solvent, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, obtained brombutyl
The relative amount of the secondary position allylic structure of bromo is 74% in product, and the relative amount of bromo uncle position allylic configuration is 15%,
Bromine content is 2.2wt%, degree of unsaturation 1.6%.
Embodiment 6:
The butyl rubber glue 3000mL of solwution method synthesis is added in reaction kettle, n-hexane and pyridine composition are added
Gelatin concentration is diluted to 40% by mixed solvent, and wherein pyridine accounts for the 40% of overall solution volume, and the weight of 68.63g/L is added later
Chromic acid aqueous solutions of potassium 500mL, the degree of unsaturation of butyl rubber are 2.0%；By hexane solution 5mL (n-hexane and the liquid of bromine
The volume ratio of bromine is 16:7) it is added in storage tank；Temperature of charge in reaction kettle is heated to 50 DEG C, passes through multiple spot into reaction kettle
The hexane solution of bromine in storage tank is added in injection method, after bromination reaction 2.5min, is added 500mL mass fraction 2.0wt%'s
NaOH solution terminates, and stops stirring after neutralization reaction 20min；Glue is washed with distilled water to pH value close to neutrality, matter is added
The tetrabutyl phosphonium bromide aqueous ammonium 150mL for measuring score 1.0%, is stirred to react 15min at 90 DEG C, is eventually adding iron naphthenate
The auxiliary agents such as (0.1wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%), addition boiling water flash off molten
Agent, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, the secondary position allyl of bromo in obtained brombutyl product
The relative amount of structure is 74%, and the relative amount of bromo uncle position allylic configuration is 15%, bromine content 2.2wt%, insatiable hunger
With degree 1.6%.
Embodiment 7:
The butyl rubber glue 3000mL of solwution method synthesis is added in reaction kettle, n-hexane and N, N- dimethyl are added
The mixed solvent of formamide composition, is diluted to 40% for gelatin concentration, wherein n,N-Dimethylformamide accounts for overall solution volume
50%, the potassium permanganate solution 300mL of 35.85g/L is added later, the degree of unsaturation of butyl rubber is 2.0%；By bromine
Hexane solution 20mL (volume ratio of n-hexane and bromine is 13:8) is added in storage tank；By the temperature of charge heating in reaction kettle
To 50 DEG C, the hexane solution of bromine in storage tank is added by multiple spot injection method into reaction kettle, after bromination reaction 2.5min, adds
The NaOH solution for entering 700mL mass fraction 2.0wt% terminates, and stops stirring after neutralization reaction 20min；By glue distillation washing
It washs to pH value close to neutrality, the tetraethylammonium bromide aqueous solution 150mL of mass fraction 1.0% is added, is stirred to react at 70 DEG C
15min is eventually adding iron naphthenate (1.5wt%), antioxidant 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%)
Equal auxiliary agents are added boiling water and flash off solvent, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, obtained brominated butyl
The relative amount of the secondary position allylic structure of bromo is 74% in rubber product, and the relative amount of bromo uncle position allylic configuration is
15%, bromine content 2.2wt%, degree of unsaturation 1.6%.
Comparative example 1:
The butyl rubber glue 2000mL of solwution method synthesis is added in reaction kettle, hexane is added and is diluted to gelatin concentration
15%, the degree of unsaturation of butyl rubber is 1.9%；By the hexane solution 20mL of bromine, (volume ratio of n-hexane and bromine is
25:1) it is added in storage tank；Temperature of charge in reaction kettle is heated to 45 DEG C, into reaction kettle be added storage tank in bromine just oneself
Alkane solution, after bromination reaction 2min, the NaOH solution that 400mL mass fraction 1.5wt% is added is terminated, after neutralization reaction 15min
Stop stirring；Glue is washed with distilled water to pH value close to neutrality, boiling water is added and flashes off solvent, through dehydration, drying and squeezes
After being pressed into the aftertreatment technologies such as block, the relative amount of the secondary position allylic structure of bromo is in obtained brombutyl product
46%, the relative amount of bromo uncle position allylic configuration is 28%, bromine content 1.7wt%, degree of unsaturation 1.3%.
Comparative example 2:
The butyl rubber glue 2000mL of solwution method synthesis is added in reaction kettle, hexane is added and is diluted to gelatin concentration
15%, the potassium dichromate aqueous solution 100mL of 27.59g/L is added later, the degree of unsaturation of butyl rubber is 1.9%；By bromine
Hexane solution 20mL (volume ratio of n-hexane and bromine is 25:1) is added in storage tank；By the temperature of charge heating in reaction kettle
To 45 DEG C, the hexane solution of bromine in storage tank is added by multiple spot injection method into reaction kettle, after bromination reaction 2min, is added
The NaOH solution of 400mL mass fraction 1.5wt% terminates, and stops stirring after neutralization reaction 15min；Glue is washed with distilled water
To pH value close to neutrality, boiling water is added and flashes off solvent, after dehydration, drying and squeezing the aftertreatment technologies such as blocking, obtains
In brombutyl product the relative amount of the secondary position allylic structure of bromo be 52%, bromo uncle position allylic configuration it is opposite
Content is 36%, bromine content 2.0wt%, degree of unsaturation 1.2%.
Claims (9)
1. a kind of control method of solwution method butyl rubber bromo structure, which comprises the following steps:
(a) butyl rubber glue is synthesized by solwution method, 0.5~6h of heating stirring in 40~80 DEG C of waters bath with thermostatic control removes glue
Unreacted monomer in liquid；
(b) electrophilicity reagent is added into the synthesis butyl rubber glue for removed unreacted monomer, adds Strong oxdiative later
Property reagent；
(c) alkane solution that bromine is added into reaction kettle carries out bromination reaction；
(d) after bromination reaction, the NaOH solution that 1.0~20wt% of mass fraction is added, which terminates, reacts, and neutralization reaction 5~
Stop stirring after 30min, glue is washed with distilled water to pH value close to neutrality；
(e) structure regulator is added into the glue that step (d) obtains；
(f) bromo structural stabilizing agent, antioxidant and deacidification agent are added into the glue that step (e) obtains；
(g) boiling water is added into the glue that step (f) obtains, then solvent is flashed and is removed, the post-treated dehydration of products therefrom,
It is dry and squeeze it is blocking after obtain product,
Wherein, in step (b), the strong oxidizing property reagent be potassium bichromate, sodium metaperiodate, potassium permanganate or hydrogen peroxide,
Wherein, in step (e), the structure regulator is tetrabutylammonium bromide, tetraethylammonium bromide or benzyl triethyl ammonium bromination
Ammonium,
Wherein, in step (f), the bromo structural stabilizing agent is dibutyl tin dilaurate, zinc stearate, magnesium stearate, ring
Alkanoic acid iron or epoxidized soybean oil, the antioxidant are 1010, and the deacidification agent is calcium stearate.
2. the control method of solwution method butyl rubber bromo structure as described in claim 1, which is characterized in that in step (b),
It is 10~40wt% that the synthesis butyl rubber glue, which is diluted to concentration with mixed solvent,.
3. the control method of solwution method butyl rubber bromo structure as claimed in claim 2, which is characterized in that in step (b),
The mixed solvent, which contains, to be accounted for total solvent volume no more than 50% and is not 0.
4. the control method of solwution method butyl rubber bromo structure as claimed in claim 3, which is characterized in that in step (b),
The electrophilicity reagent is methylene chloride, dichloroethanes, ethylene oxide, pyridine or N,N-dimethylformamide.
5. the control method of solwution method butyl rubber bromo structure as described in claim 1, which is characterized in that in step (b),
The dosage of the strong oxidizing property reagent is 0.1~5 times of bromine molal quantity.
6. the control method of solwution method butyl rubber bromo structure as described in claim 1, which is characterized in that in step (c),
The alkane solution of the bromine is the bromine hexane solution of 0.1~3mol/L.
7. the control method of solwution method butyl rubber bromo structure as described in claim 1 or 6, which is characterized in that step (c)
In, the bromine solution is added under the conditions of normal pressure is protected from light by multiple spot injection method.
8. the control method of solwution method butyl rubber bromo structure as described in claim 1, which is characterized in that in step (e),
The mass percent that the dosage of the structure regulator accounts for brombutyl is 0.5~3%, is stirred after addition at 10~90 DEG C
React 5~30min.
9. the control method of solwution method butyl rubber bromo structure as described in claim 1, which is characterized in that in step (f),
The bromo structural stabilizing agent is added in the glue that step (e) is obtained after being dissolved in mineral oil, the bromo structural stabilizing agent
The percentage that dosage accounts for brombutyl quality is 0.1~3.0%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510303041.2A CN106243250B (en) | 2015-06-04 | 2015-06-04 | The control method of solwution method butyl rubber bromo structure |
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| CN106749816B (en) * | 2016-11-30 | 2020-05-12 | 黄河三角洲京博化工研究院有限公司 | Preparation method of brominated butyl rubber |
| CN110642965A (en) * | 2019-10-30 | 2020-01-03 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber |
| CN112142884B (en) * | 2020-09-01 | 2023-06-09 | 中北大学 | Brominated butyl rubber synthesis device and process |
| CN114790256B (en) * | 2022-04-28 | 2023-12-01 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber under action of phase transfer agent |
| CN115232238B (en) * | 2022-09-21 | 2023-01-17 | 山东海化集团有限公司 | Method for preparing brominated butyl rubber by using microchannel reactor |
| CN115947881B (en) * | 2023-03-15 | 2023-05-30 | 山东润科化工股份有限公司 | Synthesis method of brominated ethylene propylene diene monomer |
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| Title |
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| Effects of Assistant Solvents and Mixing Intensity on the Bromination Process of Butyl Rubber;WANG Wei ,et.al;《Chinese Journal of Chemical Engineering》;20140403;第22卷(第4期);pages 398-404, |
| 溴化丁基橡胶合成过程中影响因素的研究;胡云鹏;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20071215;第14页 |
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