CN103724542B

CN103724542B - A kind of preparation method of dark SBR styrene butadiene rubbers

Info

Publication number: CN103724542B
Application number: CN201310690653.2A
Authority: CN
Inventors: 包春斌
Original assignee: HANGZHOU ZHECHEN RUBBER Co Ltd
Current assignee: HANGZHOU ZHECHEN RUBBER Co Ltd
Priority date: 2013-12-17
Filing date: 2013-12-17
Publication date: 2016-09-21
Anticipated expiration: 2033-12-17
Also published as: CN103724542A

Abstract

The present invention relates to the preparation method of a kind of rubber, particularly relate to the preparation method of a kind of dark styrene butadiene ribber.Sequentially include the following steps: blending butadiene and prepare → blend the preparation → polyreaction → unreacted monomer recovery → unreacted butadiene recovery → unreacted benzene ethylene recovery → dark color age resistor preparation → mother liquor → cohesion → washing → dehydration → dry → briquetting → face inspection → packaging of styrene preparation → soap lye preparation → activator preparation → oxygen scavenger preparation → terminator preparation → oxidant and regulator.The preparation method of a kind of dark styrene butadiene ribber, optimizes serviceability, and product suitability is high.

Description

A kind of preparation method of dark SBR styrene butadiene rubbers

Technical field

The present invention relates to the preparation method of a kind of rubber, particularly relate to the preparation method of a kind of dark SBR styrene butadiene rubbers.

Background technology

The production of SBR of emulsion polymerization starts from Germany, obtain and develop rapidly, be in the U.S., before World War II terminates, Germany and the U.S. all use Buna-S technology full-boiled process emulsion polymerization technique to produce butadiene-styrene rubber, after Great War terminates for the second time, the U.S., initially with cold process SBR of emulsion polymerization technique, uses redox initiation system as polymerization formula.The SBR of emulsion polymerization of other country then develops later, be all just realize after the 1950's industrial.Being polymerized from the full-boiled process of persulfate initiating system turns to the cold process of redox initiation system to be polymerized, and is the breakthrough producing emulsion polymerized styrene butadiene rubber polymerization technique.But some serviceability relative deficiency of product.

Summary of the invention

The present invention mainly solves the deficiencies in the prior art, there is provided a kind of cohesiveness and processing characteristics the most excellent, the preferable butadiene-styrene rubber of the anti-wear performance of vulcanizate, hot strength, tearing strength and ageing-resistant performance, to be widely used in white carbon black as reinforcing agent and product less demanding to color, such as the preparation method of a kind of dark SBR styrene butadiene rubbers of tire tread, tyre retreading tyre surface, conveyer belt, sebific duct, mechanograph and extruded article.

The above-mentioned technical problem of the present invention is mainly addressed by following technical proposals:

The preparation method of a kind of dark SBR styrene butadiene rubbers, sequentially includes the following steps:

(1), blend butadiene to prepare:

Fresh butadiene is stored in spherical tank, the storage pressure of spherical tank is≤0.36MPa, being controlled storage temperature by ammonia cold heat exchanger is≤18 DEG C, butadiene is blended with recovery butadiene preparation after alkali cleaning, the purity controlling to blend butadiene is 91.0%～97.0%, TBC content is≤10ppm, use to be polymerized；Reclaim purity >=78.0% of butadiene

During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.2～1.5 parts, mixed by pipeline, alkali liquor recycles；

Fresh butadiene refers to the butadiene used first；Reclaim butadiene to refer to through the butadiene that preparation recycling obtains.

(2), blend styrene to prepare:

Fresh benzene ethylene is stored in storage tank, ammonia cold heat exchanger control storage temperature≤18 DEG C, and fresh benzene ethylene blends styrene with reclaiming styrene preparation, and controlling to blend styrene purity is 91.0%～97.0%, use to be polymerized；

Reclaim cinnamic purity >=87.0%, TBC≤10ppm；

(3), soap lye preparation:

Soap lye is prepared in groove bucket, whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, in groove bucket, add condensed water that 522 parts of temperature are 90 DEG C, 22.77 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, the time of stirring is 0.5 hour, the fatty acid of 11 parts, the KCL of 4.09 parts and the diffusant of 1.29 parts is added after dissolving to Colophonium, being stirred for sample analysis after 0.5 hour, discharging treated by qualified rear surge tank of sending into；

(4), activator preparation:

Activator is prepared in groove bucket, and the desalted water adding 992 parts in groove bucket opens stirring, adds the EDETATE SODIUM ferrum of 1.4 parts and the rongalite of 6.3 parts is stirred sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into；

(5), oxygen scavenger preparation:

Oxygen scavenger is prepared in groove bucket, being passed through nitrogen in oxygen scavenger configuration forward slot bucket has stoped oxygen to enter, the desalted water adding 39 parts in groove bucket opens stirring, add 0.9 part of concentration and be the KOH solution of 48% and the oxygen scavenger of 5 parts is stirred sample analysis after 10 minutes, qualified after send into surge tank and treat discharging；

(6), terminator preparation:

Terminator is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter in terminator configuration forward slot bucket, and the desalted water adding 989 parts in groove bucket opens stirring, adds the terminator solution & stir of 9.2 parts sample analysis, the NaNO of qualified rear addition 2 parts after 10 minutes₂, send into surge tank after stirring 10 minutes and treat discharging；

(7), oxidant and the preparation of regulator:

Oxidant and regulator are stored in groove bucket, use nitrogen to maintain the pressure of 0.85MPa, by nitrogen pressure feeding；

(8), polyreaction:

SBR styrene butadiene rubbers polymerization employing emulsion polymerization at low temperature:

A, step (1) blend in butadiene 71.3 parts, step (2) and blend styrene 28.7 parts through static mixer on-line mixing, in desalted water with 180 parts, step (5) in oxygen scavenger 0.06 part, step (3) in soap lye 5.0 parts, step (7) regulator 0.15 part again after static mixer on-line mixing, it is cooled to 8～12 DEG C through ammonia cooler, add 0.015 part of activator in step (4), enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7)；

B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, be furnished with ammonia cold heat exchanger in each polymeric kettle controlling polymeric reaction temperature is 5～12 DEG C, being controlled polymerization reaction time by polymerization inventory and use polymeric kettle number is 8～11 hours, and reaction pressure controls 0.2～0.5MPa；

C, when polymerization reaches requirement conversion ratio 62～70%, and Mooney point reaches 46～56, add terminator 0.065 part in step (6) afterwards, complete polyreaction, formed solids content be 21.5～24.0% rubber cement deliver to unreacted monomer recovery unit；

(9), unreacted monomer reclaims:

Because polymerisation conversion is 62.0～70.0%, therefore product has 30.0～38.0% monomer do not participate in reaction, these monomers are reclaimed；Monomer refers to butadiene and styrene；

(10), unreacted butadiene reclaims:

The rubber cement that polyreaction produces enters pressure flash groove from still top, end, using steam and desalted water are configured to moist steam to control flash temperature is 35～42 DEG C, pressure 0.10～0.16MPa carries out butadiene flash distillation, the second pressure flash groove is entered through the rubber cement of primary flash distillation, controlling pressure 0.015～0.025MPa and carry out blood pressure lowering flash distillation, the butadiene flashed off enters compressor and is compressed；

A, in pressure flash groove rubber cement out sends into vacuum flashing groove, control pressure 0.015～0.025MPa and carry out vacuum flashing, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.25～0.35MPa, send into water cooler and be cooled to 30～38 DEG C, entering back into ammonia cooler and be cooled to 20～26 DEG C of condensations, butadiene fluid storage is sent in groove bucket and is reclaimed butadiene in memory element i.e. step (1)；

The butadiene that B, vacuum flashing groove flash off enters butadiene suction port of compressor after butadiene vacuum pump is forced into 0.015～0.025MPa and carries out step A.

In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, kerosene is used to absorb the butadiene carried secretly in on-condensible gas, kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve and controls pressure, discharge capacity 10～18m³/h；

(11), unreacted benzene ethylene recovery:

Latex after removing butadiene enters the first Styrene degassing tower top；

A, degassing desalted water and low-pressure steam are configured to moistening saturated vapor by the low entrance of tower, and latex contact through column plate with steam counter-flow, and abjection styrene vapor and water vapour are from tower top extraction；

B, entered by the first Styrene degassing tower tower reactor out latex second Styrene degassing tower repeat step A, latex storage tank delivered to by tower reactor out latex；

In C, step A, step B, tower top temperature controls at 55～65 DEG C, and pressure is-0.070～-0.090MPa；Temperature in tower reactor is 60～70 DEG C, and pressure is-0.060～-0.075MPa, and in tower, pressure is controlled by tower vacuum pump；

In D, step A, step B, styrene vapor and water vapour are through foam separator, the liquid trapped enters in the vacuum flashing groove in step (10-A), the water cooled but device of gas phase is cooled to 38～45 DEG C and enters back into ammonia cooler and be cooled to 32～26 DEG C, condenses out liquid and enters styrene through styrene Suction cop and strain and carry out the styrene separation with water in wash rice device；

In E, step D, gas enters tower vacuum pump after tower vacuum pump supercharging and seals water pot, after gas-liquid separation, the styrene separated is sent into styrene in step D and strains wash rice device, in gas feeding step (10-B) in butadiene vacuum pump；

Condensed fluid during styrene strains wash rice device in F, step D is after being continuously separated, and sewage delivers to sewage disposal through overflow launder, and styrene enters to send in styrene liquid storing tank bucket and reclaims styrene in memory element i.e. step (2)；Styrene liquid storing tank bucket is maintained pressure 0.0002MPa to deposit by nitrogen；

(12), latex entrance storage tank:

Removing styrene latex in step (11) and enter latex storage tank, for improving rubber color reduction finished product not Buddhist nun's viscosity degradation, groove bucket is maintained pressure 0.0002MPa to deposit by nitrogen；

(13), dark age resistor preparation:

A, by 18 parts of N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine and N-(1,4-dimethyl amyl group) the two mixture of-N '-diphenyl-para-phenylene diamine is transported to heating chamber and is heated up to 65.0～70.0 DEG C, confirms that it has mobility；Age resistor is dark age resistor；

B, in groove bucket, add soap lye in 7.82 parts of steps (3), beat slotted drum steam to heat, control flume barrel temperature is 60～65 DEG C, add 18 parts of mixture in step A, it is sufficiently stirred for 1 hour, mixing speed is 970r.p.m, and the desalted water adding 5.17 parts is stirred for 0.5 hour, analyze qualified after to send into surge tank to be used；

(14), mother liquor:

Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, the desalted water of 40 parts is added in collection surface bucket, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, using the temperature in automatic steam control collection surface is 65 DEG C, adds the flocculation aid of 0.025 part, and adding concentrated sulphuric acid control ph is 3.5～4.5, circulate 0.5 hour, form mother solution；

(15), cohesion:

37 parts of latex in step (12), 70 parts of mother solution in step (14), dark 0.33 part of age resistor in step (13), flocculation aid 0.025 part, enter after pipeline mixes and reduce pipe and accelerate into collection surface, temperature in collection surface is 60.0～70.0 DEG C, pH value is 3.8～4.5, stir 15 minutes, mixing speed is 101r.p.m, rear formation is loosened, porous, spongy rubber granule forms suspension with mother solution, suspension enters conversion tank from upper end discharging opening under stirring, the overflow of inverting groove top enters vibrosieve, micelle is made to separate with major part mother solution, Recycling Mother Solution re-uses；

(16), washing:

The micelle sent here from step (15) continuously enters sink, add in sink NaOH control ph be 5.0～6.5,40.0 parts of mother solution adding in step (14), after stir 10 minutes, mixing speed is 101r.p.m, entrance vibrosieve；

(17), dehydration:

Carry out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, control outlet micelle water content less than or equal to 15%, it is broken that micelle exports out entrance wet-milling from dewaterer, after rubber grain is crushed to 5～50mm indefinite form sizing materials, form wet sizing material, send into cyclone separator with feeding fan；

(18), it is dried:

A, wet sizing material in step (17) is by distributing device before gravity entrance drying baker, it is evenly distributed on drying baker carrier bar by the vibrating distributor being arranged on drying baker feed end, it is 80～150mm by adjust drying baker carrier bar pace controlling sizing material fabric thickness, wet micelle moves along with carrier bar, 6 districts of drying baker are passed sequentially through by the order in a district to 6th district, suck above the waste gas self-desiccation case cooling zone that cyclone separator is discharged, five are sequentially entered by circulating fan through air heater, four, three, 2nd district, first, by waste gas exhaust fan, humid air is evacuated to emission-control equipment above 2nd district；

A, each district control drying time be 30～60 minutes, the baking temperature in drying baker one district is 75～90 DEG C, the baking temperature in drying baker two district is 80～95 DEG C, the baking temperature in drying baker three district is 80～95 DEG C, the baking temperature in drying baker four district is 80～95 DEG C, the baking temperature in drying baker five district is 75～80 DEG C, 6th district adjust according to sizing material temperature, controls drying baker outlet sizing material temperature more than or equal to 45 DEG C with less than or equal to 60 DEG C；

C, sizing material less than 2.0%, are entered jigging conveyer to packaging unit by playing after disintegrating machine extremely conjunction material conveyer played by glue machine to drying baker afterbody water content；

(19), briquetting:

A, the sizing material sent here from step (18) fall to jigging conveyer and sizing material are delivered to powder device of weighing, sizing material is from the inclination sieve plate of tripper lower end, larger-size sizing material is separated, big sizing material is directly entered electronic scale weighing case and carries out thick feed, the tiny sizing material spilt through sieve aperture is fallen on oscillating feeder, send into electronic quantitative scale weight box by vibrating transportation, carry out essence feed；

B, when feed starts, top gate is opened, bottom hopper bottom door is closed, when weight reaches thick feed predetermined value 33.0Kg, feeding machine carries out thin feed, when weight reaches predetermined value 35.0Kg, and top closing gate, bottom hopper cuts out, and rubber grain is put into cuber by transition hopper and carried out briquetting process；After blowing terminates, bottom hopper cuts out, and top gate is opened and carried out new round weighing process, and weight 35.0Kg of weighing, precision is ± 0.175Kg, 180 pieces/h of speed of weighing；

C, charging enter cuber after weighing and carry out briquetting, press chamber a size of 700 × 350 × 190mm, form blob of viscose；

(20), face inspection:

From step (19) blob of viscose injection out, it is delivered to manual detection, surface abnormalities blob of viscose rejecting is processed, after manual detection, blob of viscose enters and rechecks scale, the blob of viscose being unsatisfactory for component requirement is rejected, blob of viscose carries out metal detection from rechecking scale entrance metal detector, and the internal blob of viscose containing metal is rejected；

(21), packaging:

Being sent into thin film packaging from the blob of viscose of metal detector discharging by track, blob of viscose uses the encapsulating of PE film, prevents blob of viscose from placing cause surface adhesion paper bag because of long-time, and after thin film encapsulation, blob of viscose is sent into man power encasement's outbound after paper bag packing, coding by track.

As preferably, in step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm；Purity >=99.3%；Dimer≤1000ppm；TBC content 50～150ppm；In step (2), fresh benzene ethylene technical specification: purity >=99.5%；TBC content 10～30ppm；In step (3), mixing speed is 105r.p.m；In step (5), the speed being passed through nitrogen is 2～4m³/h；In step (6), the speed being passed through nitrogen is 2～4m³/h；In step (13), N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine accounts for 38～42%, N-(1,4-dimethyl amyl group)-N '-diphenyl-para-phenylene diamine accounts for 58～62%.

Therefore, the preparation method of a kind of dark SBR styrene butadiene rubbers of the present invention, optimize serviceability, product suitability is high.

Detailed description of the invention

Below by embodiment, technical scheme is described in further detail.

Embodiment 1: the preparation method of a kind of dark SBR styrene butadiene rubbers, sequentially includes the following steps:

(1), blend butadiene to prepare:

Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger controlling storage temperature is≤18 DEG C, butadiene is blended with recovery butadiene preparation after alkali cleaning, the purity controlling to blend butadiene is 91.0%, and TBC content is≤10ppm, use to be polymerized；Reclaim purity >=78.0% of butadiene

During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.2 parts, mixed by pipeline, alkali liquor recycles；

(2), blend styrene to prepare:

Fresh benzene ethylene is stored in storage tank, ammonia cold heat exchanger control storage temperature≤18 DEG C, and fresh benzene ethylene blends styrene with reclaiming styrene preparation, and controlling to blend styrene purity is 91.0%, use to be polymerized；

Reclaim cinnamic purity >=87.0%, TBC≤10ppm；

(3), soap lye preparation:

(4), activator preparation:

(5), oxygen scavenger preparation:

(6), terminator preparation:

(7), oxidant and the preparation of regulator:

(8), polyreaction:

A, step (1) blend in butadiene 71.3 parts, step (2) and blend styrene 28.7 parts through static mixer on-line mixing, in desalted water with 180 parts, step (5) in oxygen scavenger 0.06 part, step (3) in soap lye 5.0 parts, step (7) regulator 0.15 part again after static mixer on-line mixing, it is cooled to 8 DEG C through ammonia cooler, add 0.015 part of activator in step (4), enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7)；

B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, be furnished with ammonia cold heat exchanger in each polymeric kettle controlling polymeric reaction temperature is 5 DEG C, being controlled polymerization reaction time by polymerization inventory and use polymeric kettle number is 8 hours, and reaction pressure controls at 0.2MPa；

C, when polymerization reaches requirement conversion ratio 62%, and Mooney point reaches 46, add terminator 0.065 part in step (6) afterwards, complete polyreaction, form the rubber cement that solids content is 21.5% and deliver to unreacted monomer recovery unit；

(9), unreacted monomer reclaims:

Because polymerisation conversion is 62.0%, therefore having 38.0% monomer not participate in reaction in product, these monomers are reclaimed；Monomer refers to butadiene and styrene；

(10), unreacted butadiene reclaims:

The rubber cement that polyreaction produces enters pressure flash groove from still top, end, using steam and desalted water are configured to moist steam to control flash temperature is 35 DEG C, pressure 0.10MPa carries out butadiene flash distillation, the second pressure flash groove is entered through the rubber cement of primary flash distillation, controlling pressure 0.015MPa and carry out blood pressure lowering flash distillation, the butadiene flashed off enters compressor and is compressed；

A, in pressure flash groove rubber cement out sends into vacuum flashing groove, control pressure 0.015MPa and carry out vacuum flashing, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.25MPa, send into water cooler and be cooled to 30 DEG C, entering back into ammonia cooler and be cooled to 20 DEG C of condensations, butadiene fluid storage is sent in groove bucket and is reclaimed butadiene in memory element i.e. step (1)；

The butadiene that B, vacuum flashing groove flash off enters butadiene suction port of compressor after butadiene vacuum pump is forced into 0.015MPa and carries out step A.

In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to absorb the butadiene carried secretly in on-condensible gas, and kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve and controls pressure, discharge capacity 10m³/h；

(11), unreacted benzene ethylene recovery:

Latex after removing butadiene enters the first Styrene degassing tower top；

In C, step A, step B, tower top temperature controls at 55 DEG C, and pressure is-0.070MPa；Temperature in tower reactor is 60 DEG C, and pressure is-0.060MPa, and in tower, pressure is controlled by tower vacuum pump；

In D, step A, step B, styrene vapor and water vapour are through foam separator, the liquid trapped enters in the vacuum flashing groove in step (10-A), the water cooled but device of gas phase is cooled to 38～45 DEG C and enters back into ammonia cooler and be cooled to 26 DEG C, condenses out liquid and enters styrene through styrene Suction cop and strain and carry out the styrene separation with water in wash rice device；

(12), latex entrance storage tank:

(13), dark age resistor preparation:

A, by 18 parts of N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine and N-(1,4-dimethyl amyl group) the two mixture of-N '-diphenyl-para-phenylene diamine is transported to heating chamber and is heated up to 65.0 DEG C, confirms that it has mobility；Age resistor is dark age resistor；

B, in groove bucket, add soap lye in 7.82 parts of steps (3), beat slotted drum steam to heat, control flume barrel temperature is 60 DEG C, add 18 parts of mixture in step A, it is sufficiently stirred for 1 hour, mixing speed is 970r.p.m, and the desalted water adding 5.17 parts is stirred for 0.5 hour, analyze qualified after to send into surge tank to be used；

(14), mother liquor:

Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, the desalted water of 40 parts is added in collection surface bucket, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, using the temperature in automatic steam control collection surface is 65 DEG C, adds the flocculation aid of 0.025 part, and adding concentrated sulphuric acid control ph is 3.5, circulate 0.5 hour, form mother solution；

(15), cohesion:

37 parts of latex in step (12), 70 parts of mother solution in step (14), dark 0.45 part of age resistor in step (13), flocculation aid 0.01 part, enter after pipeline mixes and reduce pipe and accelerate into collection surface, temperature in collection surface is 60.0 DEG C, pH value is 3.8, stir 15 minutes, mixing speed is 101r.p.m, rear formation is loosened, porous, spongy rubber granule forms suspension with mother solution, suspension enters conversion tank from upper end discharging opening under stirring, the overflow of inverting groove top enters vibrosieve, micelle is made to separate with major part mother solution, Recycling Mother Solution re-uses；

(16), washing:

The micelle sent here from step (15) continuously enters sink, add in sink NaOH control ph be 5.0,40.0 parts of mother solution adding in step (14), after stir 10 minutes, mixing speed is 101r.p.m, entrance vibrosieve；

(17), dehydration:

Carry out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, control outlet micelle water content less than or equal to 15%, it is broken that micelle exports out entrance wet-milling from dewaterer, after rubber grain is crushed to 5m indefinite form sizing material, form wet sizing material, send into cyclone separator with feeding fan；

(18), it is dried:

A, wet sizing material in step (17) is by distributing device before gravity entrance drying baker, it is evenly distributed on drying baker carrier bar by the vibrating distributor being arranged on drying baker feed end, it is 80mm by adjust drying baker carrier bar pace controlling sizing material fabric thickness, wet micelle moves along with carrier bar, 6 districts of drying baker are passed sequentially through by the order in a district to 6th district, suck above the waste gas self-desiccation case cooling zone that cyclone separator is discharged, five are sequentially entered by circulating fan through air heater, four, three, 2nd district, first, by waste gas exhaust fan, humid air is evacuated to emission-control equipment above 2nd district；

A, each district control drying time be 30 minutes, the baking temperature in drying baker one district is 75 DEG C, the baking temperature in drying baker two district is 80 DEG C, the baking temperature in drying baker three district is 80 DEG C, the baking temperature in drying baker four district is 80 DEG C, the baking temperature in drying baker five district is 75 DEG C, 6th district adjust according to sizing material temperature, controls drying baker outlet sizing material temperature more than or equal to 45 DEG C with less than or equal to 60 DEG C；

(19), briquetting:

(20), face inspection:

(21), packaging:

In step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm；Purity >=99.3%；Dimer≤1000ppm；TBC content 50ppm；In step (2), fresh benzene ethylene technical specification: purity >=99.5%；TBC content 10ppm；In step (3), mixing speed is 105r.p.m；In step (5), the speed being passed through nitrogen is 2m³/h；In step (6), the speed being passed through nitrogen is 2m³/h；In step (13), N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine accounts for 38%, N-(1,4-dimethyl amyl group)-N '-diphenyl-para-phenylene diamine accounts for 62%.

Embodiment 2: the preparation method of a kind of dark SBR styrene butadiene rubbers, sequentially includes the following steps:

(1), blend butadiene to prepare:

Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger controlling storage temperature is≤18 DEG C, butadiene is blended with recovery butadiene preparation after alkali cleaning, the purity controlling to blend butadiene is 95.0%, and TBC content is≤10ppm, use to be polymerized；Reclaim purity >=78.0% of butadiene

During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.4 parts, mixed by pipeline, alkali liquor recycles；

(2), blend styrene to prepare:

Fresh benzene ethylene is stored in storage tank, ammonia cold heat exchanger control storage temperature≤18 DEG C, and fresh benzene ethylene blends styrene with reclaiming styrene preparation, and controlling to blend styrene purity is 95.0%, use to be polymerized；

Reclaim cinnamic purity >=87.0%, TBC≤10ppm；

(3), soap lye preparation:

(4), activator preparation:

(5), oxygen scavenger preparation:

(6), terminator preparation:

(7), oxidant and the preparation of regulator:

(8), polyreaction:

A, step (1) blend in butadiene 71.3 parts, step (2) and blend styrene 28.7 parts through static mixer on-line mixing, in desalted water with 180 parts, step (5) in oxygen scavenger 0.06 part, step (3) in soap lye 5.0 parts, step (7) regulator 0.15 part again after static mixer on-line mixing, it is cooled to 10 DEG C through ammonia cooler, add 0.015 part of activator in step (4), enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7)；

B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, be furnished with ammonia cold heat exchanger in each polymeric kettle controlling polymeric reaction temperature is 8 DEG C, being controlled polymerization reaction time by polymerization inventory and use polymeric kettle number is 10 hours, and reaction pressure controls at 0.4MPa；

C, when polymerization reaches requirement conversion ratio 65%, and Mooney point reaches 50, add terminator 0.065 part in step (6) afterwards, complete polyreaction, form the rubber cement that solids content is 22.0% and deliver to unreacted monomer recovery unit；

(9), unreacted monomer reclaims:

Because polymerisation conversion is 65%, therefore having 35.0% monomer not participate in reaction in product, these monomers are reclaimed；Monomer refers to butadiene and styrene；

(10), unreacted butadiene reclaims:

The rubber cement that polyreaction produces enters pressure flash groove from still top, end, using steam and desalted water are configured to moist steam to control flash temperature is 40 DEG C, pressure 0.13MPa carries out butadiene flash distillation, the second pressure flash groove is entered through the rubber cement of primary flash distillation, controlling pressure 0.020MPa and carry out blood pressure lowering flash distillation, the butadiene flashed off enters compressor and is compressed；

A, in pressure flash groove rubber cement out sends into vacuum flashing groove, control pressure 0.020MPa and carry out vacuum flashing, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.30MPa, send into water cooler and be cooled to 30～38 DEG C, entering back into ammonia cooler and be cooled to 22 DEG C of condensations, butadiene fluid storage is sent in groove bucket and is reclaimed butadiene in memory element i.e. step (1)；

The butadiene that B, vacuum flashing groove flash off enters butadiene suction port of compressor after butadiene vacuum pump is forced into 0.020MPa and carries out step A.

In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to absorb the butadiene carried secretly in on-condensible gas, and kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve and controls pressure, discharge capacity 15m³/h；

(11), unreacted benzene ethylene recovery:

Latex after removing butadiene enters the first Styrene degassing tower top；

In C, step A, step B, tower top temperature controls at 60 DEG C, and pressure is-0.080MPa；Temperature in tower reactor is 65 DEG C, and pressure is-0.070MPa, and in tower, pressure is controlled by tower vacuum pump；

In D, step A, step B, styrene vapor and water vapour are through foam separator, the liquid trapped enters in the vacuum flashing groove in step (10-A), the water cooled but device of gas phase is cooled to 40 DEG C and enters back into ammonia cooler and be cooled to 30 DEG C, condenses out liquid and enters styrene through styrene Suction cop and strain and carry out the styrene separation with water in wash rice device；

(12), latex entrance storage tank:

(13), dark age resistor preparation:

A, by 18 parts of N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine and N-(1,4-dimethyl amyl group) the two mixture of-N '-diphenyl-para-phenylene diamine is transported to heating chamber and is heated up to 68.0 DEG C, confirms that it has mobility；Age resistor is dark age resistor；

B, in groove bucket, add soap lye in 7.82 parts of steps (3), beat slotted drum steam to heat, control flume barrel temperature is 62 DEG C, add 18 parts of mixture in step A, it is sufficiently stirred for 1 hour, mixing speed is 970r.p.m, and the desalted water adding 5.17 parts is stirred for 0.5 hour, analyze qualified after to send into surge tank to be used；

(14), mother liquor:

Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, the desalted water of 40 parts is added in collection surface bucket, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, using the temperature in automatic steam control collection surface is 65 DEG C, adds the flocculation aid of 0.025 part, and adding concentrated sulphuric acid control ph is 4.0, circulate 0.5 hour, form mother solution；

(15), cohesion:

37 parts of latex in step (12), 70 parts of mother solution in step (14), dark 0.33 part of age resistor in step (13), flocculation aid 0.025 part, enter after pipeline mixes and reduce pipe and accelerate into collection surface, temperature in collection surface is 65.0 DEG C, pH value is 4.0, stir 15 minutes, mixing speed is 101r.p.m, rear formation is loosened, porous, spongy rubber granule forms suspension with mother solution, suspension enters conversion tank from upper end discharging opening under stirring, the overflow of inverting groove top enters vibrosieve, micelle is made to separate with major part mother solution, Recycling Mother Solution re-uses；

(16), washing:

The micelle sent here from step (15) continuously enters sink, add in sink NaOH control ph be 6.0,40.0 parts of mother solution adding in step (13), after stir 10 minutes, mixing speed is 101r.p.m, entrance vibrosieve；

(17), dehydration:

Carry out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, control outlet micelle water content less than or equal to 15%, it is broken that micelle exports out entrance wet-milling from dewaterer, after rubber grain is crushed to 20mm indefinite form sizing material, form wet sizing material, send into cyclone separator with feeding fan；

(18), it is dried:

A, wet sizing material in step (17) is by distributing device before gravity entrance drying baker, it is evenly distributed on drying baker carrier bar by the vibrating distributor being arranged on drying baker feed end, it is 100mm by adjust drying baker carrier bar pace controlling sizing material fabric thickness, wet micelle moves along with carrier bar, 6 districts of drying baker are passed sequentially through by the order in a district to 6th district, suck above the waste gas self-desiccation case cooling zone that cyclone separator is discharged, five are sequentially entered by circulating fan through air heater, four, three, 2nd district, first, by waste gas exhaust fan, humid air is evacuated to emission-control equipment above 2nd district；

A, each district control drying time be 50 minutes, the baking temperature in drying baker one district is 80 DEG C, the baking temperature in drying baker two district is 85 DEG C, the baking temperature in drying baker three district is 90 DEG C, the baking temperature in drying baker four district is 90 DEG C, the baking temperature in drying baker five district is 77 DEG C, 6th district adjust according to sizing material temperature, controls drying baker outlet sizing material temperature more than or equal to 45 DEG C with less than or equal to 60 DEG C；

(19), briquetting:

(20), face inspection:

(21), packaging:

In step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm；Purity >=99.3%；Dimer≤1000ppm；TBC content 100ppm；In step (2), fresh benzene ethylene technical specification: purity >=99.5%；TBC content 20ppm；In step (3), mixing speed is 105r.p.m；In step (5), the speed being passed through nitrogen is 3m³/h；In step (6), the speed being passed through nitrogen is 3m³/h；In step (13), N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine accounts for 40%, N-(1,4-dimethyl amyl group)-N '-diphenyl-para-phenylene diamine accounts for 60%.

Embodiment 3: the preparation method of a kind of dark SBR styrene butadiene rubbers, sequentially includes the following steps:

(1), blend butadiene to prepare:

Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger controlling storage temperature is≤18 DEG C, butadiene is blended with recovery butadiene preparation after alkali cleaning, the purity controlling to blend butadiene is 97.0%, and TBC content is≤10ppm, use to be polymerized；Reclaim purity >=78.0% of butadiene

During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.5 parts, mixed by pipeline, alkali liquor recycles；

(2), blend styrene to prepare:

Fresh benzene ethylene is stored in storage tank, ammonia cold heat exchanger control storage temperature≤18 DEG C, and fresh benzene ethylene blends styrene with reclaiming styrene preparation, and controlling to blend styrene purity is 97.0%, use to be polymerized；

Reclaim cinnamic purity >=87.0%, TBC≤10ppm；

(3), soap lye preparation:

(4), activator preparation:

(5), oxygen scavenger preparation:

(6), terminator preparation:

(7), oxidant and the preparation of regulator:

(8), polyreaction:

A, step (1) blend in butadiene 71.3 parts, step (2) and blend styrene 28.7 parts through static mixer on-line mixing, in desalted water with 180 parts, step (5) in oxygen scavenger 0.06 part, step (3) in soap lye 5.0 parts, step (7) regulator 0.15 part again after static mixer on-line mixing, it is cooled to 12 DEG C through ammonia cooler, add 0.015 part of activator in step (4), enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7)；

B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, be furnished with ammonia cold heat exchanger in each polymeric kettle controlling polymeric reaction temperature is 12 DEG C, being controlled polymerization reaction time by polymerization inventory and use polymeric kettle number is 11 hours, and reaction pressure controls at 0.5MPa；

C, when polymerization reaches requirement conversion ratio 70%, and Mooney point reaches 56, add terminator 0.065 part in step (6) afterwards, complete polyreaction, form the rubber cement that solids content is 24.0% and deliver to unreacted monomer recovery unit；

(9), unreacted monomer reclaims:

Because polymerisation conversion is 70.0%, therefore having 30.0% monomer not participate in reaction in product, these monomers are reclaimed；Monomer refers to butadiene and styrene；

(10), unreacted butadiene reclaims:

The rubber cement that polyreaction produces enters pressure flash groove from still top, end, using steam and desalted water are configured to moist steam to control flash temperature is 42 DEG C, pressure 0.16MPa carries out butadiene flash distillation, the second pressure flash groove is entered through the rubber cement of primary flash distillation, controlling pressure 0.025MPa and carry out blood pressure lowering flash distillation, the butadiene flashed off enters compressor and is compressed；

A, in pressure flash groove rubber cement out sends into vacuum flashing groove, control pressure 0.025MPa and carry out vacuum flashing, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.35MPa, send into water cooler and be cooled to 38 DEG C, entering back into ammonia cooler and be cooled to 26 DEG C of condensations, butadiene fluid storage is sent in groove bucket and is reclaimed butadiene in memory element i.e. step (1)；

The butadiene that B, vacuum flashing groove flash off enters butadiene suction port of compressor after butadiene vacuum pump is forced into 0.025MPa and carries out step A.

In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to absorb the butadiene carried secretly in on-condensible gas, and kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve and controls pressure, discharge capacity 18m³/h；

(11), unreacted benzene ethylene recovery:

Latex after removing butadiene enters the first Styrene degassing tower top；

In C, step A, step B, tower top temperature controls at 65 DEG C, and pressure is-0.090MPa；Temperature in tower reactor is 70 DEG C, and pressure is-0.075MPa, and in tower, pressure is controlled by tower vacuum pump；

In D, step A, step B, styrene vapor and water vapour are through foam separator, the liquid trapped enters in the vacuum flashing groove in step (10-A), the water cooled but device of gas phase is cooled to 45 DEG C and enters back into ammonia cooler and be cooled to 26 DEG C, condenses out liquid and enters styrene through styrene Suction cop and strain and carry out the styrene separation with water in wash rice device；

(12), latex entrance storage tank:

(13), dark age resistor preparation:

A, by 18 parts of N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine and N-(1,4-dimethyl amyl group) the two mixture of-N '-diphenyl-para-phenylene diamine is transported to heating chamber and is heated up to 70.0 DEG C, confirms that it has mobility；Age resistor is dark age resistor；

B, in groove bucket, add soap lye in 7.82 parts of steps (3), beat slotted drum steam to heat, control flume barrel temperature is 65 DEG C, add 18 parts of mixture in step A, it is sufficiently stirred for 1 hour, mixing speed is 970r.p.m, and the desalted water adding 5.17 parts is stirred for 0.5 hour, analyze qualified after to send into surge tank to be used；

(14), mother liquor:

Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, the desalted water of 40 parts is added in collection surface bucket, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, using the temperature in automatic steam control collection surface is 65 DEG C, adds the flocculation aid of 0.025 part, and adding concentrated sulphuric acid control ph is 4.5, circulate 0.5 hour, form mother solution；

(15), cohesion:

37 parts of latex in step (12), 70 parts of mother solution in step (14), dark 0.33 part of age resistor in step (13), flocculation aid 0.025 part, enter after pipeline mixes and reduce pipe and accelerate into collection surface, temperature in collection surface is 70.0 DEG C, pH value is 4.5, stir 15 minutes, mixing speed is 101r.p.m, rear formation is loosened, porous, spongy rubber granule forms suspension with mother solution, suspension enters conversion tank from upper end discharging opening under stirring, the overflow of inverting groove top enters vibrosieve, micelle is made to separate with major part mother solution, Recycling Mother Solution re-uses；

(16), washing:

The micelle sent here from step (15) continuously enters sink, add in sink NaOH control ph be 6.5,40.0 parts of mother solution adding in step (14), after stir 10 minutes, mixing speed is 101r.p.m, entrance vibrosieve；

(17), dehydration:

Carry out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, control outlet micelle water content less than or equal to 15%, it is broken that micelle exports out entrance wet-milling from dewaterer, after rubber grain is crushed to 50mm indefinite form sizing material, form wet sizing material, send into cyclone separator with feeding fan；

(18), it is dried:

A, wet sizing material in step (17) is by distributing device before gravity entrance drying baker, it is evenly distributed on drying baker carrier bar by the vibrating distributor being arranged on drying baker feed end, it is 150mm by adjust drying baker carrier bar pace controlling sizing material fabric thickness, wet micelle moves along with carrier bar, 6 districts of drying baker are passed sequentially through by the order in a district to 6th district, suck above the waste gas self-desiccation case cooling zone that cyclone separator is discharged, five are sequentially entered by circulating fan through air heater, four, three, 2nd district, first, by waste gas exhaust fan, humid air is evacuated to emission-control equipment above 2nd district；

A, each district control drying time be 60 minutes, the baking temperature in drying baker one district is 90 DEG C, the baking temperature in drying baker two district is 95 DEG C, the baking temperature in drying baker three district is 95 DEG C, the baking temperature in drying baker four district is 95 DEG C, the baking temperature in drying baker five district is 80 DEG C, 6th district adjust according to sizing material temperature, controls drying baker outlet sizing material temperature more than or equal to 45 DEG C with less than or equal to 60 DEG C；

(19), briquetting:

(20), face inspection:

(21), packaging:

In step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm；Purity >=99.3%；Dimer≤1000ppm；TBC content 150ppm；In step (2), fresh benzene ethylene technical specification: purity >=99.5%；TBC content 30ppm；In step (3), mixing speed is 105r.p.m；In step (5), the speed being passed through nitrogen is 4m³/h；In step (6), the speed being passed through nitrogen is 4m³/h；In step (13), N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine accounts for 42%, N-(1,4-dimethyl amyl group)-N '-diphenyl-para-phenylene diamine accounts for 58%.

Claims

1. the preparation method of a dark SBR styrene butadiene rubbers, it is characterised in that sequentially include the following steps:

(1), blend butadiene to prepare:

Fresh butadiene technical specification: gas phase oxygen content≤2000ppm；Purity >=99.3%；Dimer≤1000ppm；TBC content 50～150ppm；

(2), blend styrene to prepare:

Reclaim cinnamic purity >=87.0%, TBC≤10ppm；

Fresh benzene ethylene technical specification: purity >=99.5%；TBC content 10～30ppm；

(3), soap lye preparation:

Soap lye is prepared in groove bucket, whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, in groove bucket, add condensed water that 522 parts of temperature are 90 DEG C, 22.77 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, the time of stirring is 0.5 hour, add after dissolving to Colophonium 11 parts fatty acid, 4.09 parts KCl and the diffusant of 1.29 parts, be stirred for sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into；

(4), activator preparation:

(5), oxygen scavenger preparation:

(6), terminator preparation:

(7), oxidant and the preparation of regulator:

(8), polyreaction:

(9), unreacted monomer reclaims:

(10), unreacted butadiene reclaims:

The butadiene that B, vacuum flashing groove flash off enters butadiene suction port of compressor after butadiene vacuum pump is forced into 0.015～0.025MPa and carries out step A；

(11), unreacted benzene ethylene recovery:

Latex after removing butadiene enters the first Styrene degassing tower top；

A, degassing desalted water and low-pressure steam be configured to moistening saturated vapor by Entering at the bottom of tower, latex contacts through column plate with steam counter-flow, and abjection styrene vapor and water vapour are drawn from tower top；

(12), latex entrance storage tank:

(13), dark age resistor preparation:

A, by 18 parts of N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine and N-(1,4-dimethyl amyl group) the two mixture of-N '-diphenyl-para-phenylene diamine is transported to heating chamber and is heated up to 65.0～70.0 DEG C, confirms that it has mobility；

(14), mother liquor:

Confirming that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, add the desalted water of 40 parts in collection surface bucket, desalted water sequentially enters collection surface, conversion tank , open stirring, ON cycle, 60 parts/h of circulating load, using the temperature in automatic steam control collection surface is 65 DEG C, adds the flocculation aid of 0.025 part, and adding concentrated sulphuric acid control ph is 3.5～4.5, circulates 0.5 hour, forms mother solution；

(15), cohesion:

(16), washing:

(17), dehydration:

(18), it is dried:

(19), briquetting:

(20), face inspection:

(21), packaging:

The preparation method of dark SBR styrene butadiene rubbers the most according to claim 1, it is characterised in that: in step (3), mixing speed is 105r.p.m；In step (5), the speed being passed through nitrogen is 2～4m³/h；In step (6), the speed being passed through nitrogen is 2～4m³/h；In step (13), N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine accounts for 38～42%, N-(1,4-dimethyl amyl group)-N '-diphenyl-para-phenylene diamine accounts for 58～62%.