CN109824804B - Preparation method of chlorinated polyethylene rubber - Google Patents
Preparation method of chlorinated polyethylene rubber Download PDFInfo
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Abstract
The invention provides a preparation method of chlorinated polyethylene rubber, which relates to the technical field of rubber preparation, mainly adopts a water phase suspension method, comprises the steps of chlorination, deacidification, neutralization, dealkalization, centrifugation, drying and the like, has short production period, less water resource consumption and low equipment requirement, achieves the aim of environmental protection, and the prepared chlorinated polyethylene rubber has stable quality, higher chlorination degree and strong tensile property. The steps of deacidification, neutralization and dealkalization in the method all adopt a belt type vacuum filter, so that the time for preparing the chlorinated polyethylene by the aqueous phase suspension method is shortened, and the effects of deacidification and dealkalization are more thorough. In addition, the waste liquid is neutralized by taking shells as fillers, so that low-concentration waste acid/waste alkali liquid generated by the aqueous suspension method can be recycled, and the aim of environmental protection is fulfilled.
Description
Technical Field
The invention relates to the technical field of rubber preparation, in particular to a preparation method of chlorinated polyethylene rubber.
Background
The chlorinated polyethylene is a high polymer material prepared by chlorination substitution reaction of high-density polyethylene, has excellent weather resistance, ozone resistance, chemical resistance, aging resistance, oil resistance, flame retardance and coloring performance, and can be divided into resin type chlorinated polyethylene and rubber type chlorinated polyethylene according to the chlorine content and the residual crystallinity. The former has high relative molecular mass, plasticizing temperature, melting temperature, mechanical strength and the like, is mainly used as a modifier for general resins such as PE, ABS, PP and the like, and the latter has low melting viscosity and plasticizing temperature and moderate mechanical strength and softness, and is mainly used for special rubber.
The production method of chlorinated polyethylene generally includes a solid phase method and a solvent method, in which chlorine gas is introduced into polyethylene solid powder to directly perform a gas-solid reaction in a fluidized bed, but this method is unstable in quality, difficult to control and likely to cause environmental pollution, and therefore, has been gradually eliminated in recent years. The latter dissolves polyethylene in carbon tetrachloride solution, and the homogeneous reaction is carried out after chlorine gas is introduced, although the method is easy to control and has stable quality, the ozone layer is easy to damage when carbon tetrachloride enters the atmosphere, and further the environment is damaged. Therefore, in recent years, chlorinated polyethylene produced by the aqueous phase suspension method and the acid phase suspension method is gradually accepted by more people, and is widely used for industrial production.
Because the acid phase suspension method faces the problems of high corrosion resistance requirement of post-treatment equipment, higher equipment investment cost, grinding of dried materials and higher production cost, more manufacturers are willing to adopt the water phase suspension method to prepare the chlorinated polyethylene in reality. Compared with other preparation methods of chlorinated polyethylene, the aqueous phase suspension method generally has the advantages of less equipment investment, stable product quality, low raw material consumption and the like.
The patent application No. 200610007861.8 discloses a chlorinated polyethylene with high elongation at break and its preparation method and application. The chlorinated polyethylene prepared by the aqueous phase suspension method has higher elongation at break and impact resistance, can be applied to processing modified polyvinyl chloride resin, can have excellent impact resistance under the condition of extremely small addition amount, and simultaneously improves the mechanical property and weather resistance of the polyvinyl chloride resin. However, a large amount of low-concentration hydrochloric acid generated in the chlorination process needs deacidification, neutralization and dealkalization, which causes time waste and large amount of water resource consumption.
The patent with application number 201110190159.0 discloses a method for preparing chlorinated polyethylene by an aqueous phase suspension method, which is improved by combining an acid phase suspension method on the basis of the aqueous phase suspension method and comprises the steps of chlorination, deacidification, centrifugation, drying and the like, wherein an acid-resistant belt type vacuum filter is adopted in the deacidification step, water is added into the chlorinated material for spray filtration to remove acid, and a fluidized drying bed is adopted in the drying step. However, the wastewater generated in the process of the method still faces the problem of difficult reasonable utilization and treatment, and the quality of the finally prepared chlorinated polyethylene cannot be ensured. In addition, the subsequent acid gas treatment device is arranged, so that certain cost is increased invisibly.
Therefore, a method for preparing chlorinated polyethylene with short time consumption, small water consumption, low cost and small environmental pollution needs to be found, so that the chlorinated polyethylene with excellent performance can be prepared while the processes of deacidification, neutralization and dealkalization of low-concentration hydrochloric acid are realized, resources are saved, and the cost is reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of chlorinated polyethylene rubber, which adopts a water phase suspension method and comprises the steps of chlorination, deacidification, neutralization, dealkalization, centrifugation, drying and the like, has short production period, less water resource consumption and low equipment requirement, and achieves the aim of environmental protection.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the chlorinated polyethylene rubber comprises the following steps:
(1) chlorination: adding polyethylene, a dispersing agent, a surfactant and a free radical initiator into water, stirring, introducing chlorine gas and heating to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: and centrifuging the material D and drying to obtain the chlorinated polyethylene rubber.
In some specific embodiments, the amount of the water in step (1) is 500-700 parts, the amount of the polyethylene is 55-70 parts, the amount of the dispersant is 0.15-0.3 part, the amount of the surfactant is 0.1-0.3 part, and the amount of the radical initiator is 0.05-0.1 part by weight.
Preferably, the water in the step (1) is 600 parts, the polyethylene is 60 parts, the dispersant is 0.2 part, the surfactant is 0.2 part, and the free radical initiator is 0.08 part by weight.
Further, the dispersant in the step (1) is one or more selected from gelatin, polyvinyl alcohol, polyvinylpyrrolidone and silicon dioxide.
Further, the surfactant in step (1) is selected from one or more of polyoxyethylene ether, cyclohexanone peroxide, azobisisobutyronitrile, sodium dodecylbenzene sulfonate, sodium stearate and potassium stearate.
Further, the radical initiator described in the step (1) is selected from one or more of diisopropylbenzene hydroperoxide, cyclohexanone peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisoheptonitrile and azobisisobutyronitrile.
Further, the heating in step (1) is performed by three-stage heating, and the three-stage heating sequentially comprises:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.1-0.2MPa, and the reaction time is 0.8-1.2 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.3-0.4MPa, and the reaction time is 0.8 h.
Further, the total amount of the chlorine gas introduced in the step (1) is 3-7 times of the weight of the polyethylene; preferably, the total amount of chlorine introduced in step (1) is 5 times the weight of the polyethylene;
further, the three-stage heating process comprises the following chlorine gas introduction amount in each stage of heating process: a low-temperature section: 15-20% of the total amount of chlorine, and a medium temperature section: 30-35% of the total amount of chlorine, high temperature section: accounting for 45-55% of the total chlorine, and stopping the introduction of the chlorine when each section of chlorine meets the introduction amount requirement.
Further, the deacidification, the neutralization and the dealkalization in the step (2) are respectively carried out on three belt type vacuum filters, the belt type vacuum filters are high-efficiency filtering equipment which takes vacuum negative pressure as a driving force to realize solid-liquid separation, and the steps of blanking, filtering, washing, sucking, discharging, cleaning filter cloth and the like can be automatically completed. In the invention, the three belt vacuum filters are all made of heat-resistant and acid-resistant materials such as stainless steel, etc., and the processes of deacidification, neutralization and dealkalization are sequentially realized by spraying water or treating fluid A, adding alkali fluid and adding water in the filtering section and simultaneously adsorbing the liquid on the material by negative pressure.
Further, the alkali liquor in the step (2) is a sodium hydroxide solution with the mass fraction of 30-45%.
Further, the preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A. The shell is a complete common shell, the main component of the shell is calcium carbonate, the shell has rich porous surfaces, is common and easily available in coastal areas, and can replace materials such as limestone and the like.
Further, the drying in the step (3) refers to conveying the material to a fluidized bed dryer for drying by wind power, wherein the wind speed is 0.8m/s, and the drying temperature is 100-120 ℃.
The beneficial effects obtained by the invention are as follows:
(1) the chlorination reaction is carried out in three stages, the first stage reaction is slowly carried out near the melting point (92 ℃) of the polyethylene, so that the polyethylene is partially chlorinated, the surface is hardened, and the caking phenomenon of the polyethylene in the chlorination reaction process is avoided. In addition, the three-stage reaction ensures the stability of the finally obtained chlorinated polyethylene by controlling the temperature, the chlorine flow rate and the pressure, and simultaneously ensures that the prepared product has higher chlorination degree and stronger tensile property.
(2) The steps of deacidification, neutralization and dealkalization all adopt belt vacuum filter, adopt the mode of spraying to carry out deacidification, neutralization and dealkalization process, need not the alkali and boil the inside acid of chlorinated polyethylene material and carry out the neutralization, when saving time, deacidification, dealkalization effect are more thorough. Waste liquid generated in the neutralization process and the dealkalization process is collected and is neutralized by the shell filler, so that the waste liquid is recycled, and the water consumption in the deacidification process is saved. Meanwhile, the waste liquid is neutralized by adopting shell filler, so that the neutralization of low-concentration acid/alkali liquor is realized, the consumption of materials such as limestone is avoided, and the neutralization efficiency is relatively high.
(3) The method simplifies the steps of deacidification, neutralization and dealkalization, shortens the time for preparing the chlorinated polyethylene by the aqueous phase suspension method, has more thorough deacidification and dealkalization effects, and simultaneously recycles the low-concentration waste acid/waste alkali liquor generated by the aqueous phase suspension method, thereby achieving the aim of environmental protection and preparing the chlorinated polyethylene with excellent performance.
Detailed Description
Example 1
A preparation method of chlorinated polyethylene rubber comprises the following steps:
(1) chlorination: adding 55 parts by weight of polyethylene, 0.15 part by weight of gelatin, 0.1 part by weight of polyoxyethylene ether and 0.05 part by weight of dicumyl peroxide into 500 parts by weight of water, stirring, introducing chlorine gas, and heating in a three-stage manner to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: and (3) centrifuging the material D, conveying the material D into a fluidized bed dryer by wind power, and drying the material D under the conditions that the wind speed is 0.8m/s and the drying temperature is 100 ℃ to obtain the chlorinated polyethylene rubber.
The three-stage heating in the step (1) sequentially comprises the following steps:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.1MPa, and the reaction time is 0.8 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.3MPa, and the reaction time is 0.8 h.
The total amount of the introduced chlorine in the step (1) is 3 times of the weight of the polyethylene; the three-stage heating is carried out, and the chlorine gas introduction amount in each stage of heating process is respectively as follows: a low-temperature section: accounting for 15 percent of the total amount of chlorine, and a medium temperature section: accounting for 30 percent of the total amount of chlorine, and a high-temperature section: accounting for 55 percent of the total amount of the chlorine, and stopping the chlorine introduction when each section of the chlorine meets the introduction amount requirement.
The deacidification, neutralization and dealkalization in the step (2) are respectively carried out on three belt type vacuum filters (Vide WDDU 1 rubber belt type vacuum filter, China) by adopting the prior art means, the three filters are all made of heat-resistant and acid-base-resistant materials such as stainless steel, etc., the processes of deacidification, neutralization and dealkalization are sequentially realized by adding water or treating fluid A, adding alkali liquid and water in the filtering section in a spraying mode and simultaneously adsorbing the liquid on the materials by negative pressure.
The preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A.
Example 2
A preparation method of chlorinated polyethylene rubber comprises the following steps:
(1) chlorination: adding 70 parts by weight of polyethylene, 0.3 part by weight of polyvinyl alcohol, 0.3 part by weight of sodium dodecyl benzene sulfonate and 0.1 part by weight of cyclohexanone peroxide into 700 parts by weight of water, stirring, introducing chlorine gas, and heating in a three-stage manner to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: and (3) centrifuging the material D, conveying the material D into a fluidized bed dryer by wind power, and drying the material D under the conditions that the wind speed is 0.8m/s and the drying temperature is 120 ℃ to obtain the chlorinated polyethylene rubber.
The three-stage heating in the step (1) sequentially comprises the following steps:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.2MPa, and the reaction time is 1.2 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.4MPa, and the reaction time is 0.8 h.
The total amount of the introduced chlorine in the step (1) is 7 times of the weight of the polyethylene; the three-stage heating is carried out, and the chlorine gas introduction amount in each stage of heating process is respectively as follows: a low-temperature section: 20% of the total amount of chlorine, and a medium temperature section: 35% of the total amount of chlorine, high temperature section: accounting for 45 percent of the total amount of the chlorine, and stopping the chlorine introduction when each section of the chlorine meets the introduction amount requirement.
The deacidification, neutralization and dealkalization in the step (2) are respectively carried out on three belt type vacuum filters (Vide WDDU 1 rubber belt type vacuum filter, China) by adopting the prior art means, the three filters are all made of heat-resistant and acid-base-resistant materials such as stainless steel, etc., the processes of deacidification, neutralization and dealkalization are sequentially realized by adding water or treating fluid A, adding alkali liquid and water in the filtering section in a spraying mode and simultaneously adsorbing the liquid on the materials by negative pressure.
The preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A.
Example 3
A preparation method of chlorinated polyethylene rubber comprises the following steps:
(1) chlorination: adding 60 parts by weight of polyethylene, 0.2 part by weight of polyvinylpyrrolidone, 0.2 part by weight of azobisisobutyronitrile and 0.08 part by weight of ammonium persulfate into 600 parts by weight of water, stirring, introducing chlorine gas, and heating in a three-stage manner to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: and (3) centrifuging the material D, conveying the material D into a fluidized bed dryer by wind power, and drying the material D under the conditions that the wind speed is 0.8m/s and the drying temperature is 100 ℃ to obtain the chlorinated polyethylene rubber.
The three-stage heating in the step (1) sequentially comprises the following steps:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.15MPa, and the reaction time is 1 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.35MPa, and the reaction time is 0.8 h.
The total amount of the introduced chlorine in the step (1) is 5 times of the weight of the polyethylene; the three-stage heating is carried out, and the chlorine gas introduction amount in each stage of heating process is respectively as follows: a low-temperature section: accounting for 18 percent of the total amount of chlorine, and a medium-temperature section: 32% of the total amount of chlorine, high temperature stage: accounting for 50 percent of the total amount of the chlorine, and stopping the chlorine introduction when each section of the chlorine meets the introduction amount requirement.
The deacidification, neutralization and dealkalization in the step (2) are respectively carried out on three belt type vacuum filters (Vide WDDU 1 rubber belt type vacuum filter, China) by adopting the prior art means, the three filters are all made of heat-resistant and acid-base-resistant materials such as stainless steel, etc., the processes of deacidification, neutralization and dealkalization are sequentially realized by adding water or treating fluid A, adding alkali liquid and water in the filtering section in a spraying mode and simultaneously adsorbing the liquid on the materials by negative pressure.
The preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A.
Example 4
A preparation method of chlorinated polyethylene rubber comprises the following steps:
(1) chlorination: adding 58 parts by weight of polyethylene, 0.18 part by weight of silicon dioxide, 0.15 part by weight of sodium stearate and 0.06 part by weight of tert-butyl hydroperoxide into 550 parts by weight of water, stirring, introducing chlorine gas, and heating in a three-stage manner to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: and (3) centrifuging the material D, conveying the material D into a fluidized bed dryer by wind power, and drying the material D under the conditions that the wind speed is 0.8m/s and the drying temperature is 100 ℃ to obtain the chlorinated polyethylene rubber.
The three-stage heating in the step (1) sequentially comprises the following steps:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.1MPa, and the reaction time is 0.9 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.3MPa, and the reaction time is 0.8 h.
The total amount of the introduced chlorine in the step (1) is 4 times of the weight of the polyethylene; the three-stage heating is carried out, and the chlorine gas introduction amount in each stage of heating process is respectively as follows: a low-temperature section: 16% of the total amount of chlorine, and a medium temperature section: 31% of the total amount of chlorine, high temperature stage: accounting for 53 percent of the total amount of the chlorine, and stopping the chlorine introduction when each section of the chlorine meets the introduction amount requirement.
The deacidification, neutralization and dealkalization in the step (2) are respectively carried out on three belt type vacuum filters (Vide WDDU 1 rubber belt type vacuum filter, China) by adopting the prior art means, the three filters are all made of heat-resistant and acid-base-resistant materials such as stainless steel, etc., the processes of deacidification, neutralization and dealkalization are sequentially realized by adding water or treating fluid A, adding alkali liquid and water in the filtering section in a spraying mode and simultaneously adsorbing the liquid on the materials by negative pressure.
The preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A.
Example 5
A preparation method of chlorinated polyethylene rubber comprises the following steps:
(1) chlorination: adding 65 parts by weight of polyethylene, 0.25 part by weight of gelatin, 0.25 part by weight of polyoxyethylene ether and 0.09 part by weight of dicumyl peroxide into 650 parts by weight of water, stirring, introducing chlorine gas, and heating in a three-stage manner to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: and (3) centrifuging the material D, conveying the material D into a fluidized bed dryer by wind power, and drying the material D under the conditions that the wind speed is 0.8m/s and the drying temperature is 120 ℃ to obtain the chlorinated polyethylene rubber.
The three-stage heating in the step (1) sequentially comprises the following steps:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.2MPa, and the reaction time is 1.1 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.4MPa, and the reaction time is 0.8 h.
The total amount of the introduced chlorine in the step (1) is 6 times of the weight of the polyethylene; the three-stage heating is carried out, and the chlorine gas introduction amount in each stage of heating process is respectively as follows: a low-temperature section: 16% of the total amount of chlorine, and a medium temperature section: 33% of the total amount of chlorine, high temperature stage: accounting for 51 percent of the total amount of the chlorine, and stopping the chlorine introduction when each section of the chlorine meets the introduction amount requirement.
The deacidification, neutralization and dealkalization in the step (2) are respectively carried out on three belt type vacuum filters (Vide WDDU 1 rubber belt type vacuum filter, China) by adopting the prior art means, the three filters are all made of heat-resistant and acid-base-resistant materials such as stainless steel, etc., the processes of deacidification, neutralization and dealkalization are sequentially realized by adding water or treating fluid A, adding alkali liquid and water in the filtering section in a spraying mode and simultaneously adsorbing the liquid on the materials by negative pressure.
The preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A.
Comparative example 1
The difference from example 1 is that, in the step (1), the water is 400 parts, the polyethylene is 50 parts, the dispersant is 0.1 part, the surfactant is 0.05 part, and the radical initiator is 0.03 part by weight.
Comparative example 2
The difference from the example 1 is that, in the step (1), the water is 800 parts, the polyethylene is 80 parts, the dispersant is 0.5 part, the surfactant is 0.5 part, and the radical initiator is 0.15 part by weight.
Comparative example 3
The difference from the example 1 is that the heating in the step (1) is performed by a three-stage temperature rise, which comprises in sequence:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.1MPa, and the reaction time is 0.5 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.3MPa, and the reaction time is 0.5 h.
Comparative example 4
The difference from the example 1 is that the heating in the step (1) is performed by a three-stage temperature rise, which comprises in sequence:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.1MPa, and the reaction time is 1.5 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.3MPa, and the reaction time is 1 h.
Comparative example 5
The difference from the example 1 is that the temperature rise in the step (1) is carried out in three stages, and the chlorine gas introduction amount in each stage of temperature rise is respectively as follows: a low-temperature section: 10% of the total amount of chlorine, and a medium temperature section: 25% of the total amount of chlorine, high temperature section: accounting for 65 percent of the total amount of the chlorine, and stopping the chlorine introduction when each section of the chlorine meets the introduction amount requirement.
Comparative example 6
The difference from the example 1 is that the temperature rise in the step (1) is carried out in three stages, and the chlorine gas introduction amount in each stage of temperature rise is respectively as follows: a low-temperature section: accounting for 25 percent of the total amount of chlorine, and a medium temperature section: 40% of the total amount of chlorine, high temperature section: accounting for 35 percent of the total amount of chlorine, and stopping the chlorine introduction when each section of chlorine meets the introduction amount requirement.
First, elongation at break and impact strength detection
The elongation at break of the chlorinated polyethylene rubber in examples 1-5 and comparative examples 1-6 is determined by GB/T528-.
TABLE 1 elongation at break and impact strength of chlorinated polyethylene rubber
| Examples of the invention | Elongation at Break (%) | Impact strength (KJ/m)2) |
| Example 1 | 872 | 19.95 |
| Example 2 | 875 | 20.12 |
| Example 3 | 880 | 20.45 |
| Example 4 | 880 | 20.40 |
| Example 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 can be seen from Table 1, the chlorinated polyethylene rubbers in examples 1 to 5 all had an elongation at break of 870% or more and an impact strength of more than 19KJ/m2While the elongation at break of the chlorinated polyethylene rubbers in comparative examples 1 to 6 is less than 600%, and the impact strength is less than 15KJ/m2. From the above results, it is understood that the chlorinated polyethylene rubber having a higher elongation at break has a higher impact strength, and the elongation at break and the impact strength of the chlorinated polyethylene rubber are affected by the amount of chlorine introduced into different reaction stages, the reaction time, and the contents of the substances involved in the reaction.
Second, detection of degree of chlorination and thermal stability
The chlorine content and chlorine distribution in chlorinated polyethylene rubber directly affect the properties of the whole material. The invention adopts GB/T9872 plus 1998 oxygen bottle combustion method to determine the content of bromine and chlorine in rubber and rubber products to detect the chlorination degree of the chlorinated polyethylene rubber in examples 1-5 and comparative examples 1-6; meanwhile, the weight loss of the chlorinated polyethylene rubbers in examples 1 to 5 and comparative examples 1 to 6 was measured using a thermogravimetric analyzer (Perkinelmer TGA4000, USA), as shown in Table 2.
TABLE 2 chlorinated polyethylene Chlorination and thermal stability
| Examples of the invention | Degree of chlorination (%) | Maximum temperature of weight loss Rate (. degree.C.) |
| Example 1 | 34 | 350 |
| Example 2 | 34 | 352 |
| Example 3 | 35 | 358 |
| Example 4 | 35 | 357 |
| Example 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 can be seen from Table 2, the chlorinated polyethylene rubbers in examples 1 to 5 are superior in the degree of chlorination and thermal stability, the degree of chlorination is in the range of 25 to 40%, the thermal stability is also the best, the maximum temperature of the weight loss rate is above 350 ℃, while the chlorinated polyethylene rubbers in comparative examples 1 to 6 are relatively inferior in the degree of chlorination and thermal stability. Namely, the chlorination degree and the thermal stability of the chlorinated polyethylene rubber are mainly influenced by the reaction time, the chlorine gas introduction amount and the components of the raw materials.
In conclusion, the chlorinated polyethylene rubber prepared by the method has good thermal stability, and high chlorination degree and impact strength.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. A preparation method of chlorinated polyethylene rubber is characterized by comprising the following steps:
(1) chlorination: adding polyethylene, a dispersing agent, a surfactant and a free radical initiator into water, stirring, introducing chlorine gas and heating to obtain a material A;
(2) deacidifying, neutralizing and dealkalizing: spraying water or treatment liquid A on the material A in the step (1) for deacidification on a belt type vacuum filter to obtain a material B; spraying and neutralizing the material B on a belt type vacuum filter by using alkali liquor to obtain a material C; spraying, cleaning and dealkalizing the material C on a belt type vacuum filter by using water to obtain a material D;
(3) centrifuging and drying: centrifuging the material D and drying to obtain chlorinated polyethylene rubber;
according to the parts by weight, the water in the step (1) is 500-700 parts, the polyethylene is 55-70 parts, the dispersant is 0.15-0.3 part, the surfactant is 0.1-0.3 part, and the free radical initiator is 0.05-0.1 part;
the heating in the step (1) is carried out through three-stage heating, and the three-stage heating sequentially comprises the following steps:
s1: a low-temperature section: the reaction temperature range is 70-110 ℃, the reaction pressure is 0.1-0.2MPa, and the reaction time is 0.8-1.2 h;
s2: and (3) in a medium-temperature section: the reaction temperature range is 110-;
s3: a high-temperature section: the reaction temperature range is 130-135 ℃, the reaction pressure is 0.3-0.4MPa, and the reaction time is 0.8 h;
the three-stage heating is carried out, and the chlorine gas introduction amount in each stage of heating process is respectively as follows: a low-temperature section: 15-20% of the total amount of chlorine, and a medium temperature section: 30-35% of the total amount of chlorine, high temperature section: accounting for 45-55% of the total amount of chlorine;
the preparation method of the treating fluid A in the step (2) comprises the following steps: spraying water on the material A obtained in the step (1) for deacidification, and collecting deacidification waste liquid; performing spray neutralization on the material B in the step (2) by using alkali liquor, and collecting neutralization waste liquid; mixing the deacidification waste liquid and the neutralization waste liquid, and passing through a packing column filled with shells to obtain a treatment liquid A.
2. The method of claim 1, wherein: the dispersing agent in the step (1) is one or more of gelatin, polyvinyl alcohol, polyvinylpyrrolidone and silicon dioxide.
3. The method of claim 1, wherein: the surfactant in the step (1) is one or more of polyoxyethylene ether, sodium dodecyl benzene sulfonate, sodium stearate and potassium stearate.
4. The method of claim 1, wherein: the free radical initiator in the step (1) is one or more of diisopropylbenzene hydroperoxide, cyclohexanone peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisoheptonitrile and azobisisobutyronitrile.
5. The method of claim 1, wherein: the total amount of the introduced chlorine in the step (1) is 3-7 times of the weight of the polyethylene.
6. The method of claim 1, wherein: the alkali liquor in the step (2) is a sodium hydroxide solution with the mass fraction of 30-45%.
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