CN102786618A - Preparation method for brominated and chlorinated butyl rubber - Google Patents

Preparation method for brominated and chlorinated butyl rubber Download PDF

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Publication number
CN102786618A
CN102786618A CN2012102556520A CN201210255652A CN102786618A CN 102786618 A CN102786618 A CN 102786618A CN 2012102556520 A CN2012102556520 A CN 2012102556520A CN 201210255652 A CN201210255652 A CN 201210255652A CN 102786618 A CN102786618 A CN 102786618A
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Prior art keywords
chlorobutyl
bromine
chlorination
preparation
butyl rubber
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袁荞龙
漆刚
刘青
刘峰
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East China University of Science and Technology
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7485—Systems, i.e. flow charts or diagrams; Plants with consecutive mixers, e.g. with premixing some of the components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/823—Temperature control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
    • B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/76—Venting, drying means; Degassing means
    • B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
    • B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
    • B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/18—Polymers of hydrocarbons having four or more carbon atoms, e.g. polymers of butylene, e.g. PB, i.e. polybutylene
    • B29K2023/22—Copolymers of isobutene, e.g. butyl rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers

Abstract

The invention relates to a preparation method for brominated and chlorinated butyl rubber. The preparation method comprises the following steps: carrying out solid phase chlorination on butyl rubber in a reactive extrusion device and finishing chlorination, neutralization and devolatilization of the butyl rubber in the process of reactive extrusion so as to obtain chlorinated butyl rubber; and then carrying out bromination on chlorinated butyl rubber by using a solution process so as to prepare the brominated and chlorinated butyl rubber. The method adopts the preparation process of chlorination at first and bromination next, providing a novel preparation technology for brominated and chlorinated butyl rubber, and the method has the advantages of high halogenation efficiency and controllable halogen content.

Description

A kind of preparation method of bromine Chlorobutyl
Technical field
The present invention relates to the preparation of halogenated polymer, the preparation method of the bromine Chlorobutyl that particularly a kind of content of halogen is controlled.
Background technology
Butyl rubber is widely used as the base mateiral of tire because of its excellent resistance to air loss.Butyl rubber after halogenation (chlorination or bromination), can improve greatly butyl rubber and tree elastomer and other unsaturated rubber the co-cure characteristic, cohere characteristic and thermotolerance; Can in non-sulfur cross-linking system, vulcanize, in radial and tubeless tyre and Medical bottle stopper, be applied.Brominated butyl rubber is superior to Chlorobutyl on processibility and cured properties, but the preparation condition of Chlorobutyl and production unit do not have brominated butyl rubber to require harshness, and the production cost of Chlorobutyl is relatively low.The controllability of Chlorobutyl work in-process is higher than brominated butyl rubber.Therefore; The advantages of Chlorobutyl and brominated butyl rubber is got up to prepare one type of new modified butyl rubber; Be the bromine Chlorobutyl, have the advantage of Chlorobutyl and brominated butyl rubber concurrently, introduce bromine in the butyl rubber halogenation and can reach content of halogen in the butyl rubber easily; Have excellent processing characteristics, can improve the thermostability of halogenated butyl rubber again.
Chinese patent 200510038032 discloses a kind of preparation method of Chlorobutyl, and dissolving, chlorination, neutralization, adding assistant through butyl rubber have made Chlorobutyl.This method has adopted traditional solution method prepared, has solvent recuperation energy consumption height and environmental protection problem.Chinese patent 200810059405 discloses a kind of working method of brominated butyl rubber; Butyl rubber is dissolved in forms glue in the solvent; Carry out bromination reaction then; Behind neutralization, water repetitive scrubbing, adding dispersion agent and antiheat agent, reclaim the solvent in the glue, obtain the brominated butyl rubber micelle.Chinese patent 200610109248 discloses a kind of method of making halogenated rubber like polymer; The halogenating reaction of rubber is in the dehumidification system of spiral and screw extruder reactor sealing, to produce the halogenated rubber like polymer product, the content of halogen may command through plasticizing, the degassing, softening, multistage halogenation, stable, devolatilization, discharging stripping and slicing.
English Patent 1483063 discloses the bromine chlorination method of polyhutadiene or divinyl and isoprene copolymer; Polymer dissolution is made into 5% solution in solvent, to have carried out prepared in reaction fire-retardant and the bromine chlorination polyhutadiene of thermally-stabilised excellence to splash into liquid bromine chloride.English Patent 1483064 discloses a kind of bromine chlorating method of TR 301; TR 301 is dissolved in is made into 5% TR 301 solution in the solvent; Splash into the bromine chloride solution reaction; Or chlorine and bromine feed the TR 301 solution reaction simultaneously, or the carbon tetrachloride solution that adds chlorine earlier imports the liquid bromine again, can prepare the bromine chlorination TR 301 with thermostability and flame retardant resistance.But all need in the above-mentioned patent polymkeric substance is carried out bromine chlorination again behind the chemical degradation earlier, and chemical degradation needs the above times in 2 weeks under the room temperature.Chinese patent 200910181102 provides a kind of method with multi-stage type twin screw extruder realization 1-polyolefin halogenation, provides a kind of and in the reaction extrusion device, has extruded the technology of preparing that obtains the bromine Chlorobutyl through butyl rubber and bromine chloride gas reaction.But this method is not bright specifically to the control of content of halogen in the bromine Chlorobutyl.The present invention realizes the controlled of content of halogen in the bromine Chlorobutyl on this basis.Butyl rubber is the multipolymer that iso-butylene and isoprene obtain through cationoid polymerisation, and wherein the massfraction of isoprene is 1～5%.Extrude the Chlorobutyl of the certain cl content of preparation through chlorination reaction, control isoprene chlorination degree, the chlorating isoprene segment can be not further and bromine reaction in the butyl rubber, generates the bromine Chlorobutyl through bromination reaction.
USP 4563506 discloses the technology of the continuous bromination of a kind of butyl rubber; And the various configurations of halogenated butyl rubber are discussed in detail; Carry out instrumental analysis for the structure of halogenated butyl rubber, especially use the structure of nuclear magnetic resonance technique (NMR) research halogenated butyl rubber that foundation is provided.Among the present invention the hydrogen nuclear magnetic resonance technology is adopted in the structure determination of bromine Chlorobutyl.
Measuring the method that cl content is commonly used in the polymkeric substance has: nmr analysis methods such as uv analysis method, elemental microanalysis method, oxygen bottle burning-NaOH volumetry, oxygen bottle burning-potentiometric titration, oxygen bottle burning-ion chromatography.During related bromine Chlorobutyl prepared among the present invention, the cl content of polymkeric substance and the mensuration of bromine content adopted oxygen bottle burning-volumetry.
Summary of the invention
The present invention provides a kind of preparation method of bromine chlorination fourth rubber, comprises the following steps: successively
(1) chlorination process
1. pre-treatment: in the feeding machine in the butyl rubber feeding twin screw extruder reactor assembly that drying is good, carry out softening in advance plasticizing.
2. chlorination reaction: the material that 1. step was handled gets into the conversion zone of twin screw extruder with the reinforced standard measure of hunger; Feed chlorine at conversion zone with the certain proportion nitrogen dilution; Control conversion zone temperature is at 90-120 ℃, simultaneously at an amount of stabilization aid of the terminal injection of conversion zone.Chlorine and butyl rubber thorough mixing in this reaction zone, uniform contact and the generation Chlorobutyl that reacts.Through cl content in the import volume may command Chlorobutyl of control chlorine, the massfraction of chlorine is 0.1-1.0% in the Chlorobutyl.
3. aftertreatment: Chlorobutyl gets into the devolatilization section of forcing machine after stablizing, and injects in the devolatilization section and helps the devolatilization agent, deviates from hydrogenchloride, nitrogen, a small amount of halogen and low boilers.Controlled temperature is discharged gas recovery at 100-130 ℃.Product carries out granulation after the terminal cooling of forcing machine.
(2) bromination process
1. dissolving: Chlorobutyl is put into the solvent dissolving make glue, the solubleness of Chlorobutyl in solvent is 5～20%.The used organic solvent of dissolving butyl rubber is normal hexane, hexanaphthene, chloroform, tetracol phenixin, 1, one or more mixed solvents in 2-ethylene dichloride and the 4-vinylchlorid.Solvent temperature is 25～45 ℃, and dissolution time is 8～12 hours.
2. bromination: the dilution of liquid bromine is dissolved in the solvent, joins bromination in the Chlorobutyl glue under the vigorous stirring fast, temperature of reaction is 60～90 ℃ in the bromination, and the reaction times is 3～10 minutes.Can realize of the regulation and control of the massfraction of bromine in the bromine Chlorobutyl through bromine liquid add-on in 0.1～1.0% scope.
3. neutralization: with glue after the bromination use massfraction be 2% dilute sodium hydroxide alkali lye to be neutralized to pH be 7.0～9.0, use deionized water wash to be neutrality to pH again, separate and remove water.
4. adding assistant makes product: in the glue that neutralizing treatment obtains, add dispersion agent and thermo-stabilizer.Stablizer is an epoxy soybean oil, and its consumption is 1～3% of a bromine Chlorobutyl glue massfraction.Dispersion agent is talcum powder or calcium stearate, and its consumption is 0.1～2% of a bromine Chlorobutyl glue massfraction.Bromine Chlorobutyl glue behind the adding auxiliary agent removes with rotary distillation and desolvates, and vacuum-drying gets bromine Chlorobutyl product.
Technology of the present invention can be operated, safety and stability, and halogenation efficient height and content of halogen are controlled, and the bromine Chlorobutyl can be used as a kind of novel halogenated butyl rubber and uses.
Description of drawings
Fig. 1 extrudes preparation 1-polyolefin halogenation process flow diagram for reaction, illustrates as follows:
1-solid polyolefin particles or fragment raw materials line 1, low-pressure nitrogen pipeline 2, the broken plasticizing of duplex feeding machine 3, sealing nitrogen 4, liquid raw material feed-pipe 5, liquid raw material jar 6; Reclaim hydrocarbon steam 60 and 61, gas exhauster 62, buffering separating tank 63, reactor drum plasticizing/mixing section 7 reclaims hydrocarbon steam 8, reactor drum degassing stages 9; The middle purity nitrogen pipeline 64 of pressing, high boiling point softening agent pipe 10, lower boiling tenderizer pipe 11 stirs homogenizing still 12, metered charge pump 13, the softening section 14 of reactor drum; Rare gas element 15, halogen gas 16, hybrid buffer 17, supercharger 18, preceding halogenation conversion zone 19; Regulator pipeline 20, liquid halogen pipeline 21 oozes and mixes still 22, metered charge pump 23, middle halogenating reaction section 24; Back halogenating reaction section 25, solvent line 26, stablizer 27, mixing kettle 28, metered charge pump 29; Reactor drum stable section 30 and 31, reactor drum devolatilization section 32,33 helps devolatilization agent pipe 34,35, dried hydrogen halide exhausting line 36, cooler condenser 37; Condensate drum 38 reclaims lower boiling property management 39, steam cooler 40,41, vacuum exhaust machine 42, reactor drum discharging metering zone 43; Product section (grain) machine 44, halogenation 1-polyolefin products 45, ultrasonic generator Us-46 and Us-47, temperature of reactor control point T-48～T-57, pressure monitor point P-58～P-59.
Embodiment
Below in conjunction with instance the present invention is described further, but protection scope of the present invention is not limited to the following example.
Instance 1
Present embodiment is used to prepare the equipment configuration synoptic diagram of Chlorobutyl and sees Figure of description.The primary device of butyl rubber chlorating is a reverse twin screw extruder group (reactor drum), screw diameter φ 36mm, and length-to-diameter ratio L/D=60 is except that the metering discharging section is that all the other each sections are non-engagement the engagement.Simplified is the sectional temperature control, and cold medium is 0 ℃ of white oil in the cylindrical shell, and urceolus heats with electric heating brasses heating jacket.The solid butyl rubber fragment of employing chopping or rectangular, its largest contours physical dimension or cross section＜20mm.Add the broken plasticizing machine of feeding machine-spiral hopper 3., weight is 6kg, and its specification is a degree of unsaturation 2%, the commercially available general butyl rubber of Mooney 34.Do not stop to feed the 0.01MPa pressure nitrogen gas in the hopper bottom, the about 0.2NM of flow rate 3/ h.The broken plasticizing machine of spiral temperature 3. is controlled at 50～80 ℃, tears and be squeezed into rubber to shreds porous softening not viscosity floss, sends into the downstream reaction system.On feeding-passage, contrary material direction feeds sealing nitrogen.In the plasticizing (mixing) of reactor drum section 7., the twin screw of staggered arrangement spiral shell shuttle band cutting mixing functions plastifies softening raw material, and feeds nitrogen and mixing of materials simultaneously, and the fluxing zone temperature can be controlled at about 90 ℃.Reacting 9. venting port of degassing stages, material is by step-down, and nitrogen entrapped air, moisture and possible unsaturated monomer or low boiling hydrocarbon are deflated the machine extraction, and control cushions the pressure and the middle pressure nitrogen amount of separating tank, and raw material reaches requirement after outgasing with assurance.Get into the softening section of reactor drum after the degassing in the hexanaphthene that stirs 0.2 times of rubber weight of homogenizing still
Figure BSA00000753245300042
adding and the naphthenic oil of 0.1 times of rubber weight; 0.01 the tenderizer of the adipic acid ester of rubber weight doubly; Three kinds of tenderizers are with preceding processing of all sloughing minor amount of water and oxygen, on average below 20ppm.The above-mentioned mixing tenderizer that is mixed in proportion after sparing adds softening section with the supercharging of metering charge pump, and the material temperature will be reduced to 60～70 ℃, and attach with the UW viscosity reduction.At reaction zone, with 0.1Kg chlorine purity nitrogen diluted mixture gas (1/10 being made into halogenating agent by volume), in 50%, 30%, 20% ratio; Halogenating reaction section before, during and after adding in due order; Reaction belongs to low exothermic process, easy temperature control, 50～70 ℃ of preceding halogenation temperature of reaction; 70～100 ℃ of middle halogenating reaction temperature, 90～130 ℃ of back halogenating reaction temperature.The halogenating reaction section has occupied screw extruder reactor 40% space, has guaranteed enough time of halogenating reaction and halogenating agent nearly 99% above utilization ratio.At two degassing stages, feed the purity nitrogen of rubber mass 5～10%, 120～130 ℃ of the first devolatilization mouth temperature, pressure 50KPa respectively.140～150 ℃ of the second devolatilization mouth temperature, pressure 20KPa.That gets rid of contains hydrogenchloride, nitrogen, a small amount of chlorine and low boiling point solvent, after water cooler, cooling, use the gas exhauster supercharging, again after condensing surface reclaims solvent, and pure dried hydrogen chloride gas recycling.
Slough the Chlorobutyl of by-product hydrogen halide; Through metering zone, the current stabilization cooling is boosted and is sent into out mouth template, is aided with ultrasonic viscosity reduction device; Lower the temperature through stripping and slicing of die face slitting shear machine and flash distillation at this; Obtain chloride massfraction and be 0.9% Chlorobutyl, product mooney viscosity 38 contains NO 4.3% (wt).
Instance 2
Adopt Chlorobutyl broken glue in mill of embodiment 1 preparation, be pressed into thin slice, be cut into the small-particle of 0.5cm * 0.5cm * 0.5cm.The dry good Chlorobutyl of 10 grams is put into the reaction kettle swelling that the 120mL normal hexane is housed, and stirring is fully dissolved it under the room temperature, forms glue after 12 hours.
0.3mL liquid bromine is diluted in an amount of normal hexane, rapidly it is added dropwise in the Chlorobutyl glue vigorous stirring under the dark condition.Control reaction temperature is cooled to room temperature at 68 ℃ of reaction times 5min then.The sodium hydroxide solution that adds rapidly massfraction 2% is regulated pH value to neutral, in use the deionized water thorough washing after 15 minutes, isolating oily liquid continuation is with behind the deionized water wash 3 times, separation obtains the glue of bromine Chlorobutyl.The adding massfraction is that the epoxy soybean oil and the massfraction of bromine Chlorobutyl glue 1.5% are the calcium stearate of bromine Chlorobutyl glue 0.9% under stirring.After fully stirring, remove through rotary distillation and to desolvate, after the vacuum-drying, in 100 ℃ mill, open refining 2min, remove moisture, obtain lurid bromine Chlorobutyl.The massfraction that uses oxygen bottle burning-volumetry to record chlorine in the bromine Chlorobutyl is 0.8%, and the massfraction of bromine is 0.4%.
Embodiment 3
Adopt Chlorobutyl broken glue in mill of embodiment 1 preparation, be pressed into thin slice, be cut into the small-particle of 0.5cm * 0.5cm * 0.5cm.The dry good Chlorobutyl of 10 grams is put into the reaction kettle swelling that the 120mL normal hexane is housed, and stirring is fully dissolved it under the room temperature, forms glue after 12 hours.
0.7mL liquid bromine is diluted in an amount of normal hexane, rapidly it is added dropwise in the Chlorobutyl glue vigorous stirring under the dark condition.Control reaction temperature is cooled to room temperature at 68 ℃ of reaction times 5min then.The sodium hydroxide solution that adds rapidly massfraction 2% is regulated pH value to neutral, in use the deionized water thorough washing after 15 minutes, isolating oily liquid continuation is with behind the deionized water wash 3 times, separation obtains the glue of bromine Chlorobutyl.The adding massfraction is that the epoxy soybean oil and the massfraction of bromine Chlorobutyl glue 1.5% are the calcium stearate of bromine Chlorobutyl glue 0.9% under stirring.After fully stirring, remove through rotary distillation and to desolvate, after the vacuum-drying, in 100 ℃ mill, open refining 2min, remove moisture, obtain lurid bromine Chlorobutyl.The massfraction that uses oxygen bottle burning-volumetry to record chlorine in the bromine Chlorobutyl is 0.8%, and the massfraction of bromine is 0.8%.
Bromination process in present method can also be amplified to industrial production, thereby becomes a kind of method of feasible industrial production bromine Chlorobutyl.
Embodiment 4
Adopt Chlorobutyl broken glue in mill of embodiment 1 preparation, be pressed into thin slice, be cut into the small-particle of 0.5cm * 0.5cm * 0.5cm.The dry good Chlorobutyl of 10 grams put into 120mL 1 is housed, swelling in the reaction kettle of 2-ethylene dichloride stirs under the room temperature it is fully dissolved, and forms glue after 12 hours.
0.6mL liquid bromine an amount of 1, is diluted in the 2-ethylene dichloride, rapidly it is added dropwise in the Chlorobutyl glue vigorous stirring under the dark condition.Control reaction temperature is cooled to room temperature at 80 ℃ of reaction times 5min then.The sodium hydroxide solution that adds rapidly massfraction 2% is regulated pH value to neutral, in use the deionized water thorough washing after 15 minutes, isolating oily liquid continuation is with behind the deionized water wash 3 times, separation obtains the glue of bromine Chlorobutyl.The adding massfraction is that the epoxy soybean oil and the massfraction of bromine Chlorobutyl glue 1.5% are the calcium stearate of bromine Chlorobutyl glue 0.9% under stirring.After fully stirring, remove through rotary distillation and to desolvate, after the vacuum-drying, in 100 ℃ mill, open refining 2min, remove moisture, obtain lurid bromine Chlorobutyl.The massfraction that uses oxygen bottle burning-volumetry to record chlorine in the bromine Chlorobutyl is 0.9%, and the massfraction of bromine is 0.8%.
Bromination process in present method can also be amplified to industrial production, thereby becomes a kind of method of feasible industrial production bromine Chlorobutyl.

Claims (10)

1. the preparation method of a bromine Chlorobutyl is characterized in that in the reaction extrusion device, realizing earlier the chlorination of butyl rubber, and Chlorobutyl is accomplished bromination process with solution method again, prepares the bromine Chlorobutyl through aftertreatment.
2. the preparation method of bromine chlorination fourth rubber according to claim 1, the solid-phase chlorination that it is characterized in that butyl rubber is plasticizing, the chlorination of gas-solid phase of in twin screw reaction extrusion device, carrying out butyl rubber, stablize devolatilization and extruding pelletization and obtain Chlorobutyl.
3. the preparation method of bromine chlorination fourth rubber according to claim 1, the bromination that it is characterized in that Chlorobutyl adds bromine in solution carries out, and the bromination certain hour can obtain the bromine Chlorobutyl of certain bromine content.
4. the preparation method of bromine chlorination fourth rubber according to claim 1 is characterized in that carrying out the butyl rubber chlorination in the extrusion device in reaction extrudes that the chlorine massfraction is 0.1-1.0% in the Chlorobutyl that obtains.
5. the preparation method of bromine chlorination fourth rubber according to claim 1; It is characterized in that Chlorobutyl accomplishes bromination with solution method; Be Chlorobutyl to be dissolved in earlier form solution in the organic solvent, the massfraction of Chlorobutyl in solution is 5～20%.
6. the preparation method of bromine chlorination fourth rubber according to claim 1, it is characterized in that Chlorobutyl splashes into the liquid bromine in solution after, bromination reaction under certain condition, the bromine massfraction is 0.1-1.0% in the bromine Chlorobutyl that obtains.
7. the preparation method of chlorination fourth rubber solutions according to claim 5; It is characterized in that dissolving the used organic solvent of butyl rubber is normal hexane, hexanaphthene, chloroform, tetracol phenixin, 1; One or more mixed solvents in 2-ethylene dichloride and the 4-vinylchlorid; Solvent temperature is 25～45 ℃, and dissolution time is 8～12 hours.
8. the preparation method of bromine chlorination fourth rubber according to claim 1; It is characterized in that Chlorobutyl accomplishes bromination process with solution method; The bromine drop is gone in the glue of Chlorobutyl, and temperature of reaction is 60～90 ℃ in the bromination, and the reaction times is 3～10 minutes.
9. the preparation method of bromine chlorination fourth rubber according to claim 1; After it is characterized in that Chlorobutyl is accomplished bromination with solution method; Aftertreatment be with in the sodium hydroxide solution with glue to pH be 7.0～9.0, use the deionized water wash glue to be neutrality to pH again, separate and remove water; Except that desolvating, vacuum-drying gets product with the glue rotary distillation.
10. the preparation method of bromine chlorination fourth rubber according to claim 1; After it is characterized in that Chlorobutyl is accomplished bromination with solution method; Before aftertreatment, in glue, add dispersion agent talcum powder or calcium stearate and thermo-stabilizer epoxy soybean oil; The consumption of dispersion agent is 0.1～2% of a glue massfraction, and the consumption of thermo-stabilizer is 1～3% of a glue massfraction.
CN2012102556520A 2012-07-23 2012-07-23 Preparation method for brominated and chlorinated butyl rubber Pending CN102786618A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN105111347A (en) * 2015-09-15 2015-12-02 黄河三角洲京博化工研究院有限公司 Producing method for brominating butyl rubber
CN105820281A (en) * 2015-01-09 2016-08-03 中国石油化工股份有限公司 Method for preparing halogenated polymer
CN111944076A (en) * 2020-09-04 2020-11-17 浙江信汇新材料股份有限公司 Water washing process of halogenated butyl rubber
CN112661878A (en) * 2020-12-17 2021-04-16 宁波普力通化学有限公司 High-activity synthetic rubber for single-coated rubber metal adhesive and preparation method thereof

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CN1903892A (en) * 2006-08-03 2007-01-31 江苏圣杰实业有限公司 Method of manufacturing halogenated rubber like polymer
CN101215351A (en) * 2008-01-17 2008-07-09 陈苏 Bromination reaction technique for butyl rubber

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CN1903892A (en) * 2006-08-03 2007-01-31 江苏圣杰实业有限公司 Method of manufacturing halogenated rubber like polymer
CN101215351A (en) * 2008-01-17 2008-07-09 陈苏 Bromination reaction technique for butyl rubber

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820281A (en) * 2015-01-09 2016-08-03 中国石油化工股份有限公司 Method for preparing halogenated polymer
CN105820281B (en) * 2015-01-09 2018-03-02 中国石油化工股份有限公司 A kind of preparation method of halogen polymer
CN105111347A (en) * 2015-09-15 2015-12-02 黄河三角洲京博化工研究院有限公司 Producing method for brominating butyl rubber
CN111944076A (en) * 2020-09-04 2020-11-17 浙江信汇新材料股份有限公司 Water washing process of halogenated butyl rubber
CN111944076B (en) * 2020-09-04 2022-08-12 浙江信汇新材料股份有限公司 Water washing process of halogenated butyl rubber
CN112661878A (en) * 2020-12-17 2021-04-16 宁波普力通化学有限公司 High-activity synthetic rubber for single-coated rubber metal adhesive and preparation method thereof

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Application publication date: 20121121