CN108164845A - A kind of halogenated butyl rubber and preparation method thereof - Google Patents
A kind of halogenated butyl rubber and preparation method thereof Download PDFInfo
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- CN108164845A CN108164845A CN201711443449.5A CN201711443449A CN108164845A CN 108164845 A CN108164845 A CN 108164845A CN 201711443449 A CN201711443449 A CN 201711443449A CN 108164845 A CN108164845 A CN 108164845A
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- butyl rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The present invention provides a kind of halogenated butyl rubber, including：It is one or more in the carbonate of alkali metal of the weight % of 0.01 weight %~1.0 or the carbonate or bicarbonate of bicarbonate and alkaline-earth metal；The stabilizer of the weight % of 0.1 weight %~3.0；The auxiliary agent of the weight % of 0.11 weight %~5.0；Surplus is halogenated butyl rubber；Halogen in the halogenated butyl rubber accounts for the weight % of 0.5 weight % of the halobutyl rubber compositions~3.0.The present invention is one or more in the carbonate of a small amount of alkali metal or the carbonate or bicarbonate of bicarbonate and alkaline-earth metal by being added in into product, in the case of the dosage for reducing traditional stabilizer, isomerization of the secondary bit architecture to primary bit architecture in halogenated butyl rubber can effectively be inhibited, slow down the rate of deterioration of halogenated butyl rubber.Simultaneously as reducing the content of small organic molecule epoxidized soybean oil, product is purer.
Description
Technical field
The invention belongs to field of rubber technology, and in particular to a kind of halogenated butyl rubber and preparation method thereof.
Background technology
The technique of industrial production halogenated butyl rubber is generally as follows.Butyl rubber dissolving is obtained into fourth in a solvent first
Then base rubber glue is sent into reactor progress halogenation together with halide reagent and obtains halogenated butyl rubber glue.Halogenation
Neutralization reagent is added in after the completion of reaction, to neutralize the by-product hydrogen halide of halogenation generation.Neutralization reagent is typically water solubility
, therefore the material after neutralization is the mixed material of halogenated butyl rubber glue and water.It is then added in mixed material necessary
Auxiliary agent such as dispersant calcium stearate, antioxidant, stabilizer epoxidized soybean oil.Auxiliary agent and halogenated butyl rubber are sent after mixing
Enter condensing field and remove solvent through high-temperature water vapor, while obtain the mixture of halogenated butyl rubber micelle and water.Micelle/water mixing
Object is sent into one group of dryer group system after vibrating screen removes most of water, and removing moisture content obtains the halobutyl of fugitive constituent qualification
Rubber product.
Butyl rubber is isobutene and a small amount of second comonomer one kind that for example copolymerization such as isoprene, p-methylstyrene form
Synthetic rubber.It is generally believed that in apolar medium and under the conditions of being protected from light, butyl that isobutene is obtained with isoprene copolymer
The bromination reaction of isoprene unit is a kind of ionic substitution reaction in rubber.Due to the tertiary fourth in isoprene monomer unit both ends
The presence of base, the final product of this reaction mainly replace structure (R.Vukov., Rubber Chemistry and
Technology, 1984, Vol (57), P275-283).It is, an allylic hydrogen on isoprene monomer unit is by halogen
Atom replaces, while generates the by-product hydrogen halide of a molecule.Replacing structure, there are two types of main according to halogen atom relative position different
Structure is wanted, is secondary bit architecture (TypeII) and primary bit architecture (TypeIII) respectively.In general, after halogenating butyl rubber, halogenation
The primary structure of product is secondary bit architecture.Since primary bit architecture is thermodynamically more stable relative to secondary bit architecture, in fourth
In base rubber halogenation and post processing drying and storage process, some secondary bit architecture can be isomerized to primary bit architecture.
Temperature and lewis acid, the presence of transition metal ions all have an impact the relative amount of primary bit architecture.
However, during secondary bit architecture is isomerized to primary bit architecture, always make with different degrees of dehalogenation
Product quality declines, especially during product drying and storage.With the reduction of TypeII structures, TypeIII structures
Gradually increase, variation occurs in product Mooney, product colour is gradually deepened.Therefore, must add in halogenated butyl rubber industrial products
Enter a small amount of stabilizer such as epoxidized soybean oil to inhibit isomerization speed of the secondary bit architecture to primary bit architecture, prevent product colour from adding
It is deep, ensure the stabilization of product quality.But epoxidized soybean oil is a kind of small molecule class organic compound, its introducing can be to product
Performance brings certain negative effect.First, epoxidized soybean oil can make the reduction of product Mooney；Secondly, epoxidized soybean oil is as one
The addition auxiliary agent of kind low molecular weight, easily migrates during storage.This aspect reduces its effect as stabilizer,
On the other hand to medicine plug, this application especially can't stand.Because the epoxidized soybean oil for moving to product surface may be dirty
Drug is contaminated, is even reacted with drug.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of halogenated butyl rubber and preparation method thereof,
Halogenated butyl rubber provided by the invention reduces the dosage of stabilizer so as to reduce migration of the stabilizer during storage,
And also slow down the rate of deterioration of halogenated butyl rubber.
The present invention provides a kind of halobutyl rubber compositions, including：
The carbonate or bicarbonate of the alkali metal of the weight % of 0.01 weight %~1.0 and the carbonate of alkaline-earth metal or
It is one or more in bicarbonate；
The stabilizer of the weight % of 0.1 weight %~3.0；
The auxiliary agent of the weight % of 0.11 weight %~5.0；
Surplus is halogenated butyl rubber；Halogen in the halogenated butyl rubber accounts for the halobutyl rubber compositions
The weight % of 0.5 weight %~3.0.
Preferably, in the carbonate or bicarbonate of the carbonate of the alkali metal or bicarbonate and alkaline-earth metal
It is one or more to be selected from calcium carbonate, sodium carbonate or sodium bicarbonate.
Preferably, the stabilizer is selected from epoxidation organic matter, and the epoxidation organic matter is selected from epoxidised soybean oil, castor
It is one or more in sesame oil, rubber seed oil, palm oil, cottonseed oil, rapeseed oil and corn oil.
Preferably, the auxiliary agent is one or more in dispersant and antioxidant, and the dosage of the dispersant is 0.1
The weight % of weight %~4.0, the dosage of the antioxidant are the weight % of 0.01 weight %~1.0.
Preferably, the dispersant is selected from stearic acid, oleic acid, polybasic carboxylic acid and its salt compounds；The antioxidant choosing
From one kind in amine antioxidants, hindered phenol anti-oxidants, phosphite antioxidant and sulphur-containing antioxidant or more
Kind.
Preferably, the halogen is selected from chlorine or bromine.
Preferably, the halogenated butyl rubber of the primary bit architecture comprising primary halogen atom in the halogenated butyl rubber with comprising
The molar ratio of the halogenated butyl rubber of the secondary bit architecture of secondary halogen atom is not higher than 1:4.
The present invention also provides a kind of preparation methods of above-mentioned halobutyl rubber compositions, include the following steps：
A) solution of butyl rubber is mixed to addition neutralization reagent after carrying out halogenation neutralize with halide reagent, be obtained
To halogenated butyl rubber solution；
B) halogenated butyl rubber solution and stabilizer, the carbonate of auxiliary agent and alkali metal or bicarbonate and alkaline-earth metal
Carbonate or bicarbonate in one or more mixing after, desolventizing obtains halogenated butyl rubber micelle/aqueous mixtures；
C) the halogenated butyl rubber micelle/aqueous mixtures are dried, obtain halogenated butyl rubber.
The present invention also provides a kind of preparation methods of above-mentioned halobutyl rubber compositions, include the following steps：
A) solution of butyl rubber is mixed to addition neutralization reagent after carrying out halogenation neutralize with halide reagent, be obtained
To halogenated butyl rubber solution；
B) after halogenated butyl rubber solution is mixed with auxiliary agent, desolventizing obtains halogenated butyl rubber micelle/aqueous mixtures；
C) by the halogenated butyl rubber micelle/aqueous mixtures and stabilizer, the carbonate of alkali metal or bicarbonate with
And it is dry after one or more mixing in the carbonate or bicarbonate of alkaline-earth metal, obtain halogenated butyl rubber.
Preferably, the butyl rubber is the copolymer of isobutene and isoprene, the isoprene monomer unit
Measure 0.5 mole of %~3.0 mole % of the total amount of all monomeric units based on the butyl rubber；The weight of the butyl rubber
Average molecular weight is 30 × 104~100 × 104。
Compared with prior art, the present invention provides a kind of halobutyl rubber compositions, including：0.01 weight %~
One kind or more in the carbonate or bicarbonate of the alkali metal of 1.0 weight % and the carbonate or bicarbonate of alkaline-earth metal
Kind；The stabilizer of the weight % of 0.1 weight %~3.0；The auxiliary agent of the weight % of 0.11 weight %~5.0；Surplus is halobutyl rubber
Glue；Halogen in the halogenated butyl rubber accounts for the weight % of 0.5 weight % of the halobutyl rubber compositions~3.0.This
Invention is by adding in the carbonate of a small amount of alkali metal or the carbonate or carbonic acid of bicarbonate and alkaline-earth metal into product
It is one or more in hydrogen salt, in the situation for the dosage for reducing traditional stabilizer (such as organic molecule epoxidized soybean oil)
Under, it can effectively inhibit isomerization of the secondary bit architecture to primary bit architecture in halogenated butyl rubber, slow down halogenated butyl rubber
Rate of deterioration.Simultaneously as reducing the content of small organic molecule epoxidized soybean oil, product is purer.
Description of the drawings
Fig. 1 is the preparation system schematic diagram of halobutyl rubber compositions provided by the invention.
Specific embodiment
The present invention provides a kind of halobutyl rubber compositions, including：
The carbonate or bicarbonate of the alkali metal of the weight % of 0.01 weight %~1.0 and the carbonate of alkaline-earth metal or
It is one or more in bicarbonate；
The stabilizer of the weight % of 0.1 weight %~3.0；
The auxiliary agent of the weight % of 0.11 weight %~5.0；
Surplus is halogenated butyl rubber；Halogen in the halogenated butyl rubber accounts for the halobutyl rubber compositions
The weight % of 0.5 weight %~3.0.
Halobutyl rubber compositions provided by the invention include the carbonic acid of the alkali metal of the weight % of 0.01 weight %~1.0
It is one or more in the carbonate or bicarbonate of salt or bicarbonate and alkaline-earth metal, preferably 0.05 weight %~
0.5 weight %.The alkali metal is selected from lithium, sodium or potassium；The alkaline-earth metal is selected from calcium or magnesium.The carbonate of the alkali metal or
It is one or more selected from calcium carbonate, sodium carbonate or bicarbonate in the carbonate or bicarbonate of bicarbonate and alkaline-earth metal
Sodium.One or more dosages in the carbonate or bicarbonate of alkali metal and the carbonate or bicarbonate of alkaline-earth metal
Very little, the effect of substitution stabilizer epoxidized soybean oil is not had；Too much, the ash content of product is influenced too big.
Halobutyl rubber compositions provided by the invention further include the stabilizer of the weight % of 0.1 weight %~3.0, preferably
For the weight % of 0.4 weight %~2.0.The stabilizer is most important to the performance of product.This is because halogenated butyl rubber knot
Halogen structure in structure is very unstable, under the action of heat, light and certain remaining metal ions, it is easy to elimination reaction occur
Hydrogen halides is obtained, and hydrogen halides can accelerate the elimination reaction of the halogen structure in halogenated butyl rubber structure.In order to avoid this
Product rapid deterioration caused by kind autoacceleration, it is necessary to remove the hydrogen halides generated by various factors at any time.It introduces and stablizes in product
The purpose of agent is exactly to eliminate hydrogen halides, to reduce the accumulation of hydrogen halides in product, the quality of stable prod.Certainly, stabilizer
It can select to add in drying process is post-processed.
Halobutyl rubber compositions provided by the invention further include the auxiliary agent of the weight % of 0.11 weight %~5.0.Wherein,
The auxiliary agent is one or more in dispersant and antioxidant, and the dosage of the dispersant is the weight of 0.1 weight %~4.0
Measure %, the weight % of preferably 0.5 weight %~3.5；The dosage of the antioxidant is the weight % of 0.01 weight %~1.0, preferably
For the weight % of 0.03 weight %~0.5.
The main function of dispersant is to prevent the mutual adhesion of rubber micelle in rubber micelle/water mixed system, caking, with
Facilitate the conveying of micelle/water material.Dispersant is selected from higher fatty acids and its salt compounds, preferably stearic acid, oleic acid, more
First carboxylic acid and its salt compounds.More preferably stearic acid, odium stearate, calcium stearate, zinc stearate, magnesium stearate, oleic acid,
Enuatrol, calcium oleate, zinc oleate, magnesium oleate, polybasic carboxylic acid sodium, polybasic carboxylic acid calcium, polybasic carboxylic acid zinc, polybasic carboxylic acid magnesium and its mixed
Close object, most preferably calcium stearate.
In the present invention, the antioxidant is selected from amine antioxidants, hindered phenol anti-oxidants, phosphorous acid esters antioxygen
It is one or more in agent and sulphur-containing antioxidant.
The amine antioxidants is selected from N- phenyl-1-naphthylamines (antioxidant A), N- phenyl-2-naphthylamines (antioxidant D), N,
N '-diphenyl is to aniline (antioxidant H), N- phenyl-N '-cyclohexyl p-phenylenediamine (antioxidant 4010), N, N '-two-betanaphthyl
P-phenylenediamine (antioxidant DNP) and ketoamine condensation product kind antioxidant, aldehyde-amine condensate kind antioxidant and its derivative or polymerization
Object.
The hindered phenol anti-oxidants be preferably 2,6- di-t-butyl -4- cresols (antioxidant Irgnox264), 2,2 ' -
Di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols) (antioxidant Irgnox2264), four [3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester (antioxidant Irgnox1010), (3,5- di-t-butyl -4- hydroxyls of 1,3,5- trimethyls -2,4,6- three
Base benzyl) benzene (antioxidant Irgnox1330), 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecane alcohol ester (antioxygen
Agent Irgnox1076) in it is one or more.
The phosphite antioxidant is selected from phosphorous acid three (2,4- di-tert-butyl-phenyls) phosphite ester
(Irgafos168), bis- [2- methyl -4,6- two (1,1 '-dimethyl ethyl) phenol] ethyl esters (Irgafos38), four
(2,4- di-tert-butyl-phenyls -4,4 '-xenyl) biphosphonate (IrgafosP-EPQ), four (eight alkoxy of 2,4- di-t-butyls -
4,4- xenyls) phosphate (MarkHP-10), bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites
(ADKStabPEP-36), (2,4,6- tri-tert phenyl -2- butyl -2- ethyls) -1,3- diol phosphites
(Ultranox641), two (bis- p-isopropyl phenyl of 2,4-) pentaerythritol bis-phosphites (DoverphosS-9228), 2,2 '-
Ethylenebis (4,6- di-tert-butyl-phenyls) fluorophosphite (Ethanox398), two [2,2 '-di-2-ethylhexylphosphine oxide of spiral shell ethylene glycol
(4,6- di-tert-butyl-phenyls)] it is one or more in phosphite ester (PhosphiteA).
The sulphur-containing antioxidant is selected from monothioester antioxidant, thiobisphenol antioxidant and thioether-type phenol antioxidants, such as
The double octadecyls of thio-2 acid pair lauryl alcohol ester (anti-oxidant DLTP, DLTDP), thio-2 acid (antioxidant DSTP,
DSTDP), 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate] (antioxidant 1035), 4,4 '-it is thio
It is one or more in bis- (6- tertiary butyls metacresol) (antioxidant 300s).
Present invention preferably uses hindered phenol anti-oxidants, more preferably antioxidant 1010, antioxidant 1076, antioxidant
1330。
It is mainly halogenated butyl rubber in halobutyl rubber compositions provided by the invention；The halogenated butyl rubber institute
The weight % of 0.5 weight % of total weight of the halogen quantity contained based on halogenated butyl rubber~3.0.The halogen is selected from chlorine or bromine.
The primary bit architecture comprising primary halogen atom in halogenated butyl rubber provided by the invention and the secondary bit architecture comprising secondary halogen atom
Molar ratio is not higher than 1:4, wherein following formula TypeII types and TypeIII types represents the halogen of the secondary bit architecture comprising secondary halogen atom respectively
Change the halogenated butyl rubber of butyl rubber and the primary bit architecture comprising primary halogen atom：
In formula, X represents halogen, preferably chlorine or bromine.
The present invention also provides a kind of preparation methods of above-mentioned halogenated butyl rubber, include the following steps：
A) solution of butyl rubber is mixed to addition neutralization reagent after carrying out halogenation neutralize with halide reagent, be obtained
To halogenated butyl rubber solution；
B) by the halogenated butyl rubber solution and stabilizer, the carbonate of auxiliary agent and alkali metal or bicarbonate and alkali
After one or more mixing in the carbonate or bicarbonate of earth metal, desolventizing obtains halogenated butyl rubber micelle/water and mixes
Close object；
C) the halogenated butyl rubber micelle/aqueous mixtures are dried, obtain halogenated butyl rubber.
The present invention also provides a kind of preparation methods of above-mentioned halogenated butyl rubber, include the following steps：
A) solution of butyl rubber is mixed to addition neutralization reagent after carrying out halogenation neutralize with halide reagent, be obtained
To halogenated butyl rubber solution；
B) after the halogenated butyl rubber solution is mixed with auxiliary agent, desolventizing obtains halogenated butyl rubber micelle/water and mixes
Close object；
C) by the halogenated butyl rubber micelle/aqueous mixtures and stabilizer, the carbonate of alkali metal or bicarbonate with
And it is dry after one or more mixing in the carbonate or bicarbonate of alkaline-earth metal, obtain halogenated butyl rubber.
In the present invention, the carbonate or bicarbonate of the carbonate of the alkali metal or bicarbonate and alkaline-earth metal
In one or more opportunitys that reaction system is added in stabilizer can with together with auxiliary agent before condensing field is entered together plus
Enter.In order to facilitate addition, carbonate or bicarbonate are preferably prepared into the suspension of water.
It can also be added in dryer group is post-processed.When selecting carbonate or during bicarbonate powder, can directly with
Sizing material enters dryer group together；When the water slurry for selecting carbonate or bicarbonate, it can select and shake by dehydration
The dynamic dewatered aqueous micelle of sieve enters dryer group together.
Due to calcium carbonate, solubility is minimum in water phase, no matter is added in this way in which position, can reduce calcium carbonate
Loss late.
In the present invention, the halogenation carries out at a temperature of not higher than 65 DEG C, preferably at 20 DEG C~60 DEG C into
Row.The halogenation time depends on institute's halogenation degree to be achieved, preferably 1~20 minute, more preferably 2~15 minutes, most
Preferably 3~6 minutes.
Basic glue butyl rubber before halogenation is selected from isobutene and a small amount of conjugated diene (isoprene or styrene list
Syntaxy object such as p-methylstyrene) it is copolymerized the copolymer formed.In the present invention, for isobutene and isoprene copolymer,
The total amount of all monomeric units based on butyl rubber, the content of isoprene monomer unit is usually 0.5 to rub in butyl rubber
You are %~3.0 mole %.
In the present invention, the molecular weight of basic glue butyl rubber is not particularly limited, as long as the butyl rubber energy
It enough carries out halogenation and introduces halogen atom.Preferably, the weight average molecular weight of basic glue butyl rubber is 30 × 104~
100×104。
In the present invention, basic glue butyl rubber both commercially available acquisitions, for example, in poly- rubber production Chambroad
IIR1953 can also be prepared by the known method of this field.
In order to which butyl rubber is carried out halogenation, usually by butyl rubber be dissolved in solvent in the form of butyl rubber solution with
Halide reagent is contacted.The principle that solvent is selected is not influence the halogenation of butyl rubber, nor affects on butyl rubber halogen
Change the structure of product.In this regard, the solvent for suitably forming the solution usually can be in alkane, cycloalkane, aromatic hydrocarbons and halogenated hydrocarbons
It is one or more.It is preferable to use nonpolar inertia alkane and cycloalkane, the more preferably alkane containing 5~15 carbon atoms
Or cycloalkane, such as pentane, hexane, isohexane, heptane, hexamethylene or its mixture etc..
As long as the concentration of butyl rubber solution can carry out halogenation.Preferably, based on the total of butyl rubber solution
Weight, the content of the butyl rubber in butyl rubber solution are the weight % of 5 weight %~30, the weight of preferably 8 weight %~25
Measure %.
In the present invention, the halide reagent is selected from mol-chloric, molecular bromine or mol-chloric is discharged under halogenation conditions, is divided
It is one or more in the compound of sub- bromine, preferably molecular bromine.
After halogenation completion, it is necessary first to neutralizer is added in into halogenated butyl rubber solution, to neutralize hydrogen
Hydrohalogenic acid byproducts obtain halogenated butyl rubber solution.
In the present invention, the neutralization reagent is neutralizing halogen acids by-product.In the present invention, it is any to be somebody's turn to do
The chemical reagent for neutralizing purpose can be used.Neutralization reagent is usually alkaline aqueous solution, and the alkaline aqueous solution is selected from following alkali
Property substance aqueous solution, the alkaline matter be selected from alkali metal hydroxide, ammonium hydroxide, alkali carbonate, alkali metal carbon
Sour hydrogen salt, it is one or more in ammonium carbonate and ammonium hydrogen carbonate.The alkali metal hydroxide is selected from sodium hydroxide and/or hydrogen-oxygen
Change potassium.
After obtaining halogenated butyl rubber, by the halogenated butyl rubber solution and the carbon of stabilizer, auxiliary agent and alkali metal
Mixture is obtained after one or more mixing in the carbonate or bicarbonate of hydrochlorate or bicarbonate and alkaline-earth metal.It will
The mixture desolventizing obtains halogenated butyl rubber micelle/aqueous mixtures.
In the present invention, the desolventizing is that the mixture is placed in condensing field, is contacted with high-temperature water and water vapour,
Solvent is removed, and halogenated butyl rubber forms micelle and is dispersed in the condensed water phase of water vapour, forms halogenated butyl rubber glue
Grain/aqueous mixtures.
Then the halogenated butyl rubber micelle/aqueous mixtures are dried, obtain halogenated butyl rubber.
Specifically, by halogenated butyl rubber micelle/aqueous mixtures by vibrating screen, most of water is removed, aqueous micelle
One group of dryer group is admitted to, the volatile ingredients such as remaining solvent and water in micelle is removed, obtains the halogenation of fugitive constituent qualification
Butyl rubber product.
When the carbonate or bicarbonate of the stabilizer and alkali metal and the carbonate or bicarbonate of alkaline-earth metal
In it is one or more when being added in post-processing dryer group, preparation method is specific as follows：
Halogenated butyl rubber solution is prepared first, and this will not be repeated here as described above for specific method.
Then, after the halogenated butyl rubber solution is mixed with auxiliary agent, mixture is obtained, by the mixture precipitation
Agent obtains halogenated butyl rubber micelle/aqueous mixtures.
In the present invention, the desolventizing is that the mixture is placed in condensing field, is contacted with high-temperature water and water vapour,
Solvent is removed, and halogenated butyl rubber forms micelle and is dispersed in the condensed water phase of water vapour, forms halogenated butyl rubber glue
Grain/aqueous mixtures.
Then, by the halogenated butyl rubber micelle/aqueous mixtures and stabilizer, the carbonate or bicarbonate of alkali metal
And mixture is obtained after one or more mixing in the carbonate or bicarbonate of alkaline-earth metal, the mixture is done
It is dry, obtain halogenated butyl rubber.
Specifically, by the mixture by vibrating screen, most of water is removed, and aqueous micelle is admitted to one group of drying machine
Group removes the volatile ingredients such as remaining solvent and water in micelle, obtains the halogenated butyl rubber product of fugitive constituent qualification.
The present invention also provides a kind of preparation systems of halobutyl rubber compositions, are carried referring to Fig. 1, Fig. 1 for the present invention
The preparation system schematic diagram of the halobutyl rubber compositions of confession.
Including：
Bromination reactor 1；
The neutralization reactor 2 that entrance is connected with the outlet of the bromination reactor；In bromination reactor outlet and institute
Setting neutralizes solution inlet between stating the pipeline that neutralization reactor entrance is connected；
The auxiliary agent mixer 3 that entrance is connected with the outlet of the neutralization reactor 2, in the outlet of the reactor 2 and institute
It states and offers auxiliary agent entrance a between the pipeline between the entrance of auxiliary agent mixer 3；
The condensing field 4 that entrance is connected with the outlet of the auxiliary agent mixer 3；
The micelle water surge tank 5 that entrance is connected with the outlet of the condensing field 4；
The dehydration and vibration sieve 6 that entrance is connected with the outlet of the micelle water surge tank 5；
The dryer group that entrance is connected with the outlet of dehydration and vibration sieve 6, the dryer group include what is be sequentially connected
Extruding-desiccation machine 7 squeezes out drying machine 8 and twin-screw drying machine 9.
Due to one in the carbonate or bicarbonate of the alkali metal and the carbonate or bicarbonate of alkaline-earth metal
Kind or a variety of opportunitys that reaction system is added in stabilizer can with added in together before condensing field is entered together with auxiliary agent.Cause
This, in the carbonate or bicarbonate of the alkali metal and the carbonate or bicarbonate of alkaline-earth metal it is one or more with
Stabilizer is added in from auxiliary agent entrance a or b.
It can also be added in dryer group is post-processed.When selection carbonate or bicarbonate powder or water slurry/
During aqueous solution, directly it can enter dryer group with sizing material；Therefore, it is necessary to de- with squeezing in the outlet of dehydration and vibration sieve 6
Pipeline enclosure that the entrance of water dispenser 7 is connected setting auxiliary agent entrance c, at this point, the carbonate or bicarbonate of the alkali metal and
One or more and stabilizer in the carbonate or bicarbonate of alkaline-earth metal is added in from auxiliary agent entrance c.
When the water slurry for selecting carbonate or bicarbonate, it can select and contain by dehydration and vibration sieve is dewatered
Glue grain enters dryer group together.Therefore, it is necessary to open up auxiliary agent entrance b on 4 top of condensing field.At this point, the alkali metal
One or more in the carbonate or bicarbonate of carbonate or bicarbonate and alkaline-earth metal enter with stabilizer from auxiliary agent
It is added in mouth b.
In the extruding-desiccation machine 7 and the pipeline enclosure setting auxiliary agent entrance d squeezed out between drying machine 8；
Pipeline enclosure setting auxiliary agent entrance e between the extrusion drying machine 8 and the twin-screw drying machine 9.
The carbonate or bicarbonate of the alkali metal and one kind in the carbonate or bicarbonate of alkaline-earth metal or
It is a variety of to be added in from auxiliary agent entrance c, auxiliary agent entrance d or auxiliary agent entrance e with stabilizer, wherein, the two can from it is same enter
It adds in, can also be added in from different entrances in mouthful.
The present invention is by adding in the carbonate of a small amount of alkali metal or the carbon of bicarbonate and alkaline-earth metal into product
It is one or more in hydrochlorate or bicarbonate, in the use for reducing traditional stabilizer (such as organic molecule epoxidized soybean oil)
In the case of amount, it can effectively inhibit isomerization of the secondary bit architecture to primary bit architecture in halogenated butyl rubber, slow down halogenation fourth
The rate of deterioration of base rubber.
For a further understanding of the present invention, with reference to embodiment to halogenated butyl rubber provided by the invention and its preparation
Method illustrates, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
A kind of preparation system of halobutyl rubber compositions is present embodiments provided, including：
Bromination reactor 1；
The neutralization reactor 2 that entrance is connected with the outlet of the bromination reactor；In bromination reactor outlet and institute
Setting neutralizes solution inlet between stating the pipeline that neutralization reactor entrance is connected；
The auxiliary agent mixer 3 that entrance is connected with the outlet of the neutralization reactor 2, in the outlet of the reactor 2 and institute
It states and offers auxiliary agent entrance a between the pipeline between the entrance of auxiliary agent mixer 3；
The condensing field 4 that entrance is connected with the outlet of the auxiliary agent mixer 3；
The micelle water surge tank 5 that entrance is connected with the outlet of the condensing field 4；
The dehydration and vibration sieve 6 that entrance is connected with the outlet of the micelle water surge tank 5；
The dryer group that entrance is connected with the outlet of dehydration and vibration sieve 6, the dryer group include what is be sequentially connected
Extruding-desiccation machine 7 squeezes out drying machine 8 and twin-screw drying machine 9.
The pipeline enclosure setting auxiliary agent entrance c that the outlet of the dehydration and vibration sieve 6 is connected with the entrance of extruding-desiccation machine 7.
4 top of condensing field opens up auxiliary agent entrance b.
In the extruding-desiccation machine 7 and the pipeline enclosure setting auxiliary agent entrance d squeezed out between drying machine 8；
Pipeline enclosure setting auxiliary agent entrance e between the extrusion drying machine 8 and the twin-screw drying machine 9.
By butyl rubber Chambroad1953 (125 DEG C of ML (1+8) is 52.1, degree of unsaturation 1.75mol%), dissolving
Butyl rubber hexane solution is obtained in n-hexane.Solution temperature is 55 DEG C, a concentration of 12.6 weight %.Butyl rubber solution
It is sent into bromination reactor 1 simultaneously with bromine, reaction time is 6min.Reaction after the completion of enter neutralization reactor 2, in and
NaOH aqueous solutions are added in reactor simultaneously, it is 5min to neutralize the residence time.Mixed material after neutralization is mixed into an auxiliary agent
Clutch 3 adds in antioxidant 1010 at a.Calcium stearate adds in glue condensed system at b, can also select to add at a and help
Agent mixer adds in simultaneously at a, b.
Mixed material after mixing is admitted to condensing field 4, removes the micelle water obtained after solvent, delays into micelle water
Rush tank 5.Subsequent micelle water is sent into post processing dryer group after the most of water of 6 removing of dehydration and vibration sieve.Dryer group
It is made of three machines, is respectively extruding-desiccation machine 7, extrusion drying machine 8, twin-screw drying machine 9 by flow sequence.After dehydration and drying
To brombutyl finished product.
Embodiment 2 (comparison)
Bromination reactor 1 is sent into the flow of 25.3t/h by the butyl rubber hexane solution obtained in embodiment 1, together
When bromine flow be 140kg/h.Enter neutralization reactor 2 after the completion of reaction, added in simultaneously in neutralization reactor a concentration of
The NaOH aqueous solutions of 1.0 weight %, flow 4000kg/h.Mixed material after neutralization enters an auxiliary agent mixer 3, from a
Place adds in calcium stearate, antioxidant 1010 and epoxidized soybean oil.The addition of calcium stearate is 54.2kg/h, the addition of antioxidant
Amount is 1.6kg/h, and the addition of epoxidized soybean oil is 41.4kg/h (1.3 weight % of brombutyl).After mixing
Mixed material be admitted to condensing field 4, the micelle water that micellar concentration is 5.2 weight % is obtained after removing solvent, into micelle water
Surge tank 5.Subsequent micelle water is sent into post processing dryer group after the most of water of 6 removing of dehydration and vibration sieve.Dehydration is dry
Brombutyl finished product is obtained after dry.The ageing properties data result of products obtained therefrom is shown in Table 2, and structured data the results are shown in Table 3.
Embodiment 3
Production technology is with embodiment 2, except that epoxidized soybean oil adds at d, addition is brombutyl
1.0 weight %.The calcium carbonate of 0.05 weight % of brombutyl is added at e simultaneously.The ageing properties of products obtained therefrom
Data result is shown in Table 2, and structured data the results are shown in Table 3.
Embodiment 4~6
Embodiment 3 is repeated, the difference lies in：Change the addition of epoxidized soybean oil and calcium carbonate, while coal addition position
At d, the specific data that add in are shown in Table 1.The ageing properties data result of products obtained therefrom is shown in Table 2, and structured data the results are shown in Table 3.
Embodiment 7
Embodiment 3 is repeated, the difference lies in：Change the addition of epoxidized soybean oil and calcium carbonate, while coal addition position
At a, the specific data that add in are shown in Table 1.The ageing properties data result of products obtained therefrom is shown in Table 2, and structured data the results are shown in Table 3.
Embodiment 8
Embodiment 3 is repeated, except that epoxidized soybean oil adds at e, addition is 0.6 weight of brombutyl
Measure %.The sodium carbonate for adding in 0.11 weight % of brombutyl at e simultaneously (is replaced the calcium carbonate in embodiment 3
For sodium carbonate).The ageing properties data result of products obtained therefrom is shown in Table 2, and structured data the results are shown in Table 3.
Embodiment 9
Embodiment 8 is repeated, except that sodium carbonate is changed to sodium bicarbonate.The ageing properties data knot of products obtained therefrom
Fruit is shown in Table 2, and structured data the results are shown in Table 3.
1 each embodiment promoter addition of table is had a guide look of
The relationship of 2 sample Mooney of table and ageing time
The structural parameters (Type III × 100/Type II) of 3 sample of table and the relationship of ageing time
* " TypeIII " represents the primary bit architecture for including primary halogen atom in halogenated butyl rubber, and " TypeII " represents halogenation
The secondary bit architecture for including secondary halogen atom in butyl rubber.
In terms of the result of table 2, the traditional stabilizer epoxy soybean of calcium carbonate or sodium carbonate, sodium bicarbonate partial alternative is used
After oil, gained brombutyl is after burin-in process, Mooney variation tendency and traditional bromination for only using epoxidized soybean oil
Butyl rubber product is consistent, and Mooney is all first to increase to reduce afterwards, and amplitude of variation is suitable.Only replacing ring completely with calcium carbonate
After oxygen soybean oil, increasing degree is slightly bigger than normal.
In terms of the result of table 3, the traditional stabilizer epoxy soybean of calcium carbonate or sodium carbonate, sodium bicarbonate partial alternative is used
After oil, gained brombutyl the variation tendency of microstructure and traditional only uses epoxidized soybean oil after burin-in process
Brombutyl product it is consistent, Type III/Type II ratios are increased with the extension of ageing time.But increase
Add amplitude suitable, only after with the complete substituted epoxy soybean oil of calcium carbonate, increasing degree is slightly bigger than normal.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of halobutyl rubber compositions, which is characterized in that including：
The carbonate of alkali metal or the carbonate or carbonic acid of bicarbonate and alkaline-earth metal of the weight % of 0.01 weight %~1.0
It is one or more in hydrogen salt；
The stabilizer of the weight % of 0.1 weight %~3.0；
The auxiliary agent of the weight % of 0.11 weight %~5.0；
Surplus is halogenated butyl rubber；Halogen in the halogenated butyl rubber accounts for the 0.5 of the halobutyl rubber compositions
The weight % of weight %~3.0.
2. halobutyl rubber compositions according to claim 1, which is characterized in that the carbonate or carbon of the alkali metal
It is one or more selected from calcium carbonate, sodium carbonate or bicarbonate in the carbonate or bicarbonate of sour hydrogen salt and alkaline-earth metal
Sodium.
3. halobutyl rubber compositions according to claim 1, which is characterized in that the stabilizer has selected from epoxidation
Machine object, the epoxidation organic matter be selected from epoxidised soybean oil, castor oil, rubber seed oil, palm oil, cottonseed oil, rapeseed oil and
It is one or more in corn oil.
4. halobutyl rubber compositions according to claim 1, which is characterized in that the auxiliary agent is selected from dispersant and resists
One or more in oxygen agent, the dosage of the dispersant is the weight % of 0.1 weight %~4.0, and the dosage of the antioxidant is
The weight % of 0.01 weight %~1.0.
5. halobutyl rubber compositions according to claim 4, which is characterized in that the dispersant be selected from stearic acid,
Oleic acid, polybasic carboxylic acid and its salt compounds；The antioxidant is selected from amine antioxidants, hindered phenol anti-oxidants, phosphorous
It is one or more in esters of gallic acid antioxidant and sulphur-containing antioxidant.
6. halobutyl rubber compositions according to claim 1, which is characterized in that the halogen is selected from chlorine or bromine.
7. halobutyl rubber compositions according to claim 1, which is characterized in that the packet in the halogenated butyl rubber
The halogenated butyl rubber of primary bit architecture containing primary halogen atom rubs with the halogenated butyl rubber of the secondary bit architecture comprising secondary halogen atom
You are than not higher than 1:4.
8. a kind of preparation method of halobutyl rubber compositions as described in claim 1~7 any one, feature exist
In including the following steps：
A) solution of butyl rubber is mixed to addition neutralization reagent after carrying out halogenation neutralize with halide reagent, obtain halogen
Change butyl rubber solution；
B) halogenated butyl rubber solution and stabilizer, the carbonate of auxiliary agent and alkali metal or the carbon of bicarbonate and alkaline-earth metal
After one or more mixing in hydrochlorate or bicarbonate, desolventizing obtains halogenated butyl rubber micelle/aqueous mixtures；
C) the halogenated butyl rubber micelle/aqueous mixtures are dried, obtain halogenated butyl rubber.
9. a kind of preparation method of halobutyl rubber compositions as described in claim 1~7 any one, feature exist
In including the following steps：
A) solution of butyl rubber is mixed to addition neutralization reagent after carrying out halogenation neutralize with halide reagent, obtain halogen
Change butyl rubber solution；
B) after halogenated butyl rubber solution is mixed with auxiliary agent, desolventizing obtains halogenated butyl rubber micelle/aqueous mixtures；
C) by the halogenated butyl rubber micelle/aqueous mixtures and stabilizer, the carbonate of alkali metal or bicarbonate and alkali
It is dry after one or more mixing in the carbonate or bicarbonate of earth metal, obtain halogenated butyl rubber.
10. preparation method according to claim 8 or claim 9, which is characterized in that the butyl rubber is isobutene and isoamyl two
The copolymer of alkene, the 0.5 of the total amount of all monomeric units of the amount based on the butyl rubber of the isoprene monomer unit
Mole %~3.0 mole %；The weight average molecular weight of the butyl rubber is 30 × 104~100 × 104。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110229254A (en) * | 2019-07-05 | 2019-09-13 | 黄河三角洲京博化工研究院有限公司 | A kind of bromination process and brombutyl of butyl rubber |
| CN110294812A (en) * | 2019-07-05 | 2019-10-01 | 黄河三角洲京博化工研究院有限公司 | A kind of chlorinated scoline and its preparation process |
| CN111875722A (en) * | 2020-08-31 | 2020-11-03 | 山东京博中聚新材料有限公司 | Preparation method of halogenated butyl rubber |
| CN113045833A (en) * | 2021-03-12 | 2021-06-29 | 山东京博中聚新材料有限公司 | Halogenated butyl rubber and preparation method thereof |
| CN114426743A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation of rubber assistant dispersion liquid and preparation method of brominated butyl rubber |
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| CN105218719A (en) * | 2014-06-16 | 2016-01-06 | 中国石油化工股份有限公司 | The method preparing halogenated butyl rubber and the halogenated butyl rubber obtained thus |
| CN105622821A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method of halogenated butyl rubber |
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| CN105218719A (en) * | 2014-06-16 | 2016-01-06 | 中国石油化工股份有限公司 | The method preparing halogenated butyl rubber and the halogenated butyl rubber obtained thus |
| CN105622821A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method of halogenated butyl rubber |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110229254A (en) * | 2019-07-05 | 2019-09-13 | 黄河三角洲京博化工研究院有限公司 | A kind of bromination process and brombutyl of butyl rubber |
| CN110294812A (en) * | 2019-07-05 | 2019-10-01 | 黄河三角洲京博化工研究院有限公司 | A kind of chlorinated scoline and its preparation process |
| CN110294812B (en) * | 2019-07-05 | 2022-04-22 | 黄河三角洲京博化工研究院有限公司 | Chlorinated butyl rubber and preparation process thereof |
| CN111875722A (en) * | 2020-08-31 | 2020-11-03 | 山东京博中聚新材料有限公司 | Preparation method of halogenated butyl rubber |
| CN114426743A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation of rubber assistant dispersion liquid and preparation method of brominated butyl rubber |
| CN114426743B (en) * | 2020-10-13 | 2023-08-15 | 中国石油化工股份有限公司 | Preparation of rubber auxiliary agent dispersion liquid and preparation method of brominated butyl rubber |
| CN113045833A (en) * | 2021-03-12 | 2021-06-29 | 山东京博中聚新材料有限公司 | Halogenated butyl rubber and preparation method thereof |
| CN113045833B (en) * | 2021-03-12 | 2023-01-31 | 山东京博中聚新材料有限公司 | Halogenated butyl rubber and preparation method thereof |
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Effective date of registration: 20190809 Address after: 256500 Boxing, Shandong Province Economic Development Zone, Beijing Bo Industrial Park Applicant after: Shandong Jingbo Zhongju New Materials Co., Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Applicant before: Shandong Jing Bo Petrochemical Co., Ltd. rubber branch |
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