CN109824804A - A kind of preparation method of chlorinated polyethylene rubber - Google Patents
A kind of preparation method of chlorinated polyethylene rubber Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of chlorinated polyethylene rubber, it is related to technical field of rubber preparation, mainly use water phase suspension, including chlorination, depickling, neutralization, dealkalize, centrifugation and drying and other steps, it is with short production cycle, water resources consumption is few, equipment requirement is low, environmental protection is achieved the purpose that, the chlorinated polyethylene rubber quality prepared is stable, chlorination degree is higher and tensile property is strong.Depickling, neutralization and dealkalize step in this method are all made of belt vacuum filter, shorten the time of preparing chlorinated polyethylene by aqueous phase suspension, while depickling, dealkalize effect are more thorough.In addition, neutralizing using shell as filler to waste liquid, so that low-concentration waste acid/spent lye that water phase suspension generates is reused, environmental protection is achieved the purpose that.
Description
Technical field
The present invention relates to technical field of rubber preparation, and in particular to a kind of preparation method of chlorinated polyethylene rubber.
Background technique
Haloflex is as high density polyethylene (HDPE) through high molecular material made from chlorination substitution reaction, with excellent resistance to
Hou Xing, resistance to ozone, chemical-resistant resistance, resistance to ag(e)ing, oil resistivity, anti-flammability and tinctorial property, according to chlorinity and remaining crystallization
Degree size can be divided into resin type haloflex and rubber-type chlorinated polyethylene.The former relative molecular mass, plasticization temperature, melting
Temperature and mechanical strength etc. are higher, mainly as the modifying agent of resins for universal use PE, ABS and PP etc., the latter's melt viscosity and modeling
Change temperature is lower, and mechanical strength and pliability are moderate, are mainly used for specific rubber.
The preparation method of haloflex generally includes solid phase method and solvent method, and chlorine is passed through polyethylene solids by the former
Powder, directly carries out gas-solid reaction in ebullated bed, but this method unstable quality, is difficult to control and be easy to cause environment dirty
Dye, therefore, was gradually eliminated in recent years.Polyethylene is dissolved in carbon tetrachloride solution by the latter, is passed through homogeneous reaction after chlorine,
Although this method is easily controllable, quality is stable, carbon tetrachloride enters destructible ozone layer in atmosphere, and then causes to endanger to environment
Evil.Therefore in recent years, water phase suspension and sour phase suspension method production haloflex are gradually received by more people, and extensively
For industrialized production.
Since sour phase suspension method is faced with after equipment for after-treatment corrosion resistance requires that high, equipment investment cost is higher and dry
Material need to grind, and then the higher problem of production cost, therefore more producers are ready using aqueous-phase suspending legal system in reality
Standby haloflex.Compared to the preparation method of other haloflexes, water phase suspension usually has that equipment investment is few, product
The advantages such as quality is stable and consumption of raw materials is low.
Application No. is 200610007861.8 patent disclose a kind of haloflex with high maximum elongation and
Preparation method and application.The invention is by the haloflex elongation at break with higher that water phase suspension is prepared and resists
Impact property can be applied to processing modified Corvic, and excellent anti-impact can be possessed in the case where additional amount is few
Performance is hit, while improving the mechanical performance and weather resistance of Corvic.But what is generated in chlorination process is a large amount of low dense
Degree hydrochloric acid needs to carry out depickling, neutralization and dealkalize, will cause the consumption of waste of time and great lot of water resources.
Application No. is 201110190159.0 patents to disclose a kind of method of preparing chlorinated polyethylene by aqueous phase suspension,
The invention combines sour phase suspension method to carry out process modification on the basis of water phase suspension, including chlorination, deacidification, centrifugation and
Drying and other steps, wherein deacidification step uses acid proof belt vacuum filter, adds water to spray the material after chlorination
Filtering deacidification, and drying steps then use boiling-bed drying, the equipment investment of the invention is relatively fewer, while with short production cycle,
Water consumption is small.But the waste water generated during this method is still faced with the problem of being not easy to be used appropriately, handling, and final preparation
The quality of haloflex out cannot be guaranteed.In addition, the setting of subsequent acid gas processing device, virtually increase again centainly at
This.
It is, thus, sought for a kind of time-consuming is short, water consumption is few, at low cost, and environmental pollution it is small prepare chlorinated polyethylene
The method of alkene, realize low-concentration hcl depickling, in and and dealkalize process, economize on resources, cost while, the property prepared
The excellent haloflex of energy.
Summary of the invention
In view of the problems of the existing technology the present invention, provides a kind of preparation method of chlorinated polyethylene rubber, the party
Method uses water phase suspension, including chlorination, depickling, neutralization, dealkalize, centrifugation and drying and other steps, with short production cycle, water resource to disappear
Consumption less, equipment requirement it is low, achieved the purpose that environmental protection, meanwhile, the chlorinated polyethylene rubber quality prepared using this method is steady
Determine, chlorination degree is higher and tensile property is strong.
To achieve the above object, The technical solution adopted by the invention is as follows:
The preparation method of chlorinated polyethylene rubber of the invention a kind of the following steps are included:
(1) chlorination: stirring after polyethylene, dispersing agent, surfactant and radical initiator is added in water, leads to simultaneously
Enter chlorine and heat, obtains material A；
(2) depickling, neutralization and dealkalize: by the material A in step (1) using water or treatment fluid A in belt vacuum filter
On carry out spray depickling, obtain material B；And, object is obtained in spraying on belt vacuum filter to material B using lye
Expect C；It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: will be dried after material D centrifugation to get chlorinated polyethylene rubber is arrived.
In some specific embodiments, according to parts by weight, water described in step (1) is 500-700 parts, described
Polyethylene be 55-70 part, the dispersing agent be 0.15-0.3 parts, the surfactant be 0.1-0.3 parts, it is described
Radical initiator is 0.05-0.1 parts.
Preferably, according to parts by weight, water described in step (1) is 600 parts, and the polyethylene is 60 parts, described
Dispersing agent be 0.2 part, the surfactant be 0.2 part, the radical initiator be 0.08 part.
Further, dispersing agent described in step (1) is selected from gelatin, polyvinyl alcohol, polyvinylpyrrolidone and dioxy
One of SiClx is a variety of.
Further, surfactant described in step (1) is selected from polyoxyethylene ether, cyclohexanone peroxide, azo two
Isobutyronitrile, neopelex, odium stearate and potassium stearate it is one or more.
Further, radical initiator described in step (1) is selected from di-isopropylbenzene hydroperoxide, peroxidating hexamethylene
Ketone, benzoyl peroxide, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, tert-butyl hydroperoxide, cumyl hydroperoxide, azo
Two different heptonitriles and azodiisobutyronitrile it is one or more.
Further, heating described in step (1) is heated up by three-stage and is carried out, and the three-stage heating is successively wrapped
It includes:
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.1-0.2MPa, reaction time 0.8-
1.2h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.2-0.3MPa, reaction time 1-
1.5h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.3-0.4MPa, and the reaction time is
0.8h。
Further, the total amount that chlorine is passed through described in step (1) is 3-7 times of the polyethylene weight；It is preferred that
Ground, the total amount that chlorine is passed through described in step (1) is 5 times of the polyethylene weight；
Further, three-stage heating, every section of temperature-rise period chlorine intake are respectively as follows: low-temperature zone: accounting for chlorine
Middle-temperature section: the 15-20% of total amount accounts for the 30-35% of chlorine total amount, high temperature section: accounting for the 45-55% of chlorine total amount, every section of chlorine
When reaching intake requirement, that is, stop being passed through.
Further, depickling, neutralization and dealkalize described in step (2) are enterprising in three belt vacuum filters respectively
Row, belt vacuum filter are a kind of High-cfficiency Filtration equipments that separation of solid and liquid is realized using negative pressure of vacuum as motive force, can be automatic
Complete blanking, be filtered, washed, blot, discharging and filter cloth cleaning and etc..In the present invention, three belt vacuum filters all by
The thermal resistance and acid-alkali resistances material such as stainless steel is made, its fillter section by way of spray as plus water or treatment fluid A plus lye and
Add water, while by negative pressure, the liquid on material is adsorbed, the processes such as depickling, neutralization and dealkalize are successively realized.
Further, lye described in step (2) is the sodium hydroxide solution that mass fraction is 30-45%.
Further, treatment fluid described in step (2) A's the preparation method comprises the following steps: by the material A in step (1) use water
After carrying out spray depickling, depickling waste liquid is collected；Spray neutralization is carried out using lye to material B in step (2), collects to neutralize and give up
Abandon liquid；By depickling waste liquid and after neutralizing waste liquid mixing, crosses and load conchiferous filled column to get treatment fluid A.The shellfish
Shell is complete common shell, and main component is calcium carbonate, has relatively rich hole surface, and coastal area is relatively conventional, is easy to get,
It can replace the materials such as lime stone.
Further, drying described in step (3) refers to and does material by wind model to fluidized bed dryer
Dry, wind speed 0.8m/s, drying temperature is 100-120 DEG C.
Beneficial effect obtained by the present invention is:
(1) chlorination reaction is carried out using three-stage, first segment reaction nearby slowly carries out in polyethylene fusing point (92 DEG C), makes
Polyethylene carries out partial oxidation, and then surface is hardened, and avoids polyethylene in the caking phenomenon of chlorination reaction process.In addition, three
Duan Fanying passes through the control to temperature, chlorine flow velocity and pressure, it is ensured that the stability of final gained haloflex guarantees simultaneously
The product chlorination degree prepared is higher, tensile property is stronger.
(2) depickling, neutralization and dealkalize step have been all made of in belt vacuum filter, are taken off by the way of spray
Acid, neutralization and dealkalize process, can neutralize the acid inside haloflex material without soda boiling, time-saving same
When, depickling, dealkalize effect are more thorough.The waste liquid that N-process and dealkalize process generate is collected, via shell
It after filler neutralizes, and then reuses, has saved the dosage of water in deacidification.Meanwhile using shell filler to waste liquid into
Row neutralizes, and realizes the neutralization of low concentration acid/base liquid progress, from the consumption of the materials such as lime stone, neutralizes efficiency also relatively
It is high.
(3) this invention simplifies depickling, neutralization and dealkalize step, shorten preparing chlorinated polyethylene by aqueous phase suspension when
Between, and depickling, dealkalize effect are more thorough, while low-concentration waste acid/spent lye that water phase suspension is generated is repeated
It utilizes, has achieved the purpose that environmental protection, while having prepared the haloflex haveing excellent performance.
Specific embodiment
Embodiment 1
A kind of preparation method of chlorinated polyethylene rubber, comprising the following steps:
(1) it is poly- that 55 weight account polyethylenes, 0.15 parts by weight gelatin, 0.1 parts by weight chlorination: are added in 500 parts by weight water
It is stirred after ethylene oxide ether and 0.05 parts by weight di-isopropylbenzene hydroperoxide, while being passed through chlorine and carrying out three-stage heating heating,
Obtain material A；
(2) depickling, neutralization and dealkalize: by the material A in step (1) using water or treatment fluid A in belt vacuum filter
On carry out spray depickling, obtain material B；And, object is obtained in spraying on belt vacuum filter to material B using lye
Expect C；It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: being 0.8m/ in wind speed into fluidized bed dryer by wind model after material D centrifugation
S, drying temperature are dried to arrive chlorinated polyethylene rubber under conditions of being 100 DEG C.
Three-stage described in step (1) heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.1MPa, reaction time 0.8h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.2MPa, reaction time 1h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.3MPa, reaction time 0.8h.
The total amount that chlorine is passed through described in step (1) is 3 times of the polyethylene weight；The three-stage liter
Temperature, every section of temperature-rise period chlorine intake are respectively as follows: low-temperature zone: accounting for the 15% of chlorine total amount, middle-temperature section: accounting for chlorine total amount
30%, high temperature section: accounting for the 55% of chlorine total amount, when every section of chlorine reaches intake requirement, that is, stops being passed through.
Depickling, neutralization and dealkalize described in step (2) are respectively adopted prior art means and filter in three belt vacuums
It is carried out on machine (dimension 1 rubber belt type vacuum filter of moral WDDU, China), three all by the thermal resistance and acid-alkali resistances material system such as stainless steel
At in its fillter section as added water or treatment fluid A plus lye and adding water by way of spray, while by negative pressure, to material
On liquid adsorbed, successively realize the processes such as depickling, neutralization and dealkalize.
The A's the preparation method comprises the following steps: that the material A in step (1) using water is carried out spray is de- for the treatment of fluid described in step (2)
After acid, depickling waste liquid is collected；Spray neutralization is carried out using lye to material B in step (2), collects and neutralizes waste liquid；It will take off
After sour waste liquid and neutralization waste liquid mixing, crosses and load conchiferous filled column to get treatment fluid A.
Embodiment 2
A kind of preparation method of chlorinated polyethylene rubber, comprising the following steps:
(1) 70 weight account polyethylenes, 0.3 weight account polyethylene alcohol, 0.3 parts by weight chlorination: are added in 700 parts by weight water
It is stirred after neopelex and 0.1 parts by weight cyclohexanone peroxide, while being passed through chlorine and carrying out three-stage heating and adding
Heat obtains material A；
(2) depickling, neutralization and dealkalize: by the material A in step (1) using water or treatment fluid A in belt vacuum filter
On carry out spray depickling, obtain material B；And, object is obtained in spraying on belt vacuum filter to material B using lye
Expect C；It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: being 0.8m/ in wind speed into fluidized bed dryer by wind model after material D centrifugation
S, drying temperature are dried to arrive chlorinated polyethylene rubber under conditions of being 120 DEG C.
Three-stage described in step (1) heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.2MPa, reaction time 1.2h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.3MPa, reaction time 1.5h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.4MPa, reaction time 0.8h.
The total amount that chlorine is passed through described in step (1) is 7 times of the polyethylene weight；The three-stage liter
Temperature, every section of temperature-rise period chlorine intake are respectively as follows: low-temperature zone: accounting for the 20% of chlorine total amount, middle-temperature section: accounting for chlorine total amount
35%, high temperature section: accounting for the 45% of chlorine total amount, when every section of chlorine reaches intake requirement, that is, stops being passed through.
Depickling, neutralization and dealkalize described in step (2) are respectively adopted prior art means and filter in three belt vacuums
It is carried out on machine (dimension 1 rubber belt type vacuum filter of moral WDDU, China), three all by the thermal resistance and acid-alkali resistances material system such as stainless steel
At in its fillter section as added water or treatment fluid A plus lye and adding water by way of spray, while by negative pressure, to material
On liquid adsorbed, successively realize the processes such as depickling, neutralization and dealkalize.
The A's the preparation method comprises the following steps: that the material A in step (1) using water is carried out spray is de- for the treatment of fluid described in step (2)
After acid, depickling waste liquid is collected；Spray neutralization is carried out using lye to material B in step (2), collects and neutralizes waste liquid；It will take off
After sour waste liquid and neutralization waste liquid mixing, crosses and load conchiferous filled column to get treatment fluid A.
Embodiment 3
A kind of preparation method of chlorinated polyethylene rubber, comprising the following steps:
(1) 60 weight account polyethylenes, 0.2 weight account polyethylene pyrrolidones, 0.2 chlorination: are added in 600 parts by weight water
It is stirred after parts by weight azodiisobutyronitrile and 0.08 parts by weight ammonium persulfate, while being passed through chlorine and carrying out three-stage heating and adding
Heat obtains material A；
(2) depickling, neutralization and dealkalize: by the material A in step (1) using water or treatment fluid A in belt vacuum filter
On carry out spray depickling, obtain material B；And, object is obtained in spraying on belt vacuum filter to material B using lye
Expect C；It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: being 0.8m/ in wind speed into fluidized bed dryer by wind model after material D centrifugation
S, drying temperature are dried to arrive chlorinated polyethylene rubber under conditions of being 100 DEG C.
Three-stage described in step (1) heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.15MPa, reaction time 1h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.25MPa, reaction time 1.2h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.35MPa, reaction time 0.8h.
The total amount that chlorine is passed through described in step (1) is 5 times of the polyethylene weight；The three-stage liter
Temperature, every section of temperature-rise period chlorine intake are respectively as follows: low-temperature zone: accounting for the 18% of chlorine total amount, middle-temperature section: accounting for chlorine total amount
32%, high temperature section: accounting for the 50% of chlorine total amount, when every section of chlorine reaches intake requirement, that is, stops being passed through.
Depickling, neutralization and dealkalize described in step (2) are respectively adopted prior art means and filter in three belt vacuums
It is carried out on machine (dimension 1 rubber belt type vacuum filter of moral WDDU, China), three all by the thermal resistance and acid-alkali resistances material system such as stainless steel
At in its fillter section as added water or treatment fluid A plus lye and adding water by way of spray, while by negative pressure, to material
On liquid adsorbed, successively realize the processes such as depickling, neutralization and dealkalize.
The A's the preparation method comprises the following steps: that the material A in step (1) using water is carried out spray is de- for the treatment of fluid described in step (2)
After acid, depickling waste liquid is collected；Spray neutralization is carried out using lye to material B in step (2), collects and neutralizes waste liquid；It will take off
After sour waste liquid and neutralization waste liquid mixing, crosses and load conchiferous filled column to get treatment fluid A.
Embodiment 4
A kind of preparation method of chlorinated polyethylene rubber, comprising the following steps:
(1) 58 weight account polyethylenes, 0.18 parts by weight of silica, 0.15 weight chlorination: are added in 550 parts by weight water
It is stirred after part odium stearate and 0.06 parts by weight tert-butyl hydroperoxide, while being passed through chlorine and carrying out three-stage heating heating,
Obtain material A；
(2) depickling, neutralization and dealkalize: by the material A in step (1) using water or treatment fluid A in belt vacuum filter
On carry out spray depickling, obtain material B；And, object is obtained in spraying on belt vacuum filter to material B using lye
Expect C；It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: being 0.8m/ in wind speed into fluidized bed dryer by wind model after material D centrifugation
S, drying temperature are dried to arrive chlorinated polyethylene rubber under conditions of being 100 DEG C.
Three-stage described in step (1) heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.1MPa, reaction time 0.9h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.2MPa, reaction time 1.1h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.3MPa, reaction time 0.8h.
The total amount that chlorine is passed through described in step (1) is 4 times of the polyethylene weight；The three-stage liter
Temperature, every section of temperature-rise period chlorine intake are respectively as follows: low-temperature zone: accounting for the 16% of chlorine total amount, middle-temperature section: accounting for chlorine total amount
31%, high temperature section: accounting for the 53% of chlorine total amount, when every section of chlorine reaches intake requirement, that is, stops being passed through.
Depickling, neutralization and dealkalize described in step (2) are respectively adopted prior art means and filter in three belt vacuums
It is carried out on machine (dimension 1 rubber belt type vacuum filter of moral WDDU, China), three all by the thermal resistance and acid-alkali resistances material system such as stainless steel
At in its fillter section as added water or treatment fluid A plus lye and adding water by way of spray, while by negative pressure, to material
On liquid adsorbed, successively realize the processes such as depickling, neutralization and dealkalize.
The A's the preparation method comprises the following steps: that the material A in step (1) using water is carried out spray is de- for the treatment of fluid described in step (2)
After acid, depickling waste liquid is collected；Spray neutralization is carried out using lye to material B in step (2), collects and neutralizes waste liquid；It will take off
After sour waste liquid and neutralization waste liquid mixing, crosses and load conchiferous filled column to get treatment fluid A.
Embodiment 5
A kind of preparation method of chlorinated polyethylene rubber, comprising the following steps:
(1) it is poly- that 65 weight account polyethylenes, 0.25 parts by weight gelatin, 0.25 parts by weight chlorination: are added in 650 parts by weight water
It is stirred after ethylene oxide ether and 0.09 parts by weight di-isopropylbenzene hydroperoxide, while being passed through chlorine and carrying out three-stage heating heating,
Obtain material A；
(2) depickling, neutralization and dealkalize: by the material A in step (1) using water or treatment fluid A in belt vacuum filter
On carry out spray depickling, obtain material B；And, object is obtained in spraying on belt vacuum filter to material B using lye
Expect C；It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: being 0.8m/ in wind speed into fluidized bed dryer by wind model after material D centrifugation
S, drying temperature are dried to arrive chlorinated polyethylene rubber under conditions of being 120 DEG C.
Three-stage described in step (1) heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.2MPa, reaction time 1.1h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.3MPa, reaction time 1.3h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.4MPa, reaction time 0.8h.
The total amount that chlorine is passed through described in step (1) is 6 times of the polyethylene weight；The three-stage liter
Temperature, every section of temperature-rise period chlorine intake are respectively as follows: low-temperature zone: accounting for the 16% of chlorine total amount, middle-temperature section: accounting for chlorine total amount
33%, high temperature section: accounting for the 51% of chlorine total amount, when every section of chlorine reaches intake requirement, that is, stops being passed through.
Depickling, neutralization and dealkalize described in step (2) are respectively adopted prior art means and filter in three belt vacuums
It is carried out on machine (dimension 1 rubber belt type vacuum filter of moral WDDU, China), three all by the thermal resistance and acid-alkali resistances material system such as stainless steel
At in its fillter section as added water or treatment fluid A plus lye and adding water by way of spray, while by negative pressure, to material
On liquid adsorbed, successively realize the processes such as depickling, neutralization and dealkalize.
The A's the preparation method comprises the following steps: that the material A in step (1) using water is carried out spray is de- for the treatment of fluid described in step (2)
After acid, depickling waste liquid is collected；Spray neutralization is carried out using lye to material B in step (2), collects and neutralizes waste liquid；It will take off
After sour waste liquid and neutralization waste liquid mixing, crosses and load conchiferous filled column to get treatment fluid A.
Comparative example 1
The difference from embodiment 1 is that according to parts by weight, water described in step (1) is 400 parts, the poly- second
Alkene is 50 parts, and the dispersing agent is 0.1 part, and the surfactant is 0.05 part, and the radical initiator is
0.03 part.
Comparative example 2
The difference from embodiment 1 is that according to parts by weight, water described in step (1) is 800 parts, the poly- second
Alkene is 80 parts, and the dispersing agent is 0.5 part, and the surfactant is 0.5 part, and the radical initiator is 0.15
Part.
Comparative example 3
It is carried out the difference from embodiment 1 is that heating described in step (1) is heated up by three-stage, described three sections
Formula heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.1MPa, reaction time 0.5h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.2MPa, reaction time 0.8h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.3MPa, reaction time 0.5h.
Comparative example 4
It is carried out the difference from embodiment 1 is that heating described in step (1) is heated up by three-stage, described three sections
Formula heats up
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.1MPa, reaction time 1.5h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.2MPa, reaction time 2h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.3MPa, reaction time 1h.
Comparative example 5
The difference from embodiment 1 is that three-stage described in step (1) heats up, every section of temperature-rise period chlorine intake
It is respectively as follows: low-temperature zone: accounts for the 10% of chlorine total amount, middle-temperature section: accounting for the 25% of chlorine total amount, high temperature section: accounts for chlorine total amount
65%, when every section of chlorine reaches intake requirement, that is, stop being passed through.
Comparative example 6
The difference from embodiment 1 is that three-stage described in step (1) heats up, every section of temperature-rise period chlorine intake
It is respectively as follows: low-temperature zone: accounts for the 25% of chlorine total amount, middle-temperature section: accounting for the 40% of chlorine total amount, high temperature section: accounts for chlorine total amount
35%, when every section of chlorine reaches intake requirement, that is, stop being passed through.
One, elongation at break and impact strength detection
The present invention is surveyed using " measurement of GB/T 528-2009 vulcanized rubber or thermoplastic elastomer tensile stress-strain performance "
The elongation at break for determining chlorinated polyethylene rubber in embodiment 1-5 and comparative example 1-6, using " GB/T 8814-2017, window are used
Not plasticized polyvinyl chloride (PVC-U) profile " measurement embodiment 1-5 and comparative example 1-6 in chlorinated polyethylene rubber shock resistance it is strong
Degree, as shown in table 1.
The elongation at break and impact strength of 1 chlorinated polyethylene rubber of table
| Example | Elongation at break (%) | Impact strength (KJ/m2) |
| Embodiment 1 | 872 | 19.95 |
| Embodiment 2 | 875 | 20.12 |
| Embodiment 3 | 880 | 20.45 |
| Embodiment 4 | 880 | 20.40 |
| Embodiment 5 | 878 | 20.15 |
| Comparative example 1 | 590 | 14.86 |
| Comparative example 2 | 580 | 14.39 |
| Comparative example 3 | 580 | 14.35 |
| Comparative example 4 | 570 | 14.21 |
| Comparative example 5 | 550 | 14.05 |
| Comparative example 6 | 555 | 14.12 |
As shown in Table 1, for the elongation at break of chlorinated polyethylene rubber 870% or more, shock resistance is strong in embodiment 1-5
Degree is above 19KJ/m2, and the elongation at break of the chlorinated polyethylene rubber in comparative example 1-6 is 600% hereinafter, shock resistance
Intensity is respectively less than 15KJ/m2.From the above results, the higher chlorinated polyethylene rubber of elongation at break, impact strength
Also higher, the elongation at break and impact strength of chlorinated polyethylene rubber are by the logical amount of chlorine of differential responses section, reaction time
And participate in reacting the influence of each content of material.
Two, chlorination degree and heat stability test
Chlorinity and chlorine distribution directly influence the property of entire material in chlorinated polyethylene rubber.The present invention uses " GB/
T 9872-1998 oxygen flask combustion method measures the content of bromine and chlorine in rubber and rubber product " detection embodiment 1-5 and comparative example 1-
The chlorination degree of chlorinated polyethylene rubber in 6；Meanwhile it being detected using thermogravimetric analyzer (PerkinElmer TGA4000, the U.S.) real
The reduced gravity situations of chlorinated polyethylene rubber in a 1-5 and comparative example 1-6 are applied, as shown in table 2.
2 haloflex chlorination degree of table and thermal stability
| Example | Chlorination degree (%) | Weight loss rate maximum temperature (DEG C) |
| Embodiment 1 | 34 | 350 |
| Embodiment 2 | 34 | 352 |
| Embodiment 3 | 35 | 358 |
| Embodiment 4 | 35 | 357 |
| Embodiment 5 | 35 | 356 |
| Comparative example 1 | 25 | 290 |
| Comparative example 2 | 24 | 286 |
| Comparative example 3 | 24 | 288 |
| Comparative example 4 | 25 | 291 |
| Comparative example 5 | 23 | 280 |
| Comparative example 6 | 22 | 275 |
As shown in Table 2, in embodiment 1-5 chlorinated polyethylene rubber chlorination degree and better heat stability, chlorination degree is in 25-
In 40% range, thermostabilization is preferably also, and weight loss rate maximum temperature is at 350 DEG C or more, and haloflex rubber in comparative example 1-6
The chlorination degree and thermal stability of glue are relatively poor.When i.e. the chlorination degree of chlorinated polyethylene rubber and thermal stability are mainly reacted
Between, the influence of chlorine intake and each raw material component.
In summary, the chlorinated polyethylene rubber better heat stability prepared using the method for the present invention, chlorination degree and
Impact strength is also relatively strong.
Finally it should be noted that the above content is merely illustrative of the technical solution of the present invention, rather than the present invention is protected
The limitation of range, the simple modification or equivalent replacement that those skilled in the art carry out technical solution of the present invention,
All without departing from the spirit and scope of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of chlorinated polyethylene rubber, which comprises the following steps:
(1) it chlorination: is stirred after polyethylene, dispersing agent, surfactant and radical initiator is added in water, while being passed through chlorine
Gas simultaneously heats, and obtains material A；
(2) depickling, neutralization and dealkalize: the material A in step (1) is enterprising in belt vacuum filter using water or treatment fluid A
Row spray depickling, obtains material B；And, material C is obtained in spraying on belt vacuum filter to material B using lye；
It carries out spray cleaning dealkalize on belt vacuum filter using water to material C, obtains material D；
(3) it is centrifuged and dry: will be dried after material D centrifugation to get chlorinated polyethylene rubber is arrived.
2. preparation method according to claim 1, it is characterised in that: according to parts by weight, water described in step (1) is
500-700 parts, the polyethylene is 55-70 parts, and the dispersing agent is 0.15-0.3 parts, and the surfactant is
0.1-0.3 parts, the radical initiator is 0.05-0.1 parts.
3. preparation method according to claim 1, it is characterised in that: dispersing agent described in step (1) is gelatin, poly- second
One of enol, polyvinylpyrrolidone and silica are a variety of.
4. preparation method according to claim 1, it is characterised in that: surfactant described in step (1) is polyoxy
One of vinethene, neopelex, odium stearate and potassium stearate are a variety of.
5. preparation method according to claim 1, it is characterised in that: radical initiator described in step (1) was
Hydrogen oxide diisopropylbenzene (DIPB), cyclohexanone peroxide, benzoyl peroxide, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, tert-butyl mistake
One of hydrogen oxide, cumyl hydroperoxide, azobisisoheptonitrile and azodiisobutyronitrile are a variety of.
6. preparation method according to claim 1, it is characterised in that: heating described in step (1) passes through three-stage liter
Temperature carries out, and the three-stage heating successively includes:
S1: low-temperature zone: reaction temperature section is 70-110 DEG C, reaction pressure 0.1-0.2MPa, reaction time 0.8-1.2h；
S2: middle-temperature section: reaction temperature section is 110-130 DEG C, reaction pressure 0.2-0.3MPa, reaction time 1-1.5h；
S3: high temperature section: reaction temperature section is 130-135 DEG C, reaction pressure 0.3-0.4MPa, reaction time 0.8h.
7. preparation method according to claim 1 or 6, it is characterised in that: be passed through the total amount of chlorine described in step (1)
It is 3-7 times of the polyethylene weight.
8. preparation method according to claim 6, it is characterised in that: the three-stage heating, every section of temperature-rise period chlorine
Gas intake is respectively as follows: low-temperature zone: the 15-20% of chlorine total amount accounted for, middle-temperature section: accounting for the 30-35% of chlorine total amount, high temperature section:
Account for the 45-55% of chlorine total amount.
9. preparation method according to claim 1, it is characterised in that: lye described in step (2) is that mass fraction is
The sodium hydroxide solution of 30-45%.
10. preparation method according to claim 1, it is characterised in that: the preparation side for the treatment of fluid A described in step (2)
Method are as follows: after the material A in step (1) is carried out spray depickling using water, collect depickling waste liquid；Material B in step (2) is made
Spray neutralization is carried out with lye, collects and neutralizes waste liquid；By depickling waste liquid and after neutralizing waste liquid mixing, crosses and be filled with shell
Filled column to get treatment fluid A.
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| CN112375164A (en) * | 2021-01-12 | 2021-02-19 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene suitable for manufacturing rubber-plastic magnet |
| CN112375326A (en) * | 2021-01-12 | 2021-02-19 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene with high elongation at break |
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| CN101481429A (en) * | 2009-01-13 | 2009-07-15 | 汪立波 | Industrial production method for producing chlorinated rubber by aqueous phase suspension |
| CN104193856A (en) * | 2014-09-04 | 2014-12-10 | 江苏科利新材料有限公司 | Preparation method for chlorinated polyethylene rubber |
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| CN101481429A (en) * | 2009-01-13 | 2009-07-15 | 汪立波 | Industrial production method for producing chlorinated rubber by aqueous phase suspension |
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| CN112375164A (en) * | 2021-01-12 | 2021-02-19 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene suitable for manufacturing rubber-plastic magnet |
| CN112375326A (en) * | 2021-01-12 | 2021-02-19 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene with high elongation at break |
| CN112375164B (en) * | 2021-01-12 | 2021-03-16 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene suitable for manufacturing rubber-plastic magnet |
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