CN107266614A - A kind of super high molecular weight haloflex and preparation method thereof, device and application - Google Patents
A kind of super high molecular weight haloflex and preparation method thereof, device and application Download PDFInfo
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- CN107266614A CN107266614A CN201710671704.5A CN201710671704A CN107266614A CN 107266614 A CN107266614 A CN 107266614A CN 201710671704 A CN201710671704 A CN 201710671704A CN 107266614 A CN107266614 A CN 107266614A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention provides a kind of super high molecular weight haloflex and preparation method thereof, device and application.The present invention prepares super high molecular weight haloflex by ultra-high molecular weight polyethylene chlorination, and the vapor and hydrogen chloride gas of generation are discharged and condensed in chlorination reaction process, by-product hydrochloric acid is obtained；The method production cost that the present invention is provided is low, and the by-product hydrochloric acid reusable edible of generation, no acidic discharge of wastewater, environmental pollution is small；And obtained super high molecular weight haloflex tensile strength can reach 20MPa, shore hardness (A) can reach 67, elongation at break can reach 820%, the super high molecular weight haloflex that the present invention is provided is applied in synthetic rubber, can significantly improve the tensile strength of rubber.
Description
Technical field
The present invention relates to the technical field of polymer, more particularly to a kind of super high molecular weight haloflex and its preparation side
Method, device and application.
Background technology
Haloflex (CPE) is polyethylene elastomer prepared by occur substitution reaction with chlorine, with excellent weather-proof
Property, resistance to ag(e)ing, oil resistivity, chemical proofing and anti-flammability, are mainly used as the anti-impact modifier and special type of synthetic resin
Synthetic rubber.Presently commercially available CPE molecular weight is 80000~200000, and the CPE of convenient molecular weight is widely used, but due to
It is saturability structure, it is difficult to realize that high density is crosslinked, therefore the mechanical strength of product is relatively low.
The preparation method of traditional haloflex is Aqueous phase, polyethylene is suspended in water in preparation process, is added
Chlorine is reacted and is made under certain conditions, because the hydrogen chloride produced in course of reaction is dissolved in water, after reaction terminates
5% or so watery hydrochloric acid can be formed because by-product hydrochloric acid concentration is too low, non-recovery value, it is necessary to after neutralisation treatment discharge,
Environmental pollution is easily caused, and causes whole preparation process chlorine utilization rate relatively low.
Do not have the relevant report of super high molecular weight haloflex at present.
The content of the invention
In view of this, present invention aims at provide a kind of super high molecular weight haloflex and preparation method thereof, device
And application, the preparation method step of the invention provided is simple, cost is low, chlorine utilization rate height, obtained by-product salt acid concentration height,
Reusable edible；And the ultra high molecular weight pvc of preparation is applied in synthetic rubber, the stretching that can improve rubber is strong
Degree.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of super high molecular weight haloflex, comprise the following steps：
Viscosity average molecular weigh is mixed for 1000000~6000000 polyethylene and chlorination reaction liquid, reaction system is obtained；
Chlorine is passed through into the reaction system, chlorination reaction is carried out, obtains super high molecular weight haloflex；
In the chlorination reaction process, the vapor of generation and hydrogen chloride discharge are condensed, by-product hydrochloric acid is obtained.
It is preferred that, the chlorination reaction liquid is the hydrochloric acid solution that mass concentration is 22~26%；
Also include dispersant, initiator, surfactant and suspension stabilizer in the chlorination reaction liquid；
On the basis of the quality of hydrochloric acid solution, in the chlorination reaction liquid mass content of dispersant be 0.03~
0.085%；The mass content of initiator is 0.001~0.005%；The mass content of surfactant is 0.01~0.05%；
The mass content of suspension stabilizer is 0.02~0.05%.
It is preferred that, the dispersant is hydrophabic silica and/or sodium polymethacrylate；
The initiator is the mixture of two or more peroxide；The peroxide is in 90 DEG C and 135 DEG C
Under half-life period be 0.5~2 hour；
The surfactant is nonionic surfactant；
The suspension stabilizer is polyvinylpyrrolidone and/or polyvinyl alcohol.
It is preferred that, the mass ratio of the polyethylene and chlorination reaction liquid is 1:3~8.
It is preferred that, the chlorination reaction preferably includes the first chlorination and the second chlorination successively；
The temperature of first chlorination is 70~120 DEG C；The pressure of first chlorination is 0~0.2MPa；
The dichlorated temperature is 120~138 DEG C；The dichlorated pressure is 0.2~0.6MPa；
The total time of the chlorination reaction is 2.5~4h.
The invention provides a kind of device for preparing super high molecular weight haloflex, including reactor (1), the reaction
Device is provided with chlorine inlet and gas vent on (1)；
The cooler (2) that import is connected with the reactor (1) gas vent；Cooler (2) upper end is provided with gas
Mutually export；Cooler (2) lower end is provided with liquid-phase outlet.
It is preferred that, the reactor (1) is glass lined reaction vessel；
The cooler (2) is falling liquid film graphite cooler or enamel cooler.
The invention provides the method that the device described in a kind of utilization such scheme prepares super high molecular weight haloflex,
It is characterised in that it includes following steps：
Viscosity average molecular weigh is added in reactor (1) for 1000000~6000000 polyethylene and chlorination reaction liquid, by
Chlorine inlet is passed through chlorine into reactor (1) and carries out chlorination reaction；
The vapor and hydrogen chloride that chlorination reaction is produced enter to be condensed in cooler (2), condenses obtained hydrochloric acid certainly
The liquid-phase outlet discharge of cooler (2).
The invention provides super high molecular weight haloflex prepared by preparation method described in such scheme, its feature exists
In the super high molecular weight haloflex is prepared by viscosity average molecular weigh for 1000000~6000000 polyethylene；Institute
The chlorinity for stating super high molecular weight haloflex is 25~40wt%.
The invention provides application of the super high molecular weight haloflex in synthetic rubber described in such scheme.
The invention provides a kind of preparation method of super high molecular weight haloflex, comprise the following steps：Viscous it will divide equally
Son amount is 1000000~6000000 polyethylene and chlorination reaction liquid mixing, obtains reaction system；It is passed through into reaction system
Chlorine, carries out chlorination reaction, obtains super high molecular weight haloflex；In the chlorination reaction process, by the vapor of generation
Condensed with hydrogen chloride discharge, obtain by-product hydrochloric acid.The present invention prepares superelevation by the polyethylene chlorination of super high molecular weight
Molecular weight haloflex, the vapor and hydrogen chloride gas of generation are discharged and condensed in chlorination reaction process, obtain pair
Product hydrochloric acid；The method production cost that the present invention is provided is low, the by-product hydrochloric acid reusable edible of generation, no acidic waste water row
Put, environmental pollution is small.Embodiment shows that the mass fraction for the by-product hydrochloric acid that the present invention is obtained is 26~28%, be can be used as
Chlorination reaction liquid is recycled.
Present invention also offers a kind of super high molecular weight haloflex, the super high molecular weight haloflex is by viscous equal
Molecular weight prepares for 1000000~6000000 polyethylene；The chlorinity of the super high molecular weight haloflex is 25
~40wt%.Embodiment shows that the tensile strength for the super high molecular weight haloflex that the present invention is provided can reach 20MPa,
Shore hardness (A) can reach 67, and elongation at break can reach 820%, and the super high molecular weight chlorination that the present invention is provided gathers
Ethene is applied in synthetic rubber, can significantly improve the tensile strength of rubber.
Brief description of the drawings
Fig. 1 is the installation drawing that the embodiment of the present invention prepares super high molecular weight haloflex；
In Fig. 1：1- reactors, 2- coolers.
Embodiment
The invention provides a kind of preparation method of super high molecular weight haloflex, comprise the following steps：
Viscosity average molecular weigh is mixed for 1000000~6000000 polyethylene and chlorination reaction liquid, reaction system is obtained；
Chlorine is passed through into the reaction system, chlorination reaction is carried out, obtains super high molecular weight haloflex；
In the chlorination reaction process, the vapor of generation and hydrogen chloride discharge are condensed, by-product hydrochloric acid is obtained.
The present invention mixes viscosity average molecular weigh for 1000000~6000000 polyethylene and chlorination reaction liquid, is reacted
System.In the present invention, the mass ratio of the polyethylene and chlorination reaction liquid is preferably 1:3~8, more preferably 1:3.5~5；
The viscosity average molecular weigh of the polyethylene is preferably 1500000~3000000, and more preferably 2000000~2500000；It is described poly-
Ethene is preferably polyethylene powder, and the particle diameter of the polyethylene is preferably 60~200 μm, more preferably 70~150 μm；The present invention
To the no particular/special requirement in source of the polyethylene, source is known using those skilled in the art, meets the present invention viscous respectively
The polyethylene that son amount is required, such as commercially available polyethylene.
In the present invention, the chlorination reaction liquid is preferably the hydrochloric acid solution that mass concentration is 22~26%, more preferably
Mass concentration is 23~25% hydrochloric acid solution；In the chlorination reaction liquid also include dispersant, initiator, surfactant and
Suspension stabilizer；On the basis of the quality of hydrochloric acid solution, the mass content of dispersant is preferably 0.03 in the chlorination reaction liquid
~0.085%, more preferably 0.05~0.08%, most preferably 0.06~0.07%；Initiator in the chlorination reaction liquid
Mass content is preferably 0.001~0.005%, and more preferably 0.002~0.004%；Surface-active in the chlorination reaction liquid
The mass content of agent is preferably 0.01~0.05%, and more preferably 0.02~0.03%.
In the present invention, the dispersant is preferably hydrophabic silica and/or sodium polymethacrylate；The initiator
The preferably mixture of two or more peroxide；Half-life period of the peroxide at 90 DEG C and 135 DEG C is preferred
For 0.5~2h, more preferably 1h；In a particular embodiment of the present invention, the initiator is preferably benzoyl peroxide and mistake
Aoxidize the mixture of diisopropylbenzene (DIPB)；The preferred phase of the mass ratio of benzoyl peroxide and cumyl peroxide in the mixture
Deng；The surfactant is preferably nonionic surfactant, more preferably polyethers nonionic surfactant, most preferably
For polyethers PF-10；The suspension stabilizer is preferably polyvinylpyrrolidone and/or polyvinyl alcohol.
The present invention does not have particular/special requirement to the preparation method of the chlorination reaction liquid, proportionally mixes each raw material components
It is uniform.
The present invention preferably under agitation mixes polyethylene and chlorination reaction liquid；Speed of the present invention to the stirring
There is no particular/special requirement, can be well mixed by material.In the present invention, the polyethylene is solid material, and chlorination is anti-
Answer after liquid mixing, in the presence of various auxiliary agents, polyethylene is suspended in chlorination reaction liquid.
Obtain after reaction system, the present invention is passed through chlorine into the reaction system, carry out chlorination reaction, obtain superelevation point
Son amount haloflex.The present invention does not have particular/special requirement to the intake of chlorine, in a particular embodiment of the present invention, preferably root
The intake of chlorine is determined according to the chlorinity in setting super high molecular weight haloflex.
Reaction system is preferably heated to 70~80 DEG C by the present invention, is then started to be passed through chlorine, is being passed through the process of chlorine
Temperature of continuing rising is relayed, is gradually increased with the pressure for increasing system of chlorine intake.In the present invention, the speed of the heating is excellent
Elect 5~15 DEG C/min, more preferably 10~12 DEG C/min as.
In the present invention, the chlorination reaction preferably includes the first chlorination and the second chlorination successively；First chlorination
Temperature is preferably 70~120 DEG C, more preferably 80~110 DEG C；The pressure of first chlorination is preferably 0~0.2MPa；With
Chlorine continues to be passed through the progress with chlorination reaction, and system pressure gradually increases, and when pressure reaches 0.2MPa in system, that is, enters
Second chlorination stage；The dichlorated temperature is preferably 120~138 DEG C, more preferably 125~135 DEG C；Second chlorine
The pressure of change is preferably 0.2~0.6MPa, more preferably 0.3~0.5MPa；The total time of the chlorination reaction is preferably 2.5~
4h, more preferably 3~3.5h, chlorination reaction time of the invention since chlorine be passed through when calculate.
Into after the second chlorination stage, the present invention will produce vapor in system and hydrogen chloride gas discharge is condensed,
Obtain by-product hydrochloric acid.The present invention is preferably by controlling the rate of discharge of vapor and hydrogen chloride gas to make dichlorated pressure
It is maintained at and requires pressure；The present invention does not have particular/special requirement to the rate of discharge of the vapor and hydrogen chloride gas, can be by the
The pressure of dichloride process maintains 0.2~0.6MPa.
In the present invention, it is passed through after chlorine, chlorination reaction, the present invention occur for polyethylene of the chlorine rapidly and in reaction system
It is preferred that by controlling being passed through the time and controlling the chlorination reaction time for chlorine, the present invention is whole by chlorine preferably in 2.5~4h
It is passed through, the present invention continues to react 15~25min preferably after chlorine is passed through and finished, to ensure that reaction is complete.
The invention provides a kind of device for preparing super high molecular weight haloflex, as shown in figure 1, including reactor
(1) chlorine inlet and gas vent, are provided with the reactor (1)；
The cooler (2) that import is connected with the reactor (1) gas vent；Cooler (2) upper end is provided with gas
Mutually export；Cooler (2) lower end is provided with liquid-phase outlet.
In the present invention, the reactor (1) is preferably glass lined reaction vessel；The glass lined reaction vessel preferably with
The glass lined reaction vessel of chuck, is easy to that material in reactor is heated or cooled；The cooler (2) is preferably falling liquid film stone
Black cooler or enamel cooler；The cooler bottom carries gas-liquid separator, can realize the function of gas-liquid separation.This
Invention does not have particular/special requirement to the concrete structure of the glass lined reaction vessel, anti-using enamel well known to those skilled in the art
Answer device；The present invention does not have particular/special requirement to the volume of the glass lined reaction vessel, in a particular embodiment of the present invention, can
To select the reactor of different volumes according to specific inventory；The present invention is cooled down to the falling liquid film graphite cooler and enamel
The concrete structure of device does not have particular/special requirement, uses falling liquid film graphite cooler well known to those skilled in the art and enamel cooler
.
The invention provides the method that the device described in a kind of utilization such scheme prepares super high molecular weight haloflex,
Comprise the following steps：
Viscosity average molecular weigh is added in reactor (1) for 1000000~6000000 polyethylene and chlorination reaction liquid, by
Chlorine inlet is passed through chlorine into reactor (1) and carries out chlorination reaction；
The vapor and hydrogen chloride that chlorination reaction is produced enter to be condensed in cooler (2), condenses obtained hydrochloric acid certainly
The liquid-phase outlet discharge of cooler (2).
In the present invention, valve is provided between the reactor (1) and cooler (2), in the specific implementation of the present invention
In example, chlorine is passed through into reactor (1) and carries out chlorination reaction, when reactor (1) interior pressure more than 0.2MPa (into the second chlorine
The change stage) when, Open valve enters the vapor and hydrogen chloride gas of generation and condensed in cooler (2), passes through control
Valve opening controls the rate of discharge of vapor and hydrogen chloride gas, so that reactor pressure is maintained 0.2~
0.6MPa；After chlorination reaction terminates, valve is closed.
In the present invention, the vapor and hydrogen chloride gas that chlorination reaction is produced enter after cooler, vapor and chlorination
Hydrogen is condensed, and obtains hydrochloric acid, and hydrochloric acid is discharged from the liquid-phase outlet of cooler (2), obtains hydrochloric acid by-product；If there is remaining chlorine
Change hydrogen, then hydrogen chloride gas is discharged from the gaseous phase outlet of cooler (2), obtains gaseous hydrogen chloride accessory substance.The present invention is carried
The mass fraction for the hydrochloric acid by-product that the method for confession is obtained is 26~28%, somewhat adjusts concentration and adds after reaction promoter, can
To be recycled as chlorination reaction liquid；The reaction promoter is dispersant, initiator, the surfactant described in such scheme
And suspension stabilizer, the species of each auxiliary agent is consistent with such scheme, will not be repeated here；The present invention can also obtain hydrogen chloride gas
Body, hydrogen chloride gas is important industrial chemicals, is easy to utilize.
After chlorination reaction terminates, reaction resulting material is preferably cooled to less than 80 DEG C by the present invention, is more preferably cooled to 65
Below DEG C, then material is discharged from reactor and post-processed.The present invention is preferably cold by being passed through into reactor jacket
But water accelerates the rate of temperature fall of material.
In the present invention, the post processing to the material preferably includes following steps：
Material is subjected to separation of solid and liquid, solid product is obtained；
The solid product is washed and dried successively, super high molecular weight haloflex is obtained.
The present invention does not have particular/special requirement to the specific method of the separation of solid and liquid, using well known to those skilled in the art solid
Liquid separating method, it is specific as filtered.In the present invention, the mass content of hydrochloric acid is about in the liquid obtained after filtering
For 29~31%, adjusting concentration and adding can recycle after auxiliary agent as chlorination reaction liquid.
In the present invention, the washing is preferably to wash, and the present invention preferably washs solid product to pH >=6；The present invention
, can be by the water in solid product using drying means well known to those skilled in the art to the no particular/special requirement of the drying
Divide and dry；The mass fraction of hydrochloric acid is about 6~19% in the washings obtained after washing first, can be with gained hydrochloric acid pair
Recycled after liquid mixture obtained by product or separation of solid and liquid as chlorination reaction liquid.
Present invention also offers super high molecular weight haloflex prepared by preparation method described in such scheme, the superelevation
Molecular weight haloflex is prepared by viscosity average molecular weigh for 1000000~6000000 polyethylene；It is preferred that by gluing equal molecule
Measure and prepared for 1500000~3000000 polyethylene；The chlorinity of the super high molecular weight haloflex is preferably 25
~40wt%, more preferably 30~35wt%.
The invention provides application of the super high molecular weight haloflex in synthetic rubber described in such scheme.This is sent out
The super high molecular weight haloflex of bright offer is used to prepare synthetic rubber, can improve the mechanical property of synthetic rubber.
With reference to embodiment is to super high molecular weight haloflex of the invention provided and preparation method thereof, device and answers
With being described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
By 125 μm of average grain diameter；Viscosity average molecular weigh 400000；The powdered high-density polyethylene 25Kg of 137 DEG C of fusing point and
(hydrochloric acid mass fraction is 24% to 150Kg chlorination reactions liquid in chlorination reaction liquid, in addition to 60g hydrophabic silicas, 4g peroxidating
Benzoyl, 4g cumyl peroxides, 40g polyvinylpyrrolidones, 10g polyethers PF-10) input 200L glass lined reaction vessels
(1) in, opening stirring makes material dispersed.
Being passed through steam to reactor (1) chuck makes material be warming up to 70 DEG C, then starts to be passed through chlorine, controls chlorine stream
100g/min is measured, when reaction temperature reaches 120 DEG C, during kettle pressure 0.2Mpa, reactor (1) and falling liquid film graphite cooler (2) is opened
Connecting valve, controlling opening of valve make kettle it is voltage-controlled system between 0.45~0.52Mpa, in falling liquid film graphite cooler gaseous phase outlet
Gaseous state HCl is collected, hydrochloric acid is collected in liquid-phase outlet.
120~138 DEG C of controlling reaction temperature, to being passed through after chlorine 27.5Kg, close reactor (1) and cooler (2) it
Between valve, be passed through cooling water to reacting kettle jacketing, continue to stir to temperature of charge and be down to 65 DEG C, open baiting valve by material from
Reactor is discharged into filter, isolates reaction medium 130Kg and stores for future use, HMCPE moves to other container and adds water cyclic washing extremely
Washings PH ＞ 6 (washing Water Sproading first), material centrifuge dewatering, hot-air is dried, and obtains ultra-high molecular weight polyethylene
(HMCPE) finished product.
By the 130Kg reaction mediums (HCl contents 29.7% after testing) of collection, add and wash recycle-water (after testing first
HCl contents 6.2%), it is compounded into 24%HCl standby.
Obtained super high molecular weight haloflex (HMCPE) analysis result：Chlorinity 35.4%；Shore hardness (A) 68；
Tensile strength 20.9Mpa；Elongation at break 825%.
Embodiment 2
By 135 μm of average grain diameter；Viscosity average molecular weigh 2,100,000；The powdered high-density polyethylene 500Kg of 141 DEG C of fusing point and
(hydrochloric acid mass fraction is 25% to 4000Kg chlorination reactions liquid in chlorination reaction liquid, in addition to 500g hydrophabic silicas, 60g mistakes
BP, 30g cumyl peroxides, 300g PVP K30s, 400g polyethers PF-10) input 5000L ward off
In glass reactor (1), opening stirring makes material dispersed.
Being passed through steam to reactor (1) chuck makes material be warming up to 75 DEG C, then starts to be passed through chlorine, controls chlorine stream
130g/min is measured, when reaction temperature reaches 120 DEG C, during kettle pressure 0.2Mpa, reactor (1) and falling liquid film graphite cooler (2) is opened
Connecting valve, controlling opening of valve make kettle it is voltage-controlled system between 0.2~0.6Mpa, falling liquid film graphite cooler gaseous phase outlet receive
Collect gaseous state HCl, hydrochloric acid is collected in liquid-phase outlet.
135 DEG C of controlling reaction temperature, to being passed through after chlorine 550Kg, the valve closed between reactor (1) and cooler (2)
Door, cooling water is passed through to reacting kettle jacketing, is continued to stir to temperature of charge and is down to 65 DEG C, opens baiting valve by material from reactor
Filter is discharged into, reaction medium is isolated and stores for future use, HMCPE moves to other container and adds water cyclic washing to washings PH ＞ 6
(washing Water Sproading first), material centrifuge dewatering, hot-air is dried, and obtains HMCPE finished products.
The reaction medium of collection is added and washs recycle-water first, 24%HCl is compounded into standby.
Obtained super high molecular weight haloflex (HMCPE) analysis result：Chlorinity 35.2%；Shore hardness (A) 67；
Tensile strength 20.6Mpa；Elongation at break 820%.
Embodiment 3
The HMCPE prepared using embodiments of the invention 1 prepares synthetic rubber, and mixing is made according to following rubber compounding
Glue：HMCPE 100, epoxidized soybean oil 30, carbon black 10, calcium carbonate superfine powder 25, cumyl peroxide 3, TAIC 3.
Conditions of vulcanization：170℃×30min
Physical property to gained vulcanizate detects, the data obtained:Tensile strength 16.1Mpa, elongation at break
357%, tearing strength 7.23Mpa.
As seen from the above embodiment, the present invention prepares super high molecular weight chlorination by the polyethylene chlorination of super high molecular weight and gathered
Ethene, the vapor and hydrogen chloride gas of generation are discharged and condensed in chlorination reaction process, obtain by-product hydrochloric acid；This hair
The method production cost of bright offer is low, and the by-product hydrochloric acid reusable edible of generation, wastewater discharge is few, and environmental pollution is small；
And the tensile strength of obtained super high molecular weight haloflex can reach 20.9MPa, shore hardness (A) can reach 67,
Elongation at break can reach 820%, and the super high molecular weight haloflex that the present invention is provided is applied in synthetic rubber, can
To significantly improve the tensile strength of rubber.
As seen from the above embodiment, it is only the preferred embodiment of the present invention that the present invention is described above, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, can also make it is some improvement and
Retouching, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of super high molecular weight haloflex, comprises the following steps：
Viscosity average molecular weigh is mixed for 1000000~6000000 polyethylene and chlorination reaction liquid, reaction system is obtained；
Chlorine is passed through into the reaction system, chlorination reaction is carried out, obtains super high molecular weight haloflex；
In the chlorination reaction process, the vapor of generation and hydrogen chloride discharge are condensed, by-product hydrochloric acid is obtained.
2. preparation method according to claim 1, it is characterised in that the chlorination reaction liquid be mass concentration be 22~
26% hydrochloric acid solution；
Also include dispersant, initiator, surfactant and suspension stabilizer in the chlorination reaction liquid；
On the basis of the quality of hydrochloric acid solution, the mass content of dispersant is 0.03~0.085% in the chlorination reaction liquid；Draw
The mass content for sending out agent is 0.001~0.005%；The mass content of surfactant is 0.01~0.05%；Suspension stabilizer
Mass content be 0.02~0.05%.
3. preparation method according to claim 2, it is characterised in that the dispersant is hydrophabic silica and/or poly-
Sodium methacrylate；
The initiator is the mixture of two or more peroxide；The peroxide is at 90 DEG C and 135 DEG C
Half-life period is 0.5~2 hour；
The surfactant is nonionic surfactant；
The suspension stabilizer is polyvinylpyrrolidone and/or polyvinyl alcohol.
4. preparation method according to claim 1 or 2, it is characterised in that the quality of the polyethylene and chlorination reaction liquid
Than for 1:3~8.
5. preparation method according to claim 1, it is characterised in that the chlorination reaction includes the first chlorination and the successively
Dichloride；
The temperature of first chlorination is 70~120 DEG C；The pressure of first chlorination is 0~0.2MPa；
The dichlorated temperature is 120~138 DEG C；The dichlorated pressure is 0.2~0.6MPa；
The total time of the chlorination reaction is 2.5~4h.
6. it is provided with a kind of device for preparing super high molecular weight haloflex, including reactor (1), the reactor (1)
Chlorine inlet and gas vent；
The cooler (2) that import is connected with the reactor (1) gas vent；Cooler (2) upper end is provided with gas phase and gone out
Mouthful；Cooler (2) lower end is provided with liquid-phase outlet.
7. device according to claim 6, it is characterised in that the reactor (1) is glass lined reaction vessel；
The cooler (2) is falling liquid film graphite cooler or enamel cooler.
8. the method for super high molecular weight haloflex is prepared using the device described in claim 6 or 7, it is characterised in that bag
Include following steps：
Viscosity average molecular weigh is added in reactor (1) for 1000000~6000000 polyethylene and chlorination reaction liquid, by chlorine
Import is passed through chlorine into reactor (1) and carries out chlorination reaction；
The vapor and hydrogen chloride that chlorination reaction is produced enter to be condensed in cooler (2), is condensed obtained hydrochloric acid and is cooled down certainly
The liquid-phase outlet discharge of device (2).
9. super high molecular weight haloflex prepared by preparation method described in Claims 1 to 5 or claim 8 any one,
Characterized in that, the super high molecular weight haloflex is prepared by viscosity average molecular weigh for 1000000~6000000 polyethylene
Obtain；The chlorinity of the super high molecular weight haloflex is 25~40wt%.
10. application of the super high molecular weight haloflex in synthetic rubber described in claim 9.
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