CN101671412B

CN101671412B - 1-polyolefin halogenation production method

Info

Publication number: CN101671412B
Application number: CN2009101811027A
Authority: CN
Inventors: 刘青; 袁荞龙; 刘峰; 潘泳康; 葛瑞思
Original assignee: JIANGSU SHENGJIE INDUSTRY Co Ltd
Current assignee: JIANGSU SHENGJIE INDUSTRY Co Ltd
Priority date: 2009-10-10
Filing date: 2009-10-10
Publication date: 2011-08-17
Anticipated expiration: 2029-10-10
Also published as: CN101671412A

Abstract

The invention relates to a 1-polyolefin halogenation production method which is characterized in that continuous plastication (mixing), degasification, ultrasonic wave visbreaking, softening, multistage halogenation, neutralization and stabilization, devolatilization, ultrasonic wave temperature reduction and stripping and slicing measurement are realized in a sealing drying system in a double-screw extruder reactor to produce the halogenated polyolefin. Compared with the traditional process, the process flow is shortened by three fourth, which saves investment and energy power consumption; the halogen content of the halogenated polyolefin can be controlled, and does not contain corrosive acid gas, so that the equipment can not be corroded severely, is the modern green engineering, and can widely replace the process equipment of the current halogenated polyolefin.

Description

The 1-polyolefin halogenation production method

Technical field

The present invention relates to the halogenated polymer preparation field, particularly relate to the 1-polyolefin halogenation production method of a kind of non-environmental-pollution, energy-saving safe.

Background technology

Polyethylene, polypropylene, polyvinyl chloride, polystyrene four big general purpose materials have been widely used in every field at present, are closely related with human being's production and life, and its turnout and economy and social benefit are extremely huge.This four big class common name polyolefine material has its numerous separately advantages, but shortcoming is separately also arranged.Can improve the weak point of these materials by blend or modification by copolymerization or chemical modification, very can obtain some new performances, increase the kind of material, enlarge the range of application of material.

After the general polymerization thing halogenation modification, its halogenated polymer acid and alkali-resistance can be used as etch-proof coating and tackiness agent, also can be used for modified polyolefine material.For example the chlorinated polyethylene alkene plastics can improve the erosion-resisting characteristics of polyvinyl chloride, as the permanent plasticizer of rigid polyvinyl chloride and the flame-proof modifier of polyolefin resin; Chlorinated polyethylene rubber can be used as the insulating sheath material of electric wire.Chlorinated Polypropylene III is mainly used in tackiness agent, coating and the printing-ink of polypropylene material, and the polypropylene of high cl content also can be used as fire retardant or softening agent uses.Chlorinated polyphenyl ethene and brominated Polystyrene can be applicable to the fire retardant of thermoplastics.Brominated Polystyrene (BPS) is a kind of novel, addition type high molecular weight flame retardant, bromine content height, good heat resistance is arranged, to little, the anti-advantage such as separate out of resin shock-resistance influence, and low toxicity, environmental protection are the BPS biggest advantage.The second-order transition temperature of chlorinated polyvinyl chloride is higher than polyvinyl chloride, can do the hot water hard tube and make coating.

The existing production technique of the polyolefinic halogenide of 1-normally polymer dissolution is fed halogen in halon or halide reaction forms.Though this technology reaction evenly, produces controlled steady quality, it is the weak point of this mode of production and technology that the mass consumption of the production security that brings, resource and the energy and serious environmental are polluted.Non-environmental-pollution and resource-conserving production are requirement and the development trends that current green chemical industry is produced.Solid state reaction be a kind of energy-conservation, safely, economize on resources and the reaction of the Green Chemistry of non-environmental-pollution, research and extension solid state reaction engineering and technology and the economic and social benefit of using in specific product are remarkable.

Chlorinatedpolyethylene is that polyethylene and chlorine form by substitution reaction, is divided into elastomerics and plastic resin two classes according to cl content, has premium propertiess such as heat-resisting, weather-proof and anti-combustion.The chlorinatedpolyethylene suitability for industrialized production mainly is a solution method and water (acid) suspension method mutually, and suspension method is present industrial important method.GB882 524 adopts water phase suspension to prepare chlorinatedpolyethylene (CPE), 1 part of low pressure polyethylene powder that is of a size of 0.1 to 30 μ m or 30 to 300 μ m added in 3 to 30 parts the water, excessively feed high pressure chlorine continuously and carry out aqueous-phase suspending, can also add suitable emulsifying agent or catalyzer as required.Stop when being reflected at 100-110 ℃, resulting powdered product has certain degree of crystallinity and surpasses 70% cl content, also has unformed in addition in the product and elasticity chlorination part.

Chlorination by solid state method is exactly with powder polyethylene and various auxiliary agent is following in normal pressure and the method for chlorine direct reaction production CPE in reactor, and this method is generally carried out in fluidized-bed.Because reaction process is in drying regime, equipment corrosion is less, and products obtained therefrom is purer.But whether uniformly solid-phase chlorination certainly exists the crystalline region of product and non-crystalline region chlorination problem, and a series of problems that high temperature brought, because the solid phase method temperature is higher, the reaction heat radiation is very important.Germany Hirst company proposed liquid chlorine in 1974 and adds fluidized-bed, made the liquid chlorine evaporation to reach the purpose of heat radiation.Can obtain the CPE product of chloride 35-70% with this method.The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, delivers multistage chlorating patent, and chlorination temperature is divided into multistage control, is elevated to 130 ℃ gradually, and the product residual crystallinity is less than 2%.

Chlorinated Polypropylene III is to be made through chlorination reaction by polypropylene, divide high Chlorinated Polypropylene III (chlorination degree is 63-67%) and low Chlorinated Polypropylene III (chlorination degree is 20-40%), its good wear resistance, ageing resistance and performance such as acidproof make it have purposes widely at aspects such as coating, tackiness agent, printing ink vehicle and leather treatments.Chinese patent CN 101012295A discloses a kind of production method of producing Chlorinated Polypropylene III with the trichloromethane solvent method, can enhance productivity, and improves the chlorination effect, and the color of Chlorinated Polypropylene III product, stability, ageing-resistant performance are better.The water method is external at present main synthetic route, with polypropylene powder, catalyzer, tensio-active agent and the softening water of pulverizing, add in the chlorination tank by a certain percentage, stir down, polypropylene suspension liquid is heated to about 40-50 ℃, keeps this temperature to feed chlorine, stop logical chlorine after approximately reacting 2h, termination reaction obtains low chlorating Chlorinated Polypropylene III.Chlorination by solid state method is polypropylene powder to be carried out chlorination make Chlorinated Polypropylene III in the fluidized-bed still of stirring (or have), but it belongs to inhomogeneous reaction, and chlorination is inhomogeneous, and reaction heat is removed difficulty, easily coking, variable color and bonding.

Chlorinated polyvinyl chloride (CPVC) has superior performance such as high temperature resistant, anticorrosive and fire-retardant, is widely used in making various pipeline, valve, pipe fitting etc.Because have excellent chemical stability, resistance to acids and bases and water tolerance, can be used to make protective system, the CPVC resin that molecular weight is lower has solubility property preferably than polyvinyl chloride resin.Can be used for making supervinyi chloride resin lacquer and coating.The CPVC tackiness agent can be used for binding the tube fittings of various PVC, CPVC.Suspension method is adopted in the preparation of industrial CPVC usually, and aqueous suspension chlorination method and the sour method of suspension chlorination are mutually arranged.US5216088 has invented a kind of quick, manageable two step aqueous suspension chlorination methods, and this method operation is simpler, obtains the CPVC that cl content is 69-75%.Acid phase suspension chlorination method be with the powdered polyvinyl chloride in diluted hydrochloric acid medium, introduce chlorine gas to make reaction obtains product through postprocessing working procedures such as depickling, washing, neutralization, dryings again in the presence of auxiliary agent.

Brominated Polystyrene (BPS) is a kind of novel addition type high molecular weight flame retardant, good heat resistance, no blooming, do not move, anti-characteristics such as separate out.Low toxicity, environmental protection are the BPS biggest advantage, are the best substitute products of fire retardant Polybrominated biphenyl commonly used and Poly Brominated Diphenyl Ethers.Generally be used for thermostability engineering plastic, fire-retardant as PA, PET, PBT, syndiotactic polystyrene, poly terephthalic acid tetrahydrobenzene dimethylene ester etc. is applied in electric household appliance, chemical or grain containers.Brominated Polystyrene has two kinds of production methods of solvent method non-solvent method, and solvent method consumption bromine amount is few, good product quality, but power consumption and pollution problem are still main.Preparation of Brominated Polystyrene is polystyrene and bromizating agent (bromine or bromine chloride) reaction and getting under the lewis acidic catalysis in halohydrocarbon such as ethylene dichloride, and is disclosed as United States Patent (USP) 5532322.Though ethylene dichloride has acceptable boiling point, compare methyl chloride than environmental protection, but influence one of the principal element of the color of brominated Polystyrene product.United States Patent (USP) 5916978 has pointed out bromochloromethane to make solvent, Louis acid catalysis polystyrene bromination but can not bromizate polystyrene decolouring.United States Patent (USP) 6232408 discloses the method for preparing brominated Polystyrene in bromochloroethane, 1% weightless temperature of gained brominated Polystyrene reaches more than 340 ℃, bromide anion content is less than 2000ppm, and bromine total content at least 50% can be used as fire retardant and is applied to thermoplastics.But being still, these patented technologies follow wet method halogenation technology.

United States Patent (USP) 4,650,832 disclose a process that halogenated polymer is produced in serialization, and this process is by the continuous halogenated polymer of the reaction of polymkeric substance and halogenating agent in the forcing machine device that comprises intake zone (A), reaction zone (B), neutral zone (C).This device is halogenation unsaturated ethylene alkenyl polymer and saturated polymkeric substance such as polyisobutene continuously, ethylene propylene copolymer, high density polyethylene(HDPE), new LDPE (film grade), line style density polyethylene, ethylene-vinyl alcohol copolymer and polyvinyl chloride.Chinese patent CN1903892Y discloses in the spiro rod reaction forcing machine continuously, sequentially prepare method free from environmental pollution, the controllable halogenated rubber like polymer of content of halogen through plasticizing, the degassing, softening, multistage halogenation, stable, devolatilization, discharging stripping and slicing operation.

Along with social development claims to environment protection and resources conservation, existing polymkeric substance wet method halogenation production technique is on the verge of being replaced, and the new halogenated polymer preparation method and the research and development of technology are the task of top priority.The process that continuous preparation halogenated polymer is extruded in reaction is the requirement and the trend of social development now.

Summary of the invention

The objective of the invention is to overcome deficiency and the defective that above-mentioned prior art exists, be engaged in halogenated development research of polymkeric substance and production practice for many years through the contriver, exploitation provides a kind of Technology uniqueness, energy consumption is low, non-environmental-pollution, do not cause the production system corrosion, the production method of the 1-polyolefin halogenation that halogenation is controlled.

A kind of 1-polyolefin halogenation production method provided by the invention is characterized in that comprising the following steps:

1., pre-softening

In twin screw extruder reactor assembly (or claiming the twin screw extruder reactor), the 1-polyolefine is with in dry state or the hygrometric state feeding feeding machine, carry out softening in advance, hygrometric state feeding 1-polyolefine mass content is 50-95%, and other is that solvent, softening agent, lubricant or tenderizer are mixed into hygrometric state in feeding machine.Pre-softening temperature 60-100 ℃, tear up and be squeezed into softening thing of porous or hygrometric state pulpous state material;

2., the plasticizing degassing

Step softening thing or pulpous state material 1. entered twin screw extruder reactor plasticizing degassing stages and plastify the degassing, 50-120 ℃ of plasticizing degassing temperature, this system pressure 0.2-10MPa, take off wherein non-condensable gas, moisture, low boiling hydrocarbon and residual monomer, recycling makes that water and oxygen level are below 20ppm in the material of degassing back, and degassing back material is again through the ultrasonic wave viscosity reduction, hyperacoustic amplitude is 5-30 μ m, and frequency is 5-100KHz;

3. halogenating reaction

Step viscosity reduction 1-polyolefine material is 2. entered in the I-III conversion zone or I-IV conversion zone district in the twin screw extruder reactor with the reinforced standard measure of hunger, the auxiliary agent segmentation is controlled in each section of reaction zone, the halogenating agent consumption is 0.9-1.1 a times of 1-polyolefine theoretical amount, and the amount that each section adds halogenating agent is respectively to add 50%, 30% and 20% or 40%, 30%, 20% and 10% of halogenating agent total mass; It is 0-120 ℃ that the temperature of reaction of reacting each section is respectively the I section, the II section is 3-150 ℃, the temperature of reaction of III section is 5-180 ℃ or I section temperature of reaction 0-120 a ℃, II section temperature of reaction is 3-150 ℃, III section temperature of reaction is 5-180 ℃, 8-180 ℃ of IV temperature of reaction, conversion zone pressure is 0.2-10.0MPa, halogenating agent and 1-polyolefine thorough mixing uniform contact and the generation halogenation 1-polyolefine that reacts in this reaction zone.Described auxiliary agent is respectively a stablizer, and its consumption is the 0.05-5% of 1-polyolefine total mass, initiator, and it is the 0.05-1% of 1-polyolefine total mass with quality; Catalyst levels is the 0.05-1% of 1-polyolefine quality, and halogenating agent is 1 with the diluent volume ratio: 0.1-1: 10;

4. stable

Step halogenation 1-polyolefine is 3. entered twin screw extrusion reaction device stable section with stablizer, stablize, the consumption of stablizer is the 0.05-5% of 1-polyolefine quality;

5. devolatilization

Halogenation 1-polyolefine enters the devolatilization section after stable, add respectively in the devolatilization section and to help the devolatilization agent, helping devolatilization agent add-on is 1.20% of 1-polyolefine quality, 60-120 ℃ of first section devolatilization temperature, pressure 30-60KPa, second section devolatilization temperature is 80-150 ℃, and pressure is 20-40KPa, removes hydrogen halide, N ₂, a small amount of halogen and low boilers, discharge gas recycling respectively;

6. ultrasonic wave cooling major ingredient molding, granulating

Step 5. after the devolatilization material after the ultrasonic generator cooling, enter molding, granulating and become halogenation 1-polyolefine, wherein hyperacoustic amplitude is 5-30 μ m, frequency is 5-100KHz.

In 1-polyolefin halogenation production method provided by the invention, described 1-polyolefine is meant polyethylene such as high density polyethylene(HDPE), new LDPE (film grade) or LLDPE etc., polypropylene such as isotatic polypropylene, syndiotactic polypropylene or Atactic Polypropelene etc., the homopolymer of polyvinyl chloride, polystyrene, polyisobutene or multipolymer are as iso-butylene and isoprene copolymer.

Described halogenating agent is chlorine, liquid chlorine, SULPHURYL CHLORIDE, iodine monochloride, bromine chloride, bromine gas, liquid bromine, sodium hypobromite or sulfur bromide etc., and these halogenating agents can add with liquid state, also can be to feed in the reaction zone and 1-polyolefine mixing and contacting reaction with gaseous state.The polyolefinic halogenating reaction of halogenating agent and 1-mainly is to carry out in hydrogen atom mode on the halogenating agent alternate c atoms, and halogenating agent is excessive easily to cause side reaction-polymeric main splitting of chain, so the halogenating agent consumption is 0.9-1.1 times of the theoretical halogenation amount of 1-polyolefine.Halogenating agent is quantitatively multistage adding in the twin screw extruder reactor, halogenating reaction continuously, divide multistage to carry out, its remarkable advantage is the fierce degree of reduction initial stage halogenating reaction, make the reaction process homogenizing, reduce generally and now take place, thereby improved quality product with the common macromolecular main chain fracture side reaction of halogenation technology.For example three sections halogenations, the amount of each section adding halogenating agent is respectively and is metered into 50%, 30% and 20% of halogenating agent total mass; Four sections halogenations, the amount of each section adding halogenating agent is respectively and is metered into 40%, 30%, 20% and 10% of halogenating agent total mass.

1-polyolefin halogenation production method provided by the invention is to carry out continuously in the twin screw extruder reactor of logistics continuous flow sealing.Primary device twin screw extruder reactor comprises in a whole set of preparation polyolefinic device of halogenation 1-(seeing Figure of description): plasticizing degassing ultrasonic wave viscosity reduction intake zone, I-III section or I-IV section reaction zone, stable region, devolatilization district and ultrasonic wave viscosity reduction discharge zone.1-polyolefine raw material removes non-condensable gas, moisture, low boiling hydrocarbon and residual monomer wherein in feeding machine under certain temperature and pressure, the plasticizing degassing stages in the plasticizing degassing ultrasonic wave viscosity reduction district of feeding twin screw extruder reactor further outgases.After outgasing in the 1-polyolefine water and oxygen level below 20ppm, carry out ultrasonic viscosity reduction again, its hyperacoustic amplitude is 5-30 μ m, frequency is 5-100KHz, and the 1-polyolefine enters in reaction zone I-III or the I-IV section segmentation and mixes mutually, contacts with halogenating agent and auxiliary agent and react and generate halogenation 1-polyolefine then.Product continues to enter next section and stablizes the homogenize district, this district enters the devolatilization district after can injecting a certain amount of rare gas element and/or reactive gas and halogenation 1-polyolefine again, the by product and the unreacted halogenating agent that separate halogenating reaction remove hydrogen halide, nitrogen, a small amount of halogenating agent and low boilers.At last, product discharging after ultrasonic wave produces homogenize, cooling, its hyperacoustic amplitude is 5-30 μ m, frequency is 5-100KHz, prepares halogenation 1-polyolefine.

The 1-polyolefine adds the twin screw extruder reactor via feeding machine such as the broken plasticizing of duplex feeding machine with the reinforced standard measure of hunger.The 1-polyolefine can dry state quantitatively enter the twin screw extruder reactor after feeding machine tentatively plastifies, also can quantitatively add the polyolefinic solvent of 1-, softening agent, lubricant or tenderizer in feeding machine, after mixing, be metered in the twin screw extruder reactor with hygrometric state by the liquid raw material supply system.Hygrometric state 1-polyolefine is pulpous state, and the polyolefinic quality percentage composition of 1-is 50-95%.The 1-polyolefine quantitatively adds the twin screw extruder reactor by the duplex feeding machine and adopts " hungry reinforced method ", be the speed that the quantitative speed that feeds of feeding machine is lower than twin screw extruder reactor convey materials, so that the 1-polyolefine reacts with the halogenating agent hair tonic under the non-state that is full of in reaction zone.

The effect of described tenderizer is to reduce the polyolefinic viscosity of 1-, can better mix contacting with halogenating agent, and it is overheated can not produce, and does not also have the danger of molecular breakdown and side reaction; Also can reduce polymer temperature in addition.Described tenderizer is the saturated hydrocarbon of volatilizable recovery, also can be other compound that is retained in the polymkeric substance.Hydrocarbon oils for example is as C ₆-C ₈Raffinate oil, industrial hexane, hexanaphthene, heptane, industrial naptha, paraffin oil, naphthenic oil, toluene; Halon oils is as bromochloromethane, bromochloroethane, ethylene dichloride; Ester compound such as sebate, adipic acid ester, azelate, phosphoric acid ester; Waxy compound such as low molecular weight polyethylene wax, paraffin, microcrystalline wax, blended wax, stearamide wax; Or the salt of stearic acid and calcium thereof, potassium, zinc.The tenderizer add-on is the 1-50% of polymer weight, and with raw material 1-polyolefine characteristic and different selection and the couplings of carrying out different softening types of molecular weight thereof, to satisfy the halogenating reaction requirement.C for example ₆-C ₈Raffinate oil, industrial hexane, hexanaphthene, heptane or industrial naptha (title low boilers) add-on be the 10-50% of polymer weight.Paraffin oil, naphthenic oil or toluene (title high boiling product) are the 10-30% of polymer weight.Bromochloromethane, bromochloroethane or ethylene dichloride are the 10-40% of polymer weight.Sebate, adipic acid ester, azelate or phosphoric acid ester consumption are the 5-10% of polymer weight.Paraffin, Microcrystalline Wax, blended wax or stearamide wax, consumption are the 5-20% of polymer weight.Low molecular weight polyethylene wax (relative molecular weight 1000-8000), consumption is the 3-5% of polymer weight.Stearic acid and its esters, consumption are the 1-5% of polymer weight.These tenderizers can use separately, also can compoundly use (any ratio), and preferably composite (any ratio) used, and purpose is to reduce the total consumption of tenderizer under the processing condition satisfying as far as possible.The usage quantity of composite softening agent is generally the 10-50% of 1-polyolefine quality, but in this process the consumption of supplementing solvent, softening agent, lubricant also.

Water is all influential to the side reaction and the equipment protection of the reaction of 1-polyolefin halogenation.1-polyolefine feed system and screw extruder reactor degassing stages can be reduced to water content minimum, thereby guarantee the protection against corrosion of polyolefinic halogenating reaction of 1-and equipment.

The characteristics of 1-polyolefin halogenation of the present invention reaction be in the twin screw extruder reactor continuously and multistage finish halogenating reaction, the polyolefinic halogenating reaction of 1-belongs to free radical mechanism, uses superoxide or azo-initiator initiation reaction always.Hydrogen (the CH of methylene radical in the common 1-polyolefine macromolecular chain ₂-) captured by free radical and to form new free radical behind the hydrogen atom, form halogenated (CHCI-) polymkeric substance with halogenating agent reaction back again.So halogenating reaction is the reaction zone at the twin screw extruder reactor quantitatively to be injected halogenating agent through multistage and carry out, carry out in preferred three sections or four sections.Halogenating agent consumption and flow are little in every section, generally are the 10-40% of halogenating agent stoichiometric amount total mass.The halogenating reaction of 1-polyolefine in the twin screw extruder reactor is to be continuously, again that the branch multistage carries out, its remarkable advantage is the fierce degree of reduction initial stage halogenating reaction, make the reaction process homogenizing, reduce generally and now take place, thereby improved quality product with the common macromolecular main chain fracture side reaction of halogenation technology.For example three sections halogenations, the amount of each section adding halogenating agent is respectively and is metered into 50%, 30% and 20% of halogenating agent total mass; Four sections halogenations, the amount of each section adding halogenating agent is respectively and is metered into 40%, 30%, 20% and 10% of halogenating agent total mass.For improving Measuring Precision and eliminating the too high reaction non-uniform phenomenon of partial concn, mixed the gas phase thinner in the halogenating agent.Thinner commonly used is rare gas element and/or reactive gas (can any ratio), regulates halogenating reaction under the halogenation condition, and does not liquefy under respective reaction pressure.Described diluent for gases is nitrogen, argon gas, methane, ethane, propane, carbonic acid gas, sulfurous gas, dry air or ammonia.Halogenating agent and diluent gas volume ratio are 1: 0.1-10, can select according to reinforced condition.Reinforced position, the ratio of different halogenating agents can change, in the hope of the steadily equilibrium of halogenating reaction.Rare gas element also plays halogenating agent security of system covering effect.

1-polyolefin halogenation reaction of the present invention is that the reaction zone contiguous segmentation carries out in the twin screw extruder reactor, each section temperature of reaction may command.The twin screw extruder reactor shell has two kinds of functions of heating and cooling, is equipped with special screw rod geometrical shape and size, just can realize segmentation control reaction temperature on demand.The 1-polyolefine is 50-120 ℃ at twin screw extruder reactor fluxing zone plasticization temperature, the temperature of reaction of halogenating reaction section I is 0-120 ℃, the temperature of reaction of halogenating reaction section II (C) is 3-150 ℃, the temperature of reaction of halogenating reaction section III (D) is that IV section temperature of reaction is 8-180 ℃ in 5-180 ℃ or the I-IV section, and this system response pressure is 0.2-10.0MPa.

Above-mentioned each section temperature can be selected within the specific limits according to institute's polyolefinic difference of halogenation 1-.But each section halogenating reaction section utilizes twin screw extruder reactor used in the present invention to have the characteristics of anti-more high pressure to the heterogeneous reaction pressurize, can carry out pressure according to different halogenation objects under 0.2-10.0MPa and regulate.

After the halogenation in the twin screw extruder reactor of 1-polyolefine, the stable and devolatilization, the halogenation extent control within the specific limits.For example the massfraction of chlorine is 5-70% in the chlorination 1-polyolefine; The massfraction of the bromine in the bromination 1-polyolefine is 0.1-70%; The massfraction of bromine is 0.1-70% in the bromine chlorination 1-polyolefine, and the massfraction of chlorine is 5-60%.

Can be the single screw extrusion machine reactor assembly with the twin screw extruder reactor assembly in the 1-polyolefin halogenation production method provided by the invention, can be the twin screw extruder reactor assembly also, is preferably the twin screw extruder reactor assembly.The twin screw extruder reactor that is used for the reaction of 1-polyolefin halogenation has engagement type parallel dual-screw extrusion reaction device, non-engagement/engagement reverse twin screw extrusion reaction device and self-cleaning type double-screw reactor.

The feeding machine of charging system of the present invention also is a twin screw extruder.Above-mentioned twin screw extruder reactor is formed by fixed outer cylinder body and turning axle two portions.Outer cylinder body has cold medium channel and thermal medium chuck, all uses hot and cold medium temperature control.Cylindrical shell is provided with function apertures such as charging, exhaust, thermometric, pressure measurement and sampling according to the needs of halogenating reaction, is provided with supersonic range simultaneously.

Continuous flow twin screw extruder reactor assembly of the present invention can make the 1-polyolefine in the reactor internal strain, destroys polymer surfaces, continues to produce new polymer surfaces, thereby unreacted polymkeric substance is exposed to halogenating agent.As twin screw extruder reactor inner barrel radially the arranging of pin, reversed flow, multipaths screw portion, a series of weak points alternately oppositely and forward screw portion, interrupt the flow process groove of screw portion, these are provided with enough generation deformable polymers, make the unnecessary high shearing force in the new surface that is exposed to halogenating agent, thereby reduce side reaction.Simultaneously, this device also is beneficial to the mixing contact of polymkeric substance and halogenating agent and separates.Be used for twin screw extruder reactor of the present invention, the diameter of described engagement type parallel dual-screw extruding machine reactor is 20-250mm, and length-to-diameter ratio L/D is 25-45, and 50-500 rev/min of rotating speed of axle can speed governing; The diameter of the reverse twin screw extruder reactor of non-engagement is 25-300mm, and length-to-diameter ratio L/D is 40-100,30-500 rev/min of axle rotating speed; The diameter of self-cleaning type twin screw extruder reactor is 50-1000mm, and length-to-diameter ratio is 5-10,10-100 rev/min of axle rotating speed.Spiral or screw type shape, screw thread number, spiral groove depth, pitch, spiral shell rib geometrical dimension are adjustable in the rotating shaft of twin screw extruder reactor shell inward turning.In reactor of the present invention, the screw rod of agitator effect and mass transport effect reacts, along with processing requirement plasticizing (mixings), the degassing, softening, multistage halogenation, stablize, devolatilization, each operation function difference of metering discharging stripping and slicing, can change and carry out various segmentation combinations, to adjust material and tube inwall, spiral or screw rod and acting force between materials, realization is to effective control of material pressure and temperature, thereby the control halogenating reaction makes technology combine closely with reactor apparatus and reaches optimization.In the halogenating reaction section because reactant concn increases and the high-speed screws effect, be equipped with on the cylindrical shell the radially pin of different distributions, halogenating agent and polymer reaction point unit time frequency of exposure have been improved, the performance speed of reaction has been improved about 10 times, Here it is maximum high viscosity materials stream of the present invention and low viscosity fluid effect have in a small amount obtained halogenating reaction reason efficiently.

Improving 1-polyolefin halogenation reaction efficiency among the present invention in the twin screw extruder reactor is to dispose ultrasonic viscosity reduction district in plasticizing, the degassing and halogenating reaction interval in the twin screw extruder reactor, make the 1-polyolefine enter the halogenation district at a certain temperature before reduction viscosity help halogenating reaction.When the reaction of 1-polyolefin halogenation finishes, through stable and devolatilization section, in conjunction with ultrasonic unit, can reduce the discharge zone temperature at the metering discharge zone, guarantee polyolefinic quality of halogenation 1-and output.The ultrasonic generator of above-mentioned configuration, its hyperacoustic amplitude are 5-30 μ m, and frequency is 5-100KHz.

The present invention's degassing process described in the halogenation 1-polyolefine in the twin screw extruder reactor is through plasticizing or mixture, at the degassing stages venting port, with N ₂Remove non-condensable gas, moisture, low boiling hydrocarbon in the raw material, reach requirement to guarantee degassing back material, for example the following material of oxygen and water-content 20ppm enters subsequent processing.

When the present invention prepares halogenation 1-polyolefine in the twin screw extruder reactor, except that above-mentioned need adding diluent for gases and halogenating agent cooperates, also need add other auxiliary agent in the twin screw extruder reactor, guarantee polyolefinic halogenating reaction of 1-and the polyolefinic quality of halogenation 1-.Auxiliary agent used in 1-polyolefine and the halogenating agent extrusion reaction has stablizer, as epoxy soybean oil, epoxy palm oil, dicumyl peroxide (DCP), 2,6-di-t-butyl-4-cresols (264), 2,2 '-methylene radical-two (4-methyl-6-tert butyl) phenol (2246), terephthalic acid or hexanodioic acid, its consumption is the 0.05-5% of 1-polyolefine quality; Initiator has benzoyl peroxide (PBO) or Diisopropyl azodicarboxylate (AIBN), and its consumption is the 0.05-1% of 1-polyolefine quality; Catalyzer has AlCl ₃, AlBr ₃, FeCl ₃Or FeBr ₃, its consumption is the 0.05-1% of 1-polyolefine quality.

Halogenation 1-polyolefine enter the devolatilization section can feed rare gas element to forcing machine to remove by-product hydrogen halide and remaining halogenating agent.This technology relates to the destruction polymer surfaces and is exposed to rare gas element and/or reactive gas with the continuous updating surface.The polyolefinic devolatilization purifying of halogenation 1-can guarantee long-term stability and the chemical reaction performance that stores of polymkeric substance.The 1-polyolefine after the halogenation, enters the devolatilization section through stable in the twin screw extruder reactor, described devolatilization operation is carried out the devolatilization of 2-4 section, adds respectively in the devolatilization section and helps devolatilization agent such as nitrogen (N ₂), methane (CH ₄), ammonia (NH ₃) or carbonic acid gas (CO ₂), remove hydrogen halide, N ₂, a small amount of halogen and low boilers.Helping devolatilization agent add-on is 1.20% of 1-polyolefine quality.Devolatilization hop count and its processing condition, feedstock property are different and different with product requirement.For example two sections devolatilization conditions are: 60-120 ℃ of first section devolatilization temperature, pressure 30-60KPa; Second section devolatilization temperature is 80-150 ℃, and pressure is 20-40KPa.Discharge gas recycling respectively.

The invention provides its characteristics of the polyolefinic method of manufacturing halogenation 1-is:

1, technological process and equipment are unique advanced, have wide range of applications, and can satisfy the needs that various 1-polyolefine carry out halogenating reaction, and can adapt to the requirement of solid-state and liquid two kinds of raw materials.

2, use the twin screw extruder reactor assembly, the various requirement that adapts to height, the conveying of medium viscosity fluids high-level efficiency, mixing, mass transfer, heat transfer, the degassing, devolatilization, be suitable for the halogenating reaction of high solids content, high viscosity 1-polyolefine and a small amount of halogenating agent of low viscosity especially, its macroreaction speed ratio tradition still formula halogenating reaction has improved an order of magnitude.

3, the present invention is with 1-polyolefin halogenation process, concentrate on that a very compact continuable plasticizing (mixing), the degassing, ultrasonic wave viscosity reduction, softening, multistage halogenation, neutralization are stable, realize in the operation sealing dehumidification system of devolatilization, ultrasonic wave cooling, metering discharging stripping and slicing, compare with traditional halogenation production technique, technical process has shortened 3/4, has saved investment and energy source and power consumption.The twin screw extruder reactor assembly that carries out the preparation of 1-polyolefin halogenation has the aggregation type structure, can adjust according to the product difference.The more important thing is that by-product hydrogen halide is rationally reclaimed, saved neutralization and used alkali that equipment does not have heavy corrosion, do not produce acid waste gas and a large amount of brine waste, improved the polyolefinic production status of halogenation 1-at all, very help environment protection; The content of halogen of halogenated rubber like polymer is controlled, and does not contain the corrodibility acid gas.

4, multistage halogenation technology of the present invention combines with the ingenious of twin screw extruder reactor, add halogenating agent and promoter addition, the adjusting of temperature and pressure sectional, the high efficiency smooth that can guarantee halogenating reaction carries out, avoid and reduced macromolecular main chain taking place because of the degraded side reaction of crossing halogenation and rupturing, help the raising of halogenated polymer product inner quality, this is that current traditional 1-polyolefin halogenation production technology can not be accomplished, also is a quantum jump and the advantage of halogenation 1-polyolefine technology of the present invention.

Description of drawings

Fig. 1 is twin screw extruder reactor assembly production halogenation 1-polyolefin process flow process and device synoptic diagram, 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 reclaims hydrocarbon vapour 60 and 61, gas exhauster 62; buffering separating tank 63; reactor plasticizing/mixing section 7 reclaims hydrocarbon vapour 8, reactor 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, rare gas element 15, halogenating agent 16; hybrid buffer 17; supercharger 18, halogenating reaction I section 19, conditioning agent pipeline 20; liquid halogen pipeline 21; ooze and mix still 22, metered charge pump 23, halogenating reaction II section 24; halogenating reaction III section 25; solvent line 26, stablizer 27, mixing kettle 28; metered charge pump 29; reactor stable section 30 and 31, reactor devolatilization section 32; 33, help devolatilization agent pipe 34; 35; dried hydrogen halide exhausting line 36; cooler condenser 37, condenser jar 38 reclaims lower boiling property management 39; steam condenser 40; 41; vacuum exhaust machine 42, reactor 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

The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to the following example.

Embodiment one

1-polyolefin halogenation device primary device is a reverse twin screw extruder reactor assembly as shown in Figure 1, screw diameter Ф 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.Cylindrical shell divides 10 sections temperature controls, and cold medium is 0 ℃ of white oil in the cylindrical shell, and urceolus heats with electric heating brasses heating jacket.Pellets of high density polyethylene (density 0.95g/m ³) adding the hopper of the broken plasticizing machine 3 of feeding machine-spiral, weight is 30kg.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h, the temperature of the broken plasticizing machine of spiral is controlled at 60-100 ℃.Import the 20kg tetracol phenixin that is dissolved with the 60g Diisopropyl azodicarboxylate by 6 meterings of liquid raw material jar, high density polyethylene(HDPE) softened, tears up and be squeezed into the softening thing of porous, after sending into twin screw extruder reactor plasticizing degassing stages, solvent and small amount of moisture are evaporated and reclaim, with solid content is viscous fluid more than 70%, after carrying out the ultrasonic wave viscosity reduction again, enter the halogenating reaction system.The twin screw extruder reactor is diameter Ф 100mm, the asynchronous parallel dual-screw extruding machine reactor of L/D=10, and its chuck has heating function, makes 1-polyolefine raw material protection comparatively high temps, so that before entering the halogenating reaction section, gets rid of a part of solvent again.Enter the viscous fluid of fluxing zone, only mix with small amount of nitrogen, get higherly in the pressure Be Controlled of the buffering separating tank of exhaust ports, and temperature is lower, is evaporated to prevent a large amount of solvents, this with material temperature controlling at 70-100 ℃.Be diluted to mixed gas (by volume 1: 10 be made into halogenating agent) with purity nitrogen with 5kg chlorine in mixing surge tank, 50% of the chlorine quality of this purity nitrogen dilution feeds halogenating reaction section I continuously, and I halogenation temperature is 100-120 ℃.The chlorine that mixes purity nitrogen dilution remaining in the surge tank will add II and III halogenating reaction section respectively continuously by 60% and 40% of its weight, and II halogen section temperature is 50-70 ℃, and III halogenation section temperature then rises to 70-90 ℃.With epoxy soybean oil, 2246, blended wax and hexanaphthene, with the polyethylene quality is 100, in 0.5: 0.1: 0.5: 5 ratio wiring solution-formings, inject stable reaction section 30 with the metering charge pump continuously, discharge from devolatilization auxiliary agent mouth respectively in devolatilization section 32, nitrogen gas pressure maintains 3.0-5.0MPa, about the first exhaust port pressure 50KPa, and temperature 110-130 ℃ of adjusting.About the second exhaust port pressure 20KPa, temperature is 120-150 ℃ of adjusting, to guarantee removing of free halogen and low-boiling-point substance in the halogenation product.The present embodiment products obtained therefrom is a chlorinatedpolyethylene, hourly output 41.2kg (containing 8.8% process oil), and the chlorine mass content is 30% in the product.

Embodiment 2

Adopt embodiment 1 same reaction apparatus system.Present embodiment adopts new LDPE (film grade) pellet (density 0.92g/m ³) adding the hopper of the broken plasticizing machine 3 of feeding machine-spiral, weight is 30kg.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h.The temperature of the broken plasticizing machine of spiral is controlled at 60-80 ℃.Import the 20kg tetracol phenixin that is dissolved with the 60g Diisopropyl azodicarboxylate by 6 meterings of liquid raw material jar, new LDPE (film grade) softened, tears up and be squeezed into the softening thing of porous, after sending into twin screw extruder reactor plasticizing degassing stages, solvent and small amount of moisture are evaporated and reclaim, obtain the viscous fluid of solid content more than 70%, carry out the ultrasonic wave viscosity reduction again, enter the halogenating reaction system.Twin screw extruder reactor diameter Ф 100mm, the asynchronous parallel dual-screw extruding machine reactor of L/D=10, its chuck has heating function, makes polymer raw material keep comparatively high temps, so that before entering halogenating reaction plasticizing (mixing) section, get rid of a part of solvent again.Different with embodiment 1, enter the viscous fluid of fluxing zone, only mix with small amount of nitrogen.Get higherly in the pressure Be Controlled of the buffering separating tank of exhaust ports, and temperature is lower, is evaporated to prevent a large amount of solvents.This with material temperature controlling at 70-100 ℃.Feed halogenating reaction section I continuously with 5kg chlorine purity nitrogen diluted mixture gas (1: 10 by volume be made into halogenating agent), I halogenation temperature is 70-100 ℃.Mix and press (0.25-0.4) in the surge tank: 1 mass ratio prepares sulfurous gas and chlorine, and with 10 times of purity nitrogen dilutions, to add quality then and add II, III halogenating reaction section respectively continuously by 60%, 40%, II halogen section temperature is 50-70 ℃, and III halogenation section temperature then rises to 70-90 ℃.With epoxy soybean oil, 2246, blended wax and hexanaphthene, with the polyethylene quality is 100, in 0.5: 0.1: 0.5: 5 ratio wiring solution-formings, inject the stable reaction section with the metering charge pump continuously, discharge from devolatilization auxiliary agent mouth respectively in the devolatilization section, nitrogen gas pressure maintains 3.0-5.0MPa, about the first exhaust port pressure 50KPa, and temperature 110-130 ℃ of adjusting.About the second exhaust port pressure 20KPa, temperature is 120-140 ℃ of adjusting, to guarantee removing of free halogen, sulfurous gas and low-boiling-point substance in the halogenation product.The present embodiment products obtained therefrom is a chlorosulfonated polyethylene rubber, hourly output 39.7kg (containing 8.8% process oil), product sulphur mass content 1.1%, chlorine mass content 33%.

Embodiment 3

With embodiment 1 same reactor apparatus system.Present embodiment adopts polypropylene granules to add the hopper of the broken plasticizing machine 3 of feeding machine-spiral, and weight is 30kg.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h.The temperature of the broken plasticizing machine of spiral is controlled at 80-100 ℃.Import the 20kg toluene that is dissolved with the 40g Diisopropyl azodicarboxylate by 6 meterings of liquid raw material jar, polypropylene softened, tears up and be squeezed into the softening thing of porous, after sending into twin screw extruder reactor plasticizing degassing stages, solvent and small amount of moisture are evaporated and reclaim, obtain solid content and be the viscous fluid more than 70%, carry out the ultrasonic wave viscosity reduction again, enter the halogenating reaction system.Twin screw extruder reactor diameter Ф 100mm, the asynchronous parallel dual-screw extruding machine reactor of L/D=10, its chuck has heating function, makes pp material keep comparatively high temps, so that before entering halogenating reaction plasticizing (mixing) section, get rid of a part of solvent again.Different with embodiment 1, enter the viscous fluid of fluxing zone, only mix with small amount of nitrogen.Get higherly in the pressure Be Controlled of the buffering separating tank of exhaust ports, and temperature is lower, is evaporated to prevent a large amount of solvents.This with material temperature controlling at 80-100 ℃.Be diluted to mixed gas (by volume 1: 10 be made into halogenating agent) with purity nitrogen with 5kg chlorine in mixing surge tank, 50% of the chlorine quality of this purity nitrogen dilution feeds halogenating reaction section I continuously, and I halogenation temperature is 80-105 ℃.The chlorine that mixes purity nitrogen dilution remaining in the surge tank will add II and III halogenating reaction section respectively continuously by 60% and 40% of its quality, and II halogen section temperature is 50-70 ℃, and III halogenation section temperature then rises to 70-90 ℃.With epoxy soybean oil, 2246, blended wax and hexanaphthene, with the polyethylene quality is 100, in 0.5: 0.1: 0.5: 5 ratio wiring solution-formings, inject the stable reaction section with the metering charge pump continuously, discharge from devolatilization auxiliary agent mouth respectively in the devolatilization section, nitrogen gas pressure maintains 3.0-5.0MPa, about the first exhaust port pressure 50KPa, and temperature 110-130 ℃ of adjusting.About the second exhaust port pressure 20KPa, temperature is 120-140 ℃ of adjusting, to guarantee removing of free halogen and low-boiling-point substance in the halogenation product.The present embodiment products obtained therefrom is a Chlorinated Polypropylene III rubber, product chlorine mass content 28.7%.

Embodiment 4

Adopt embodiment 1 same reaction apparatus.Present embodiment adopts the granules of polystyrene material to add the hopper of the broken plasticizing machine 3 of feeding machine-spiral, and weight is 30kg.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h.The temperature of the broken plasticizing machine of spiral is controlled at 50-80 ℃.Import the 20kg tetracol phenixin that is dissolved with 445g aluminum chloride by 6 meterings of liquid raw material jar, polystyrene softened, tears up and be squeezed into the softening not viscosity floss of porous, after sending into twin screw extruder reactor plasticizing degassing stages, solvent and small amount of moisture are evaporated and reclaim, obtain the viscous fluid of solid content more than 70%, carry out the ultrasonic wave viscosity reduction again, enter the halogenating reaction system.Twin screw extruder reactor diameter Ф 100mm, the asynchronous parallel dual-screw extruding machine reactor of L/D=10, its chuck has heating function, makes polymer raw material keep comparatively high temps, so that before entering halogenating reaction plasticizing (mixing) section, get rid of a part of solvent again.Different with embodiment 1, enter the viscous fluid of fluxing zone, only mix with small amount of nitrogen.Get higherly in the pressure Be Controlled of the buffering separating tank of exhaust ports, and temperature is lower, is evaporated to prevent a large amount of solvents.Change with raw material, the tenderizer composition changes monobromethane into: adipic acid ester: naphthenic oil is 0.1: 0.05: 0.05 mass ratio, after stirring homogenizing still homogenizing, is added to the softening section of reaction with the metering charge pump.This material is cooled to 0-10 ℃.Feed I halogenating reaction section continuously with 70kg bromine and bromochloroethane (being made into halogenating agent by weight 1: 2), I halogenation temperature is 0-5 ℃.Mix the surge tank chuck and maintain 0-2 ℃ with the cooling of circulation ethylene glycol ice bath, quality be will add then and I, II, III halogenating reaction section added respectively continuously by 50%, 30% and 20%, I halogenation section temperature is 0-5 ℃, II halogenation section temperature is 5-10 ℃, and III halogenation section temperature then rises to 10-15 ℃.With epoxy soybean oil, 2246, blended wax and hexanaphthene, with the polystyrene quality is 100, in 0.5: 0.1: 0.5: 5 ratio wiring solution-formings, inject the stable reaction section with the metering charge pump continuously, discharge from devolatilization auxiliary agent mouth respectively in the devolatilization section, nitrogen gas pressure maintains 3.0-5.0MPa, about the first exhaust port pressure 50KPa, and temperature 100-110 ℃.About the second exhaust port pressure 20KPa, temperature is at 120-150 ℃, to guarantee removing of free halogen and low-boiling-point substance in the halogenation product.The present embodiment products obtained therefrom is a brominated Polystyrene, product bromine mass content 66%.

Embodiment 5

Adopt embodiment 1 same reaction apparatus.The solid isoprene-isobutylene rubber fragment of present embodiment employing chopping or rectangular, its size or cross section＜20mm.Add the hopper of the broken plasticizing machine 3 of feeding machine-spiral, weight is 30kg.Its specification is the commercially available general isoprene-isobutylene rubber of 2 moles of % of degree of unsaturation, Mooney 34.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h.The temperature of the broken plasticizing machine of spiral is controlled at 50-80 ℃, rubber is torn up and is squeezed into the softening not viscosity floss of porous, sends into the downstream reaction system.On feeding-passage, contrary material direction feeds sealing nitrogen.In plasticizing (mixing) section 7 of reactor, the twin screw of staggered arrangement spiral shell rib band cutting mixing functions plastifies softening raw material, and feeds the pure nitrogen gas mixing simultaneously, and the fluxing zone temperature can be controlled at 90 ℃.At reaction degassing stages 9 venting ports, material is by step-down, and nitrogen entrapped air, moisture and possible unsaturated monomer or low boiling hydrocarbon are deflated the machine extraction, and the pressure and the middle pressure pure nitrogen level of control buffering separating tank reach requirement with raw material after guaranteeing the degassing.Enter reactor ultrasonic wave viscosity reduction section 14 viscosity reductions after the degassing.Stirring homogenizing still 12, add the hexanaphthene of 0.2 times of isoprene-isobutylene rubber weight and the naphthenic oil of 0.1 times of isoprene-isobutylene rubber weight, 0.01 the tenderizer of the adipic acid ester of isoprene-isobutylene 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, with softening section of metering charge pump supercharging adding, the material temperature is at 60-70 ℃, and tax is with the ultrasonic wave viscosity reduction.At reaction zone, with 0.45kg chlorine purity nitrogen diluted mixture gas (1: 10 by volume be made into halogenating agent), 50%, 30% and 20% ratio by mass percentage, add I, II in due order, III halogenating reaction section, reaction belongs to low exothermic process, easy temperature control, 50-70 ℃ of I halogenating reaction temperature, 70-100 ℃ of II halogenating reaction temperature, 90-130 ℃ of III halogenating reaction temperature.The halogenating reaction section has occupied twin screw extruder reactor 40% space, has guaranteed enough time of halogenating reaction and halogenating agent nearly 99% above utilization ratio.Hexanaphthene in 0.1 times of isoprene-isobutylene rubber weight of mixing kettle, 0.005 the calcium stearate of the phenolic type antioxidant 2246 of isoprene-isobutylene rubber weight and 0.01 times of isoprene-isobutylene rubber weight doubly, be mixed with stabiliser solution, again with the metering charge pump, be pressed into the stable section of reactor, at two degassing stages, feed the purity nitrogen of isoprene-isobutylene rubber amount 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 condenser reclaims solvent, and pure dried hydrogen chloride gas recycling.

Slough the chlorinated butyl rubber of by-product hydrogen halide, through metering zone, the current stabilization cooling is boosted and is sent into out mouth template, be aided with ultrasonic heat sink, through stripping and slicing of die face slitting shear machine and flash distillation cooling, obtain the chlorinated butyl rubber product of chlorine mass content 1.1%, mooney viscosity 38 at this, this product contains the mass percent 4.3% of naphthenic oil, deductible when making goods add operation oil, product has good comprehensive rerum natura and processibility.Its volatile matter quality content＜0.2%, do not contain free halogenide, above-mentioned continuous halogenation apparatus system, per hour can get chlorinated butyl rubber 22.7kg product, the dried hexanaphthene 6kg that recovery can be recycled, consume chlorine 0.45kg, reclaim dried hydrogen chloride gas 0.23kg, but the halogenating agent of other chemical is sold or is used in the pressure bottling for byproduct.

Embodiment 6

Adopt embodiment 1 same reaction apparatus system.The solid isoprene-isobutylene rubber fragment of present embodiment employing chopping or rectangular, its largest contours physical dimension or cross section＜20mm, mooney viscosity 50,2.2 moles of % of its dried glue degree of unsaturation.Add the hopper of the broken plasticizing machine 3 of feeding machine-spiral, weight is 30kg.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h.The temperature of the broken plasticizing machine of spiral is controlled at 50-80 ℃.Import the 20kg normal hexane by 6 meterings of liquid raw material jar, isoprene-isobutylene rubber softened, tears up and be squeezed into the softening not viscosity floss of porous, after sending into twin screw extruder reactor plasticizing degassing stages, solvent and small amount of moisture are evaporated and reclaim, obtain the viscous fluid of solid content more than 70%, enter the halogenating reaction system.Twin screw extruder reactor diameter Ф 100mm, the asynchronous parallel dual-screw extruding machine reactor of L/D=10, its chuck has heating function, makes the isoprene-isobutylene rubber raw material keep comparatively high temps, so that before entering halogenating reaction plasticizing (mixing) section, get rid of a part of solvent again.Different with embodiment 1, enter the viscous fluid of fluxing zone, only mix with small amount of nitrogen.Get higherly in the pressure Be Controlled of the buffering separating tank of exhaust ports, and temperature is lower, is evaporated to prevent a large amount of solvents.The tenderizer composition changes hexanaphthene into: adipic acid ester: naphthenic oil is 0.1: 0.05: 0.05 part by weight, after stirring homogenizing still homogenizing, is added to the softening section of reaction with the metering charge pump.This section with material constant temperature to 80-100 ℃.Feed I halogenating reaction section continuously with 0.25kg bromine purity nitrogen diluted mixture gas (1: 10 by volume be made into halogenating agent), by 50%, 30% and 20% mass ratio, add I, II successively, III halogenating reaction section, reaction belongs to low exothermic process, easy temperature control, 80-90 ℃ of I halogenating reaction temperature, 90-100 ℃ of II halogenating reaction temperature, 100-110 ℃ of III halogenating reaction temperature.The halogenating reaction section has occupied twin screw extruder reactor 40% space, has guaranteed enough time of halogenating reaction and halogenating agent nearly 99% above utilization ratio.The hexanaphthene of 0.1 times of isoprene-isobutylene rubber weight in mixing kettle, 0.005 the calcium stearate of the phenolic type antioxidant 2246 of isoprene-isobutylene rubber weight and 0.01 times of isoprene-isobutylene rubber weight doubly, be mixed with stabiliser solution, again with the metering charge pump, be pressed into the stable section of reactor, at two degassing stages, feed the purity nitrogen of isoprene-isobutylene rubber quality 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 hydrogen bromide, nitrogen, small amount of bromine gas and low boiling point solvent, after water cooler, cooling, use the gas exhauster supercharging, again after condenser reclaims solvent, and pure dried bromize hydrogen gas recycling.

Slough the brominated butyl rubber of by-product hydrogen halide, through metering zone, the current stabilization cooling is boosted and is sent into out mouth template, be aided with ultrasonic heat sink, through stripping and slicing of die face slitting shear machine and flash distillation cooling, obtain bromine content 1.2% (quality) at this, the brominated butyl rubber product of mooney viscosity 41, this product contains naphthenic oil 4.2% (quality), and deductible when making goods add operation oil, product has good comprehensive rerum natura and processibility.Its volatile content＜0.3% (quality) does not contain free halogenide.

Embodiment 7

Adopt embodiment 1 same reaction apparatus system.The solid isoprene-isobutylene rubber fragment of present embodiment employing chopping or rectangular, its largest contours physical dimension or cross section＜20mm, mooney viscosity 50,2.2 moles of % of its dried glue degree of unsaturation.Add the hopper of the broken plasticizing machine 3 of feeding machine-spiral, weight is 30kg.Feed the 0.01MPa pressure nitrogen gas in the hopper bottom, flow rate is about 0.2NM ³/ h.The temperature of the broken plasticizing machine of spiral is controlled at 50-80 ℃.Import the 20kg normal hexane by 6 meterings of liquid raw material jar, isoprene-isobutylene rubber softened, tears up and be squeezed into the softening not viscosity floss of porous, after sending into twin screw extruder reactor plasticizing degassing stages, solvent and small amount of moisture are evaporated and reclaim, obtain the viscous fluid of solid content more than 70%, enter the halogenating reaction system.The twin screw extruder reactor is diameter Ф 100mm, the asynchronous parallel dual-screw extruding machine reactor of L/D=10, its chuck has heating function, makes the isoprene-isobutylene rubber raw material keep comparatively high temps, so that before entering halogenating reaction plasticizing (mixing) section, get rid of a part of solvent again.Different with embodiment 1, enter the viscous fluid of fluxing zone, only mix with small amount of nitrogen.Get higherly in the pressure Be Controlled of the buffering separating tank of exhaust ports, and temperature is lower, is evaporated to prevent a large amount of solvents.The tenderizer composition changes hexanaphthene into: adipic acid ester: naphthenic oil is 0.1: 0.05: 0.05 part by weight, after stirring homogenizing still homogenizing, is added to the softening section of reaction with the metering charge pump.This section cools to 40-50 ℃ with material.Feed halogenating reaction section I, 60-80 ℃ of I halogenation section temperature continuously with 0.25kg chlorine purity nitrogen diluted mixture gas (1: 10 by volume be made into halogenating agent).Mixing the logical 0 ℃ of cold oil of surge tank chuck is cooled to about 5 ℃, the bromine chloride gas for preparing is maintained at-7 ℃-5 ℃, and with 10 times of pure nitrogen gas dilutions, then add-on is added II, III halogenating reaction section and IV halogenating reaction section respectively continuously by 50%, 30% and 20% mass percent, II halogenation section temperature is 50-70 ℃, III halogenation section temperature then rises to 70-120 ℃, and IV halogenating reaction section temperature is 120-180 ℃.With epoxy soybean oil, 2264, blended wax and hexanaphthene, with the isoprene-isobutylene rubber quality is 100, in 0.5: 0.1: 0.5: 5 ratio wiring solution-formings, inject the stable reaction section with the metering charge pump continuously, remove from devolatilization auxiliary agent mouth respectively in the devolatilization section, nitrogen gas pressure maintains 3.0-5.0Mpa, about the first exhaust port pressure 50KPa, and temperature 110-130 ℃ of adjusting.About the second exhaust port pressure 20KPa, temperature is 120-150 ℃ of adjusting, to guarantee removing of free halogen and low-boiling-point substance in the halogenation product.The present embodiment products obtained therefrom is the bromine chlorinated butyl, hourly output 34.1kg (containing 8.8% process oil), product bromine mass content 2%, chlorine mass content 0.5%, mooney viscosity about 42.

Claims

1. a 1-polyolefin halogenation production method is characterized in that comprising the following steps:

1., pre-softening

In the twin screw extruder reactor assembly, the 1-polyolefine is with in dry state or the hygrometric state feeding feeding machine, carry out softening in advance, pre-softening temperature 60-100 ℃, tear up and be squeezed into softening thing of porous or hygrometric state pulpous state material, described hygrometric state feeding 1-polyolefine mass content is 50-95%, and other is that solvent, softening agent, lubricant or tenderizer are mixed into hygrometric state in feeding machine;

2., the plasticizing degassing

3. halogenating reaction

Step viscosity reduction 1-polyolefine material is 2. entered in the I-III conversion zone or I-IV conversion zone district in the twin screw extruder reactor with the reinforced standard measure of hunger, the auxiliary agent segmentation is controlled in each section of reaction zone, the halogenating agent consumption is 0.9-1.1 a times of 1-polyolefine theoretical amount, and the amount that each section adds halogenating agent is respectively to add 50%, 30% and 20% or 40%, 30%, 20% and 10% of halogenating agent total mass; React each section temperature of reaction I section for 0-120 ℃, the II section is 3-150 ℃, the III section be 5-180 ℃ or I section temperature of reaction 0-120 ℃, II section temperature of reaction is 3-150 ℃, III section temperature of reaction is 5-180 ℃, 8-180 ℃ of IV temperature of reaction, conversion zone pressure is 0.2-10.0MPa, halogenating agent and 1-polyolefine thorough mixing uniform contact and the generation halogenation 1-polyolefine that reacts in this reaction zone; Described auxiliary agent is respectively a stablizer, and its consumption is the 0.05-5% of 1-polyolefine total mass, and initiator is that benzoyl peroxide or azo two isobutyls are fine, and its consumption is the 0.05-1% of 1-polyolefine total mass, and catalyzer is AlCl ₃, AlBr ₃, FeCl ₃Or FeBr ₃, its consumption is the 0.05-1% of 1-polyolefine quality, halogenating agent is 1 with the diluent volume ratio: 0.1-1: 10;

4. stable

Step halogenation 1-polyolefine is 3. entered twin screw extrusion reaction device stable section with stablizer stablize, the consumption of stablizer is the 0.05-5% of 1-polyolefine quality;

5. devolatilization

Halogenation 1-polyolefine enters the devolatilization section after stable, add respectively in the devolatilization section and to help the devolatilization agent, helping devolatilization agent add-on is 1.20% of 1-polyolefine quality, first section devolatilization temperature is 60-120 ℃, pressure is 30-60KPa, second section devolatilization temperature is 80-150 ℃, and pressure is 20-40KPa, removes hydrogen halide, N ₂, a small amount of halogen and low boilers, discharge gas recycling respectively;

6. ultrasonic wave cooling major ingredient molding, granulating

Step 5. after the devolatilization material after the ultrasonic generator cooling, carry out molding, granulating, wherein hyperacoustic amplitude is 5-30 μ m, frequency is 5-100KHz.

2. according to the 1-polyolefin halogenation production method of claim 1, it is characterized in that homopolymer or multipolymer that described 1-polyolefine is polyethylene, polypropylene, polyvinyl chloride, polystyrene or polyisobutene, described halogenating agent is chlorine, liquid chlorine, SULPHURYL CHLORIDE, iodine monochloride, bromine chloride, bromine gas, liquid bromine, sodium hypobromite or sulfur bromide.

3. according to the 1-polyolefin halogenation production method of claim 1, it is characterized in that described stablizer is epoxy soybean oil or epoxy palm oil.

4. according to the 1-polyolefin halogenation production method of claim 1, it is characterized in that described tenderizer is C ₆-C ₈Raffinate oil, the salt of industrial hexane, hexanaphthene, heptane, industrial naptha, paraffin oil, naphthenic oil, toluene, bromochloromethane, bromochloroethane, ethylene dichloride, sebate, hexanodioic acid fat, azelate, phosphoric acid ester, paraffin, microcrystalline wax, blended wax, stearamide wax or stearic acid and calcium thereof, potassium, zinc.

5. according to the 1-polyolefin halogenation production method of claim 1, it is characterized in that described to help the devolatilization agent be nitrogen, methane, ammonia or carbonic acid gas.