CN103435723A - Apparatus and method for preparing chlorinated polyethylene - Google Patents
Apparatus and method for preparing chlorinated polyethylene Download PDFInfo
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- CN103435723A CN103435723A CN2013101510632A CN201310151063A CN103435723A CN 103435723 A CN103435723 A CN 103435723A CN 2013101510632 A CN2013101510632 A CN 2013101510632A CN 201310151063 A CN201310151063 A CN 201310151063A CN 103435723 A CN103435723 A CN 103435723A
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Abstract
The invention discloses an apparatus and a method for preparing chlorinated polyethylene. The apparatus comprises a plasma generating device and a chlorination reacting device. A stirrer is disposed in the plasma generating device; a discharge power supply is disposed out of the plasma generating device; and the chlorination reacting device is provided with a stirrer. The method divides a chlorination reaction initiated by plasma into two processes being a fast reaction process of initiating a chlorine gas to react by processing PE powder with the plasma and a slow dispersion process of the chlorine gas in the PE powder, so that a violent reaction of the chlorine gas under the condition of the plasma can be prevented and chlorination security can be increased. By adopting the stirrers in both the plasma generating device and the chlorination reacting device, contact efficiency of the PE powder with the plasma and the chlorine gas is increased and deep chlorination of PE is facilitated.
Description
Technical field
The present invention relates to the cross discipline technical field of plasma science and synthesis of polymer material science, relate in particular to a kind of device and method for preparing chlorinatedpolyethylene.
Background technology
Chlorinatedpolyethylene (Chlorinated Polyethylene, referred to as CPE) is a kind of macromolecular material of excellent property.It is by polyethylene (Polyethylene, referred to as PE) through chlorination modified and the preparation macromolecular material.Universal CPE cl content is generally in 35% left and right, and the highest cl content can reach 73.2% in theory.The advantages such as that CPE has is heat-resisting, oil resistant, anti-ozone, fire-retardant, good insulating, widespread use in the fields such as plastic-steel door and window, protective system, electric wire, magneticsubstance, flame-retardant rubber pipe.And along with China's chlorine industry fast development, excessive chlorine brings serious safety and environment problem, utilizing on a large scale chlorine is the key that promotes the chlorine industry Sustainable development, and CPE is as bulk chemical, and its production is to solve one of excessive effective ways of chlorine.
The CPE production method mainly contains solvent method, water phase suspension at present.Solvent method is that the PE powder is dissolved in carbon tetrachloride solvent, carries out a kind of processing method of chlorination reaction under the organic peroxide evocating agent effect with chlorine, and this technique mainly comprises the operations such as chlorination, solution filter, resin settled, drying, solvent recuperation.This technical process is long, cost is high, easily cause environmental pollution, and carbon tetrachloride solvent has destruction to atmospheric ozone layer, signing due to Montreal Protocol on Substances that Deplete the Ozone Layer, China proposes strict index to tetracol phenixin remaining in CPE, and has closed many carbon tetrachloride solvent methods and produced the CPE device.Water phase suspension be the PE powder is suspended in water or hydrochloric acid medium in, logical chlorine under organic peroxide evocating agent or UV-light exist, a kind of processing method of through depickling, neutralization, washing, the operation such as centrifugal, dry, producing CPE.This method can be produced the CPE of good combination property, but also Shortcomings part of this technique: as wet chlorine has serious corrosion to conversion unit, so reactor must be used expensive titanium palldium alloy material; And in production process, there are a large amount of acid waste water and waste gas to produce, produce in 1 ton of CPE process, will produce approximately 20 tons of acid waste waters and 200m
3acid waste gas.With 700,000 tons of calculating of domestic 2011 annual CPE output, the acid waste water of generation is about 1,400 ten thousand tons, acid waste gas 1.4 hundred million m
3.Have serious environmental pollution because prepared in the CPE process by solvent method and water phase suspension, how to realize energy-saving and emission-reduction and to control to pollute becoming study hotspot from beginning of production, carrying out plasma body, to prepare CPE be a kind of effective solution.
Summary of the invention
The object of the invention is exactly in order to make up the defect of prior art, and a kind of device and method for preparing chlorinatedpolyethylene is provided.
The present invention is achieved by the following technical solutions:
A kind of device for preparing chlorinatedpolyethylene, include plasma producing apparatus and chlorination reaction device, described plasma producing apparatus includes plasma generator, be provided with whipping appts one in plasma generator, be provided with the unstripped gas import at the top of plasma generator, the import of PE powder and vacuum orifice, described unstripped gas import connects the raw material gas cylinder, vacuum orifice connects vacuum pump, be provided with the unstripped gas outlet and process the outlet of rear PE material on plasma generator, plasma generator also is connected with plasma electrical source with vacuum display device respectively, described chlorination reaction device includes chlorination reactor, be provided with whipping appts two in the side of chlorination reactor, be provided with gas feed and pneumatic outlet at the top of chlorination reactor, be provided with opening for feed and discharge port in the left side of chlorination reactor, right side at chlorination reactor is provided with blast inlet, described blast inlet is connected with gas blower, described gas feed is connected with gas cylinder, pneumatic outlet is connected with device for absorbing tail gas, after opening for feed connects the processing in plasma producing apparatus, the PE material exports, and discharge port is connected with the CPE treatment unit.
Also be provided with surge tank and preheating can between described gas cylinder and gas feed; Described device for absorbing tail gas includes two packed absorbers and the alkali cuvette connected by pipeline successively; Described CPE treatment unit includes strainer and the kiln connected successively.
The radio frequency plasma body device that described plasma producing apparatus is negative pressure or atmospheric operation, dielectric barrier discharge plasma device or microwave plasma device, the discharge mode of described plasma producing apparatus includes three kinds of continuous discharges, intermittent discharge, impulsive discharge.
Described plasma generator is vertical producer or horizontal producer; Vertical producer can be provided with end stirring or stir on top; Horizontal producer is cylindrical shell rotating generator or the inner producer that is provided with the axle stirring.
Described chlorination reactor is horizontal reactor or vertical reactor; Horizontal reactor is cylindrical shell rotatable reactor or the inner reactor that is provided with the axle stirring; Vertical reactor can be established the end and stir or push up and stir.
A kind of method for preparing chlorinatedpolyethylene comprises the following steps:
1) the PE powder is joined plasma generator from the import of PE powder, unstripped gas flows into plasma generator from the unstripped gas import, opens vacuum pump and is evacuated to low pressure, and PE powder median size is 30 ~ 300 microns;
2) start whipping appts one, start the plasma electrical source electric discharge, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 0.1 ~ 15W/cm
3, the PE powder is 5s ~ 30min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 20 ~ 80 ℃, and pressure is 10 ~ 10000Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor through the outlet of PE material and opening for feed, pass into chlorine from gas feed and carry out chlorination reaction, start whipping appts two, chlorination temperature is 30 ~ 140 ℃, time of chlorinating is 1 ~ 6h, and chloridating gas pressure is 1000 ~ 150000 Pa;
4) reaction end gas is discharged from pneumatic outlet, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber separates, and the complete chlorine of unreacted absorbs and processes by the alkali cuvette;
5) by gas blower, the CPE product obtained after chlorination is entered to strainer from discharge port, then dry through kiln.
The mixed gas of the mixed gas that described unstripped gas is argon gas, nitrogen or argon gas and nitrogen, chlorine or the rare gas elementes such as chlorine and argon gas.
Advantage of the present invention is: the present invention causes chlorination reaction by plasma body and is divided into two step processes, be that Cement Composite Treated by Plasma PE powder causes the fast response process of chlorine reaction and chlorine in the inner slow diffusion process of PE powder, avoided chlorine violent reaction under the condition of plasma, improved the chlorination security, adopted whipping appts at plasma generator and chlorination reactor in all, improve the contact efficiency of PE powder and plasma body, chlorine, be conducive to realize the degree of depth chlorination of PE.
The accompanying drawing explanation
Fig. 1 is the structural principle schematic diagram of the plasma body provided by the invention plasma producing apparatus for preparing CPE.
Fig. 2 is the structural principle schematic diagram of the plasma body provided by the invention chlorination reaction device for preparing CPE.
Fig. 3 is the general arrangement structural principle schematic diagram that plasma body chlorination provided by the invention prepares CPE.
Embodiment
As Fig. 1, 2, shown in 3, a kind of device for preparing chlorinatedpolyethylene, include plasma producing apparatus and chlorination reaction device, described plasma producing apparatus includes plasma generator 1, be provided with whipping appts 1 in plasma generator 1, be provided with unstripped gas import 3 at the top of plasma generator 1, the import 4 of PE powder and vacuum orifice 5, described unstripped gas import 3 connects raw material gas cylinder 6, vacuum orifice 5 connects vacuum pump 7, be provided with unstripped gas outlet 8 and process rear PE material outlet 9 on plasma generator 1, plasma generator 1 also is connected with plasma electrical source 11 with vacuum display device 10 respectively, described chlorination reaction device includes chlorination reactor 12, be provided with whipping appts 2 13 in the side of chlorination reactor 12, be provided with gas feed 14 and pneumatic outlet 15 at the top of chlorination reactor 12, be provided with opening for feed 16 and discharge port 17 in the left side of chlorination reactor 12, right side at chlorination reactor 12 is provided with blast inlet, described blast inlet is connected with gas blower 18, described gas feed 14 is connected with gas cylinder 19, pneumatic outlet 15 is connected with device for absorbing tail gas 20, PE material outlet 9 after the processing that opening for feed 16 connects in plasma producing apparatus, discharge port 17 is connected with CPE treatment unit 21.
Also be provided with surge tank 22 and preheating can 23 between described gas cylinder 19 and gas feed 14; Described device for absorbing tail gas 20 includes two packed absorbers 24 and the alkali cuvette 25 connected by pipeline successively; Described CPE treatment unit 21 includes strainer 26 and the kiln 27 connected successively.
The radio frequency plasma body device that described plasma producing apparatus is negative pressure or atmospheric operation, dielectric barrier discharge plasma device or microwave plasma device, the discharge mode of described plasma producing apparatus includes three kinds of continuous discharges, intermittent discharge, impulsive discharge.
Described plasma generator 1 is vertical producer or horizontal producer; Vertical producer can be provided with end stirring or stir on top; Horizontal producer is cylindrical shell rotating generator or the inner producer that is provided with the axle stirring.
Described chlorination reactor 12 is horizontal reactor or vertical reactor; Horizontal reactor is cylindrical shell rotatable reactor or the inner reactor that is provided with the axle stirring; Vertical reactor can be established the end and stir or push up and stir.
A kind of method for preparing chlorinatedpolyethylene comprises the following steps:
1) the PE powder is joined plasma generator 1 from PE powder import 4, unstripped gas flows into plasma generator 1 from unstripped gas import 3, opens vacuum pump 7 and is evacuated to low pressure, and PE powder median size is 30 ~ 300 microns;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 0.1 ~ 15W/cm
3, the PE powder is 5s ~ 30min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 20 ~ 80 ℃, and pressure is 10 ~ 10000Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 through the outlet 9 of PE material and opening for feed 16, pass into chlorine from gas feed 14 and carry out chlorination reaction, start whipping appts 2 13, chlorination temperature is 30 ~ 140 ℃, time of chlorinating is 1 ~ 6h, and chloridating gas pressure is 1000 ~ 150000 Pa;
4) reaction end gas is discharged from pneumatic outlet 15, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted absorbs and processes by alkali cuvette 25;
5) by gas blower 18, the CPE product obtained after chlorination is entered to strainer 26 from discharge port 17, then dry through kiln 27.
The mixed gas of the mixed gas that described unstripped gas is argon gas, nitrogen or argon gas and nitrogen, chlorine or the rare gas elementes such as chlorine and argon gas.
Embodiment mono-:
1) the PE powder is joined plasma generator 1 from PE powder import 4, argon gas flows into plasma generator 1 from unstripped gas import 3, opens vacuum pump 7 and is evacuated to low pressure;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 0.8W/cm
3; The PE powder is 10min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 30 ~ 50 ℃, and pressure is 100Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 from discharge port, passes into chlorine and carries out chlorination reaction, and chlorination temperature is at 130 ℃, and time of chlorinating is 3h, and chloridating gas pressure is 120000 Pa;
4) reaction end gas is discharged from chlorination reactor 12, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted can recycle or absorbed processing with alkali cuvette 25;
5) by gas blower 18, the CPE product obtained after chlorination is entered to strainer from discharge port, drying through kiln.After tested, in CPE, cl content is 35%.
Embodiment bis-:
1) the PE powder is joined plasma generator 1 from PE powder import 4, argon gas and chlorine flow into plasma generator 1 from unstripped gas import 3, open vacuum pump 7 and are evacuated to low pressure;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, causes chlorination reaction, and the power density of plasma body is 5W/cm
3; The PE powder is 60s in the treatment time of plasma discharge region, and the plasma discharge region temperature is 30 ~ 45 ℃, and pressure is 3000Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 from discharge port, passes into chlorine and carries out chlorination reaction, and chlorination temperature is at 130 ℃, and time of chlorinating is 2h, and chloridating gas pressure is 150000 Pa;
4) reaction end gas is discharged from chlorination reactor 12, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted can recycle or absorbed processing with alkali cuvette 25;
5) by gas blower 18, the CPE product obtained after chlorination is entered to strainer 26 from discharge port, drying through kiln 27.After tested, in CPE, cl content is 65%.
Embodiment tri-:
1) the PE powder is joined plasma generator 1 from PE powder import 4, argon gas and chlorine flow into plasma generator 1 from unstripped gas import 3, open vacuum pump 7 and are evacuated to low pressure;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 0.5W/cm
3; The PE powder is 300s in the treatment time of plasma discharge region, and the plasma discharge region temperature is 20 ~ 30 ℃, and pressure is 8000Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 from discharge port, passes into chlorine and carries out chlorination reaction, and chlorination temperature is at 100 ℃, and time of chlorinating is 4h, and chloridating gas pressure is 100000 Pa;
4) reaction end gas is discharged from chlorination reactor 12, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted can recycle or absorbed processing with alkali cuvette 25;
5) by gas blower, the CPE product obtained after chlorination is entered to strainer 26 from discharge port, drying through kiln 27.After tested, in CPE, cl content is 25%.
Embodiment tetra-:
1) the PE powder is joined plasma generator 1 from PE powder import 4, argon gas flows into plasma generator 1 from unstripped gas import 3, opens vacuum pump 7 and is evacuated to low pressure;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 1.5W/cm
3; The PE powder is 15min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 30 ~ 60 ℃, and pressure is 200Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 from discharge port, passes into chlorine and carries out chlorination reaction, and chlorination temperature is at 90 ℃, and time of chlorinating is 5h, and chloridating gas pressure is 100000 Pa;
4) reaction end gas is discharged from chlorination reactor 12, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted can recycle or absorbed processing with alkali cuvette 25;
5) by gas blower, the CPE product obtained after chlorination is entered to strainer 26 from discharge port, drying through kiln 27.After tested, in CPE, cl content is 42%.
Embodiment five:
1) the PE powder is joined plasma generator 1 from PE powder import 4, argon gas and chlorine flow into plasma generator 1 from unstripped gas import 3, open vacuum pump 7 and are evacuated to low pressure;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, causes chlorination reaction, and the power density of plasma body is 3W/cm
3; The PE powder is 10min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 45 ℃, and pressure is 1000Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 from discharge port, passes into chlorine and carries out chlorination reaction, and chlorination temperature is at 120 ℃, and time of chlorinating is 3h, and chloridating gas pressure is 140000 Pa;
4) reaction end gas is discharged from chlorination reactor 12, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted can recycle or absorbed processing with alkali cuvette 25;
5) by gas blower, the CPE product obtained after chlorination is entered to strainer 26 from discharge port, drying through kiln 27.After tested, in CPE, cl content is 69%.
Embodiment six:
1) the PE powder is joined plasma generator 1 from PE powder import 4, argon gas and chlorine flow into plasma generator 1 from unstripped gas import 3, open vacuum pump 7 and are evacuated to low pressure;
2) start whipping appts 1, start plasma electrical source 11 electric discharges, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 1.2W/cm
3; The PE powder is 20min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 25 ~ 40 ℃, and pressure is 100Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor 12 from discharge port, passes into chlorine and carries out chlorination reaction, and chlorination temperature is at 80 ℃, and time of chlorinating is 5h, and chloridating gas pressure is 90000 Pa;
4) reaction end gas is discharged from chlorination reactor 12, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber 24 separates, and the complete chlorine of unreacted can recycle or absorbed processing with alkali cuvette 25;
5) by gas blower, the CPE product obtained after chlorination is entered to strainer 26 from discharge port, drying through kiln 27.After tested, in CPE, cl content is 25%.
Claims (7)
1. a device for preparing chlorinatedpolyethylene, it is characterized in that: include plasma producing apparatus and chlorination reaction device, described plasma producing apparatus includes plasma generator, be provided with whipping appts one in plasma generator, be provided with the unstripped gas import at the top of plasma generator, the import of PE powder and vacuum orifice, described unstripped gas import connects the raw material gas cylinder, vacuum orifice connects vacuum pump, be provided with the unstripped gas outlet and process the outlet of rear PE material on plasma generator, plasma generator also is connected with plasma electrical source with vacuum display device respectively, described chlorination reaction device includes chlorination reactor, be provided with whipping appts two in the side of chlorination reactor, be provided with gas feed and pneumatic outlet at the top of chlorination reactor, be provided with opening for feed and discharge port in the left side of chlorination reactor, right side at chlorination reactor is provided with blast inlet, described blast inlet is connected with gas blower, described gas feed is connected with gas cylinder, pneumatic outlet is connected with device for absorbing tail gas, after opening for feed connects the processing in plasma producing apparatus, the PE material exports, and discharge port is connected with the CPE treatment unit.
2. the device for preparing chlorinatedpolyethylene according to claim 1, is characterized in that: also be provided with surge tank and preheating can between described gas cylinder and gas feed; Described device for absorbing tail gas includes two packed absorbers and the alkali cuvette connected by pipeline successively; Described CPE treatment unit includes strainer and the kiln connected successively.
3. the device for preparing chlorinatedpolyethylene according to claim 1, it is characterized in that: the radio frequency plasma body device that described plasma producing apparatus is negative pressure or atmospheric operation, dielectric barrier discharge plasma device or microwave plasma device, the discharge mode of described plasma producing apparatus includes three kinds of continuous discharges, intermittent discharge, impulsive discharge.
4. the device for preparing chlorinatedpolyethylene according to claim 1, it is characterized in that: described plasma generator is vertical producer or horizontal producer; Vertical producer can be provided with end stirring or stir on top; Horizontal producer is cylindrical shell rotating generator or the inner producer that is provided with the axle stirring.
5. the device for preparing chlorinatedpolyethylene according to claim 1, it is characterized in that: described chlorination reactor is horizontal reactor or vertical reactor; Horizontal reactor is cylindrical shell rotatable reactor or the inner reactor that is provided with the axle stirring; Vertical reactor can be established the end and stir or push up and stir.
6. a method for preparing chlorinatedpolyethylene is characterized in that: comprise the following steps:
1) the PE powder is joined plasma generator from the import of PE powder, unstripped gas flows into plasma generator from the unstripped gas import, opens vacuum pump and is evacuated to low pressure, and PE powder median size is 30 ~ 300 microns;
2) start whipping appts one, start the plasma electrical source electric discharge, the PE powder is fully mixed with plasma body, the PE powder is under action of plasma, and surface is activated, and forms macromolecular radical, cause chlorination reaction, the power density of plasma body is 0.1 ~ 15W/cm
3, the PE powder is 5s ~ 30min in the treatment time of plasma discharge region, and the plasma discharge region temperature is 20 ~ 80 ℃, and pressure is 10 ~ 10000Pa;
3) material of the PE after Cement Composite Treated by Plasma enters into chlorination reactor through the outlet of PE material and opening for feed, pass into chlorine from gas feed and carry out chlorination reaction, start whipping appts two, chlorination temperature is 30 ~ 140 ℃, time of chlorinating is 1 ~ 6h, and chloridating gas pressure is 1000 ~ 150000 Pa;
4) reaction end gas is discharged from pneumatic outlet, and in tail gas, HCl is prepared into highly purified hydrochloric acid after packed absorber separates, and the complete chlorine of unreacted absorbs and processes by the alkali cuvette;
5) by gas blower, the CPE product obtained after chlorination is entered to strainer from discharge port, then dry through kiln.
7. prepare according to claim 6 the method for chlorinatedpolyethylene, it is characterized in that: the mixed gas of the mixed gas that described unstripped gas is argon gas, nitrogen or argon gas and nitrogen, chlorine or the rare gas elementes such as chlorine and argon gas.
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| CN106975329A (en) * | 2017-04-13 | 2017-07-25 | 上海大学 | Vacuum plasma stacked tubular air purifier |
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| CN111978438A (en) * | 2019-05-22 | 2020-11-24 | 齐鲁工业大学 | Novel chlorinated polyvinyl chloride system |
| CN114213591A (en) * | 2022-02-24 | 2022-03-22 | 山东三义集团股份有限公司 | Chlorinated polyethylene graft copolymer and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106975329A (en) * | 2017-04-13 | 2017-07-25 | 上海大学 | Vacuum plasma stacked tubular air purifier |
| CN106975329B (en) * | 2017-04-13 | 2019-11-15 | 上海大学 | Vacuum plasma stacked tubular air purification device |
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| CN111978438B (en) * | 2019-05-22 | 2022-07-08 | 齐鲁工业大学 | Chlorinated polyvinyl chloride device |
| CN114213591A (en) * | 2022-02-24 | 2022-03-22 | 山东三义集团股份有限公司 | Chlorinated polyethylene graft copolymer and preparation method thereof |
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