CN104804318B - A kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene - Google Patents
A kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
- C08L23/34—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
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Abstract
The invention belongs to chlorosulfonated polyethylene preparation field, and in particular to a kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene, described method include：High Mooney viscosity haloflex powder and antitack agent are added in reactor, open and stir and vacuumize inside reactor, it is then charged with hot nitrogen, then pressure is released, so it is repeated several times, open ultraviolet lamp irradiation, chlorine and sulfur dioxide gaseous mixture are passed through to reactor, reaction product is moved in purified water and washed repeatedly to washings pH ＞ 6 by reaction after terminating, then material dewatering is dried, high Mooney viscosity CSM powder is obtained to put into homogenizer in proportion with rubber processing oil, heat stabilizers, it is kneaded using traditional rubber and former is kneaded and is molded, obtain oil-filled type CSM products.During the method for the present invention can solve existing gas solid method production CSM, the problems such as primary raw material low mooney viscosity CPE productions are difficult, and CSM product tensile strengths are not high, and production cost is high.
Description
Technical field
The invention belongs to chlorosulfonated polyethylene preparation field, and in particular to a kind of gas-solid phase reaction prepares oil-filled type chlorosulfonation
The method of polyethylene.
Background technology
Chlorosulfonated polyethylene (hereinafter referred to as CSM) is polyethylene through extraordinary synthesis rubber made from superchlorination and chlorosulfonation
Glue.Due to the presence of the saturability and chlorosulfonyl of structure, therefore there is good cross linkable, and the weatherability of vulcanizate,
Ozone resistance, oil resistivity, chemical proofing, wearability, radiation resistance, anti-flammability and air-tightness are excellent, and color stability is good,
It is widely used in automobile rubber spare and accessory parts, flame-retardant electric wire and cable, roof waterproof and rubber dam, chemical industry equipment corrosion protective lining, system
The field such as footwear and coating.
The production method of chlorosulfonated polyethylene has two kinds of solvent method and gas solid method.Industrial production generally uses solvent at present
Method, patent document, as US2879261, US3299014, US3542747 disclose the method that solvent method prepares CSM.Solvent legal system
It is for CSM method：Polyethylene is dissolved in carbon tetrachloride, is first passed through chlorine reaction, then passes to chlorine and sulfur dioxide
Reacted to obtain the carbon tetrachloride solution of chlorosulfonated polyethylene, then isolate carbon tetrachloride, obtain product.But due to molten
Agent method uses and consumed in process of production a large amount of carbon tetrachloride, and then atmospheric ozone layer can be damaged, the method by
It is included in the project of developmental limitation.
Gas solid method has progressively been used for CSM preparation, but use at present be fluidized-bed reactor method and stream
Journey, the method as disclosed in patent document CN101735350A, this method are to be placed in haloflex (hereinafter referred to as CPE) powder
In fluidized-bed reactor, under the conditions of ultraviolet irradiation, it is passed through chlorine and sulfur dioxide is reacted and CSM is made.Fluid bed
Reactor prepares CSM and production system long flow path be present, and equipment investment is big and seriously corroded, process control difficulties, chlorine and titanium dioxide
The problems such as Recovery ratio is low, and Dust Capacity is big in production system and is difficult to remove, and exhaust-gas treatment is difficult and alkali consumption is big, particularly product
The skewness of middle chlorosulfonyl, causing the tensile strength of vulcanizate reduces.In addition the maximization of the reactor of the method is more
It is difficult.Method disclosed in Chinese invention patent ZL201110006747.4 prepares the poly- second of chlorosulfonation using fixed bed reactors
Alkene, this method is applied to prepare the chlorosulfonated polyethylene compared with low mooney viscosity, and the production cost of product is higher, and mechanical strength is inclined
It is low.
Synthetic rubber produces the trend of the oil-filled type development of oriented HMW at present.
The content of the invention
To overcome the above-mentioned problems of the prior art, the present invention is intended to provide a kind of gas-solid phase reaction prepares oil-filled type chlorine
The method of sulfonated polyethylene, during solving existing gas solid method production CSM, primary raw material low mooney viscosity CPE productions
Difficulty, the problems such as CSM product tensile strengths are not high, and production cost is high.Oil-filled type CSM production cost is far below universal gas-solid
Phase method CSM, and mechanical performance is also improved.
To realize the goal of the invention of the present invention, inventor provides following technical scheme：
A kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene, comprises the steps：
(1) high Mooney viscosity haloflex powder (i.e. CPE powder) and antitack agent are added in reactor, wherein,
Antitack agent dosage is the 3~8% of haloflex powder quality；Described reactor uses Multilayer stirring-type fixed bed reaction
Device, its top are provided with plug-in type agitator and built-in ultraviolet lamp, and the bottom of described plug-in type agitator is spiral shell
Ribbon blender oar and top is multiple layers of vanes formula agitating paddle, the effect of multiple impellers is：Bottom ribbon impeller ensures solid
Body material uniformly stirs, and the multiple blade stirrer oars in upper strata cause chlorine, sulfur dioxide in reactor to keep being evenly distributed.
(2) reactor stirring is opened, is evacuated to reactor pressure to be filled with 50~60 DEG C after -0.1~-0.08MPa
Hot nitrogen (rises to >=0.05Mpa) to reactor pressure, then releases pressure, and repetition vacuumizes, fills hot nitrogen, pressure discharge operations
For several times (number depending on moisture in raw material CPE, such as 2~6 times, to remove moisture and oxygen in CPE).It is ultraviolet built in unlatching
Line light irradiation, reactor is vacuumized, to reactor be passed through chlorine and sulfur dioxide gaseous mixture make pressure rise to 0.05~
80 DEG C of 0.1Mpa, controlling reaction temperature ＜, react 10~30 minutes, by reactor off-gas (main component：Cl2、HCl、SO2) be discharged into
Exhaust treatment system.For several times (such as 3~6 times), the total amount for making to be passed through gaseous mixture is participation chlorosulfonation institute for operation more than repeating
1.2-2.5 times of theoretical amount is needed, reaction product is moved in purified water and washed repeatedly to washings pH ＞ 6, then takes off material
Water is dried, and obtains high Mooney viscosity CSM powder,
(3) by high Mooney viscosity CSM powder and rubber processing oil with 1:In 0.1~0.4 ratio input homogenizer,
1~3% heat stabilizer is added, is stirred, is kneaded using traditional rubber and former is kneaded and is molded, obtain granular or piece
The oil-filled type CSM products of shape.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：Described haloflex powder is：ML100 DEG C of 1+4 of Mooney viscosity is 100~150, and chlorinity is 23~40wt%,
400 μm of water content ＜ 1wt%, particle diameter ＜.As it is further preferred that haloflex powder：Water content ＜ 0.3%, particle diameter ＜ 250 μ
m.Because the properties of product that particle diameter is small and the uniform haloflex powder production of particle diameter distribution goes out are more preferable.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：The liner material of described Multilayer stirring-type fixed bed reactors is enamel or steel lining fluoroplastics.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：The addition of described gaseous mixture operates as follows：Vacuumize first make reactor pressure for -0.1~-
0.08Mpa, the gaseous mixture of chlorine and sulfur dioxide is then passed to, make speed of the reacting system pressure by 0.01~0.2MPa/10min
Degree slowly rises, if reactor pressure exceedes 0.08MPa, stops logical gaseous mixture, will be in reactor after 10~30 minutes give up
Gas is discharged into exhaust treatment system, repeats to operate (such as 3-6 times) for several times above until gaseous mixture is all passed through.The purpose so operated
Allow for reactor pressure ability to bear and keep effective gas concentration, and transfer reaction heat in time.Meanwhile in order to react
Caused heat shifts in time, material is not produced incipient scorch because of overheat, chuck can be set to cool down outside reactor.As
It is further preferred that 70 DEG C of controlling reaction temperature ＜ is answered, in case product heat endurance declines caused by reaction temperature is too high.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：Described exhaust treatment system is composed in series by sulfur dioxide absorbing tower, hydrogen chloride absorption tower and tail gas absorber, dioxy
Change sulphur absorption tower and the sulfur dioxide in waste gas and water reaction are prepared into by-product sulfuric acid, hydrogen chloride absorption tower is by the hydrogen chloride in waste gas
Absorption prepares technical hydrochloric acid, tail gas absorber using the method that alkali sprays by all acid gas purifyings in waste gas, after purification
Tail gas is discharged into air.As it is further preferred that sulfur dioxide absorbing tower and hydrogen chloride absorption tower using bubble type series connection two-stage absorb,
It is thorough to ensure to absorb.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：The agitating paddle of described plug-in type agitator is layer 2-4 to ensure the abundant flowing of gas in reactor.Plug-in type stirs
The bottom of device is ribbon impeller, and bottom agitating paddle ensures that solid material uniformly stirs, and other parts use blade stirrer
Oar, upper strata blade stirrer oar cause chlorine, sulfur dioxide in reactor to keep being evenly distributed.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：In described step (2)：Reaction product is washed to washings pH ＞ 6 repeatedly into 50-70 DEG C of purified water.As more
It is preferred that the solid-to-liquid ratio of material and water is 1：5,60 DEG C of water temperature, agitator treating 10~15 minutes, washings are removed, then add purification
Water, so wash repeatedly to washings pH ＞ 6.5, to ensure to be substantially free of acid in CSM particles.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：Described antitack agent is white carbon and superfine talcum powder or ultrafine aluminium hydroxide, wherein, the dosage of white carbon is chlorination
The dosage of the 1~2% of polyethylene powders quality, talcum powder or ultrafine aluminium hydroxide for haloflex powder quality 2~
6%.Very few addition easily causes material to bond during the course of the reaction, and the dust in excessive addition system increases
Add, cause separation difficult.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：The volume ratio of chlorine and sulfur dioxide is 1 in described gaseous mixture：0.5~1.5.More there are choosing, described gaseous mixture
The volume ratio of middle chlorine and sulfur dioxide is 1：0.8-1.Change this makes the side reaction of haloflex and chlorine increase than regular meeting.
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：Described rubber processing oil is：Trioctyl trimellitate (TOTM), phthalate, chlorinated paraffin, epoxidized soybean oil, certain herbaceous plants with big flowers
Two acid esters etc..
Preferably, the method for oil-filled type chlorosulfonated polyethylene is prepared according to a kind of gas-solid phase reaction of the present invention,
Wherein：The heat stabilizer of addition is conventional polychloroethylene heat stabilizer, such as calcium stearate.
An important factor for middle-ultraviolet lamp exposure dose of the present invention is control reaction speed, one of ordinary skill in the art's root
According to the size and structure of reactor, the quantity of haloflex is put into, creative work is not paid and is assured that light source is by work
Industry ultraviolet lamp provides.To cause ultraviolet irradiation uniform, multi-point source can be used.
Compared with prior art, advantages of the present invention has：
The present invention is using high Mooney viscosity CPE as raw material, because molecular weight is high, the product mechanical strength after chlorosulfonation
Height, even if after being filled with a certain amount of operation oil, tensile strength is still better than the low mooney viscosity product of original technology production.Due to original
Lower-molecular substance is few in material, and CPE particles gas porosity is good, enters so as to be advantageous to gaseous mixture inside its particle, is also beneficial to react
The discharge of waste gas.
The present invention is carried out due to reacting under -0.1~0.1Mpa pressure, and is repeatedly vacuumized, filled gaseous mixture, pressure release behaviour
Make.Go deep into inside haloflex being reacted so as to be advantageous to gaseous mixture so that chlorosulfonyl is evenly distributed in the product, sulphur
Change glue tensile strength to improve.
For the raw material that the present invention uses for high Mooney viscosity CPE, its softening point temperature is higher by the low Mooney of prior art use
About 20 DEG C of viscosity CPE, therefore in chlorosulfonation, is not susceptible to the caking and colour-change phenomena of material, therefore anticaking agent
Usage amount can be reduced, and product yield increases substantially, and production cost reduces.The present invention, which has, is suitable for heavy industrialization
Production, green, properties of product are high, the features such as steady quality.
Embodiment
With reference to embodiment, present disclosure is further illustrated.It should be appreciated that the implementation of the present invention is not limited to
In the following examples, any formal accommodation and/or change made to the present invention fall within the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. are equal
It is commercially available or the industry is conventional.If without specializing, the method that embodiment uses is technology generally in the art.
Embodiment 1
A kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene, using three layers of stirring-type fixed bed reactors
Gas-solid phase reaction prepares oil-filled type CSM, comprises the steps：
(1) ML100 DEG C of 1+4 of Mooney viscosity 124, moisture content 0.35wt%, chlorinity 32.3wt% haloflex are chosen
Powder, 30 mesh sieves are crossed, take 10.0Kg, add precipitated silica 0.1Kg and superfine talcum powder 0.3Kg, be well mixed, be placed in
(stirrer bottom is ribbon impeller, and upper two layers are vane type in 100L enamels, three layers of agitating paddle fixed bed reactors
Agitating paddle).
(2) it is 0.25MPa that sulfur dioxide gas to pressure is passed through into pressure-resistant 0.6MPa 1000L GB150-1998s,
Being passed through chlorine again makes pressure rise to 0.55MPa, and the gaseous mixture of generation is standby.
(3) it is -0.08MPa to be evacuated to pressure to reactor, and 60 DEG C of hot nitrogens are filled with into reactor rises to pressure
0.1MPa, release and be evacuated to -0.08MPa again after pressure, be filled with 60 DEG C of hot nitrogen, pressure release；So operate 3 times repeatedly.
Reactor stirring and built-in ultraviolet lamp (50W industry ultraviolet lamp) are opened, cooling water, control reaction are passed through to reactor jacket
70 DEG C of temperature ＜.It is slowly introducing sulfur dioxide-chlorine gaseous mixture that step (2) obtains, control pressure ramp-up rate 0.05MPa/
10min, 0.05MPa is risen to pressure, stops ventilation, continues stirring 15 minutes, releasing reactor pressure, (reaction end gas is discharged into
Exhaust treatment system), operation 5 times above are repeated, stop ultraviolet irradiation.Open air bleeding valve and reactor off-gas is discharged into exhaust-gas treatment
System (system is made up of two tandem bubble absorbing towers and a liquid-jet vacuum pump, and 5%NaOH makees absorbent).It is passed through nitrogen
Gas enters line replacement until the gas of discharge is substantially free of acid.
(4) material is placed in 50L plastic containers, adds pure water, agitator treating, washings are discharged after staticly settling,
Repeat until washings pH=6.5, filtering remove free water, material are placed in vacuum drying chamber, 80 DEG C of drying 4 are small
When, obtain high Mooney CSM powder.
The test result of high Mooney CSM powder：Chlorinity 35.5wt% (GB/T 9872-1998)；Sulfur content 1.3wt%
(GB4497-1984)；ML100 DEG C of 1+4 of Mooney viscosity 111 (GB/T 1232.1)；Volatile matter 0.32wt%.
(5) above CSM 500g, epoxidized soybean oil 100g and calcium stearate 7g are taken, is placed in stainless steel ware and mixes by hand
Close, plasticated on small size open type rubber mixing machine in flakes, obtain oil-filled type CSM test pieces.
Test piece test result：ML100 DEG C of 1+4 of Mooney viscosity 61,
Test piece vulcanizate physical property：Tensile strength 27.3Mpa,
Elongation 367%.
Embodiment 2
A kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene, using three layers of stirring-type fixed bed reactors
Gas-solid phase reaction prepares oil-filled type CSM, comprises the steps：
(1) ML100 DEG C of 1+4 of Mooney viscosity 127, moisture content 0.5wt% and chlorinity 23.5wt% haloflex are chosen
Powder, 20 mesh sieves are crossed, take 10.0Kg, add precipitated silica 0.1Kg and superfine talcum powder 0.2Kg, uniformly mixing, is placed in
(stirrer bottom is ribbon impeller, and upper two layers are leaf in 100L steel linings fluoroplastics, three layers of agitating paddle fixed bed reactors
Chip agitating paddle).
(2) it is 0.25MPa sulfur dioxide gas to pressure to be passed through into pressure-resistant 0.6MPa steel 1000L pressure vessels,
Being passed through chlorine again makes pressure rise to 0.5MPa, and the gaseous mixture of generation is standby.
(3) reactor stirring is opened, it is -0.05MPa to be evacuated to pressure to reactor, and 50 DEG C of hot nitrogens are filled with to reactor
Gas makes pressure rise to 0.4MPa, and pressure -0.08MPa is evacuated to again after releasing pressure.Ultraviolet built in unlatching irradiates (25W
Industrial ultraviolet lamp), it is passed through cooling water, 80 DEG C of controlling reaction temperature ＜ to reactor jacket.It is slowly introducing what step (2) obtained
Sulfur dioxide-chlorine gaseous mixture, control pressure ramp-up rate 0.04MPa/10min, 0.08MPa is risen to pressure, stops ventilation,
Continue stirring 10 minutes, open air bleeding valve pressure release, repetition vacuumizes, leads to gaseous mixture, pressure release, operates 4 times.Uviol lamp is closed, is led to
Enter nitrogen and enter line replacement until the gas of discharge is substantially free of acid, reaction opens baiting valve after terminating and discharges material.
(4) material is placed in 50L plastic containers, adds 60 DEG C of pure water, agitator treating, washing is discharged after staticly settling
Water, repeat twice, test washings pH=6, filter off water, to vacuum drying chamber in 70 DEG C dry 35 hours, obtain wealthy family
Buddhist nun's viscosity CSM powder.
The test result of high Mooney viscosity CSM powder：Chlorinity 25.3wt% (GB/T 9872-1998)；Sulfur content
1.2wt% (GB4497-1984)；ML100 DEG C of 1+4 of Mooney viscosity 131 (GB/T 1232.1)；Volatile matter 0.2wt%.
(5) above-mentioned CSM powder 500g, SA dibutyl ester 75g and calcium stearate 5g are taken, puts in rustless steel container and stirs by hand
Mix, be kneaded in flakes (about 100 DEG C of melting temperature) with small size open type rubber mixing machine, obtain oil-filled type CSM prints.
The test result of print：100 DEG C of 1+4 52 of Mooney viscosity ML,
Vulcanizate physical property tensile strength 27.2Mpa,
Elongation at break 331%.
Embodiment 3
A kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene, using three layers of stirring-type fixed bed reactors
Gas-solid phase reaction prepares oil-filled type CSM, comprises the steps：
(1) ML100 DEG C of 1+4 of Mooney viscosity 122, chlorinity 33wt% and moisture content 0.3wt% haloflex powder are chosen
End, 30 mesh sieves are crossed, take 125Kg, add precipitated silica 2.5Kg and superfine talcum powder 7.5Kg, uniformly mixing, is placed in 500L
In three layers of agitating paddle glass lined reaction vessel (stirrer bottom is ribbon impeller, and upper two layers are blade stirrer oar).
(2) being passed through sulfur dioxide gas into pressure-resistant 0.6MPa steel 1000L pressure vessels makes pressure rise extremely
0.25MPa, then being passed through chlorine makes pressure rise to 0.55MPa, the gaseous mixture of generation is standby.
(3) reactor stirring is opened, pressure -0.09MPa is evacuated to reactor, 55 DEG C of hot nitrogens is filled with into reactor
Gas makes pressure rise to 0.1MPa, and releasing to vacuumize again after pressure makes system pressure be -0.08MPa, so operates 3 times repeatedly,
Ultra violet lamp built in unlatching (the industrial ultraviolet lamp in 50W × 2), cooling water, controlling reaction temperature ＜ are passed through to reactor jacket
60℃.It is slowly introducing sulfur dioxide-chlorine gaseous mixture that step (2) obtains, control pressure ramp-up rate 0.01MPa/10min,
0.08MPa is risen to pressure, stops ventilation, continues stirring 20 minutes, reactor off-gas is discharged into exhaust treatment system, repeated above-mentioned
Operation 4 times, stop ultraviolet irradiation.With the acid gas in nitrogen displacement reactor until being substantially free of acid in the waste gas of discharge.Will
Material discharges reactor.
(4) material is put in enamelled vessels of the 500L with stirring, adds pure water 300L, stirred 20 minutes, leach out
About 200L water, then 200L water is added, repeat 4 times, test the water pH=6.0 of discharge.
(5) enamelled vessel bottom discharge valve is opened, material is discharged into centrifuge dewatering, then material is put into ebullated dryer
In, blow 105 DEG C of heated-air dryings 3.5 hours, discharging, cross 20 mesh sieves, obtain high Mooney viscosity CSM rubber powders.
The test result of high Mooney viscosity CSM rubber powders：Chlorinity 35.2wt% (GB/T 9872-1998)；Sulfur content
1.3wt% (GB4497-1984)；ML100 DEG C of 1+4 of Mooney viscosity 128 (GB/T 1232.1)；Volatile matter 0.28wt%.
(6)A:Above-mentioned CSM rubber powders 50Kg is taken, adds 10Kg TOTM (trioctyl trimellitate (TOTM)) and 0.5kg calcium stearates,
Be put into 70L rubber internal mixers, be kneaded to 100 DEG C, discharge sizing material, to opening rubber mixing machine on be cooled to 60 DEG C, in flakes, obtain
The oil-filled type CSM of sheet.
Sample detection result：ML1+4100 DEG C 62 of Mooney viscosity,
Sample vulcanizate physical property：Tensile strength 26.7Mpa,
Elongation at break 312%.
B:Above-mentioned CSM rubber powders 70Kg is taken, 14Kg DOTP (DOTP) and 0.7Kg calcium stearates is added, puts
Enter the stirring of homogenizer high speed, temperature rises to 60 DEG C of discharge materials.Material is added into extruding pelletization in Rubber Extruder, obtained
To granular oil-filled type CSM.
Sample tests：ML1+4100 DEG C 59 of Mooney viscosity,
Sample vulcanizate physical property：Tensile strength 27.2Mpa,
Elongation at break 333%.
Note：Cured properties method of testing：
Examine formula (mass parts PHR)：CSM 100；Extra light calcined magnesia 10；Carbon black N330 20；Carbon black N774 20；
TOTM 16；Pentaerythrite 3；DPTT 2；
Conditions of vulcanization：160 DEG C, 10 minutes.
Claims (4)
1. a kind of method that gas-solid phase reaction prepares oil-filled type chlorosulfonated polyethylene, it is characterised in that under described method includes
State step：
（1）High Mooney viscosity haloflex powder and antitack agent are added in reactor, wherein, antitack agent dosage is chlorine
Change the 3~8% of polyethylene powders quality；Described reactor uses Multilayer stirring-type fixed bed reactors, and its top is provided with insertion
Formula agitator and built-in ultraviolet lamp, the bottom of described plug-in type agitator is ribbon impeller and top is
Multiple layers of vanes formula agitating paddle,
Described haloflex powder：ML100 DEG C of 1+4 of Mooney viscosity is 100~150, and chlorinity is 23~40wt%, aqueous
＜ 1wt%, 400 μm of particle diameter ＜ are measured,
Described antitack agent is white carbon, superfine talcum powder or ultrafine aluminium hydroxide, wherein, the dosage of white carbon is gathered for chlorination
The dosage of the 1-2% of ethylene powder quality, superfine talcum powder or ultrafine aluminium hydroxide is the 2-6% of haloflex powder quality,
（2）Reactor stirring is opened, is evacuated to after -0.1~-0.08MPa and is filled with 50~60 DEG C of hot nitrogen to pressure and rises to
>=0.05Mpa, then release pressure and vacuumize again, be subsequently injected into hot nitrogen, repeat operation for several times；It is purple built in unlatching
Outside line light irradiation, reactor is vacuumized, to reactor be passed through the gaseous mixture of chlorine and sulfur dioxide to pressure 0.05~
80 DEG C of 0.1Mpa, controlling reaction temperature ＜, in 10~30 minutes reaction time, open exhaust-valve goalkeeper's reactor off-gas and drain at waste gas
Reason system；For several times, the total amount for being passed through gaseous mixture is 1.2~2.5 of theoretical amount needed for participation chlorosulfonation for operation more than repeating
Times, reaction product is washed to washings pH ＞ 6 repeatedly into 50-70 DEG C of purified water, then material dewatering is dried, obtains height
Mooney viscosity chlorosulfonated polyethylene powder,
Described gaseous mixture operates as follows：Vacuumizing first makes reactor pressure be -0.1~-0.08Mpa, Ran Houxiang
Reactor is passed through the gaseous mixture of chlorine and sulfur dioxide, makes reacting system pressure slow by 0.01~0.2MPa/10min speed
Rise, if reactor pressure stops logical gaseous mixture, be discharged into the waste gas in reactor after 10~30 minutes more than 0.08MPa
Exhaust treatment system, repeat the above and operate to gaseous mixture to be all passed through,
The volume ratio of chlorine and sulfur dioxide is 1 in described gaseous mixture：0.5~1.5,
（3）High Mooney viscosity chlorosulfonated polyethylene, rubber processing oil are pressed 1:0.1~0.4 ratio is added in homogenizer,
1~3% heat stabilizer is added, is stirred, is kneaded using traditional rubber and former is kneaded and is molded, obtain granular or piece
The oil-filled type chlorosulfonated polyethylene of shape,
Described rubber processing oil is：Trioctyl trimellitate (TOTM), phthalate, chlorinated paraffin, epoxidized soybean oil, the last of the ten Heavenly stems two
Acid esters.
2. the method that gas-solid phase reaction according to claim 1 prepares oil-filled type chlorosulfonated polyethylene, it is characterised in that：Institute
The liner material for the Multilayer stirring-type fixed bed reactors stated is enamel or steel lining fluoroplastics.
3. the method that gas-solid phase reaction according to claim 1 prepares oil-filled type chlorosulfonated polyethylene, it is characterised in that：Institute
The exhaust treatment system stated is composed in series by sulfur dioxide absorbing tower, hydrogen chloride absorption tower and tail gas absorber, and sulfur dioxide is inhaled
Receive tower and the sulfur dioxide in waste gas and water reaction are prepared into by-product sulfuric acid, hydrogen chloride absorption tower is by the hydrogen chloride absorption system in waste gas
Standby technical hydrochloric acid, tail gas absorber using the method that alkali sprays by all acid gas purifyings in waste gas, arrange by the tail gas after purification
Enter air.
4. the method that gas-solid phase reaction according to claim 1 prepares oil-filled type chlorosulfonated polyethylene, it is characterised in that：Institute
The agitating paddle for the plug-in type agitator stated is layer 2-4.
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| CN108948547A (en) * | 2018-05-29 | 2018-12-07 | 潍坊硕邑化学有限公司 | A kind of method that suspension chlorination reaction prepares oil-filled type chlorinated polyethylene rubber |
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| CN110172213B (en) * | 2019-05-09 | 2022-03-22 | 山东高信化学股份有限公司 | Method for reducing agglomeration of high chlorinated polyethylene resin on inner wall of drying bed |
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