WO2014161112A1 - METHOD FOR PREPARING PTFE SUPERFINE POWDER BY COMBINING γ RAYS WITH OZONE AND CARBON TETRACHLORIDE - Google Patents

METHOD FOR PREPARING PTFE SUPERFINE POWDER BY COMBINING γ RAYS WITH OZONE AND CARBON TETRACHLORIDE Download PDF

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WO2014161112A1
WO2014161112A1 PCT/CN2013/000796 CN2013000796W WO2014161112A1 WO 2014161112 A1 WO2014161112 A1 WO 2014161112A1 CN 2013000796 W CN2013000796 W CN 2013000796W WO 2014161112 A1 WO2014161112 A1 WO 2014161112A1
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Prior art keywords
polytetrafluoroethylene
powder
cobalt
ozone
irradiation
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PCT/CN2013/000796
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French (fr)
Chinese (zh)
Inventor
顾建忠
吴明红
蔡建球
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太仓金凯特种线缆有限公司
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Publication of WO2014161112A1 publication Critical patent/WO2014161112A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention relates to the field of chemical engineering, and in particular to a method for irradiating a polytetrafluoroethylene ultrafine powder by using a cobalt 60 device. Background technique
  • PTFE Polytetrafluoroethylene
  • plastic king is a polymer made of tetrafluoroethylene monomer. It has strong cohesiveness, and the resin is easily attached and difficult to disperse.
  • PTFE ultrafine powder micronized powder is a low molecular weight polytetrafluoroethylene, which has an ultrafine PTFE ultrafine powder, a molecular weight of less than 10,000, and a PTFE micropowder series with a particle size of 0.5-15 ⁇ , which not only maintains polytetrafluoroethylene.
  • All the excellent properties of ethylene also have many unique properties: such as no self-cohesion, no static effect, good compatibility, low molecular weight, good dispersion, high self-lubricity, reduced friction coefficient, no agglomeration, easy It is mixed with oil or organic liquid, and it can be uniformly mixed with other solid particles.
  • the average particle size of PTFE ultrafine powder is less than 5 ⁇ , the specific surface is larger than 10m 2 /g, the friction coefficient is 0.06 ⁇ 0.07, the lubricity is good, and it can be well dispersed in many materials. It can be used as anti-sticking, anti-friction and flame retardant additives for plastics, rubber, inks, coatings and lubricating greases.
  • PTFE ultrafine powder can be used as a solid lubricant alone or as an additive for plastics, rubber, paints, inks, lubricants, greases, etc. When mixing with plastic or rubber, various typical powder processing methods, such as blending, can be added. Adding PTFE ultrafine powder to oil and grease can reduce the friction coefficient, and increase the lubrication by adding a few percent. The life of the oil.
  • the organic solvent dispersion can also be used as a release agent.
  • Carbon tetrachloride (chemical formula: CC1 4 ), also known as tetrachloromethane or chloranil, is a colorless, volatile, non-flammable liquid with a boiling point of 76.8 ° C and a vapor pressure of 15.26 kPa (25 ° C). The density is 5.3 g ZL. Due to its stable chemical properties, it degrades under ⁇ -ray irradiation to produce negative oxygen ions, which are unstable and generate ozone.
  • Ozone is an allotrope of oxygen. At normal temperature, it is a blue gas with a special odor and is insoluble in carbon tetrachloride. Ozone is highly oxidizing and easily decomposed, and the hydroxyl radical (.OH) produced during the decomposition process has a strong oxidizing power.
  • the method for preparing PTFE ultrafine powder determines the structural properties, molecular weight and distribution of the PTFE ultrafine powder. There are two main preparation methods for PTFE ultrafine powder: 1. The polymerization is directly regulated by TFE. After a certain period of time, the polymerization reaction is terminated, and the product is further processed; 2. Degraded with high molecular weight PTFE, and then pulverized.
  • the pyrolysis reaction to prepare PTFE ultrafine powder mainly includes thermal cracking and irradiation cracking.
  • the degradation of PTFE is affected by the irradiation conditions, the irradiation dose, the energy source used for the irradiation, and the oxidation conditions have a great influence on the physical properties and chemical properties of the PTFE ultrafine powder.
  • Equipment and process conditions in the PTFE irradiation cracking process need to be optimized and tightly controlled.
  • a method for preparing PTFE ultrafine powder by combining Y-ray with ozone and carbon tetrachloride comprising the following steps:
  • the holder is located on an automatic assembly line running through the cobalt 60 irradiation chamber, and the holder is sealed, and at least one tetrachlorine is disposed therein a carbon shower device and at least one ozone release device, the cobalt 60 irradiation chamber comprising at least one cobalt 60 irradiation device in the middle of the irradiation chamber, an automatic assembly line passing through the cobalt 60 irradiation device, Radiation barrier and control room;
  • the polytetrafluoroethylene powder enters the irradiation chamber at a constant rate with the open automatic line, and the at least one tetrachloride is used when the polytetrafluoroethylene powder passes through at least one cobalt 60 irradiation device.
  • the carbon shower device sprays carbon tetrachloride on the polytetrafluoroethylene powder, and the at least one ozone releasing device introduces ozone into the sealed vessel, and the sprayed ozone and the polytetracycline
  • the weight ratio of the vinyl fluoride powder is 0.1% to 0.5%, and the weight ratio of the sprayed carbon tetrachloride to the polytetrafluoroethylene powder is 3% to 8%;
  • gamma rays generated by the at least one cobalt 60 irradiation device irradiate the polytetrafluoroethylene powder at a dose of 40-60 KGy when passing through the at least one cobalt 60 irradiation device.
  • the at least one ozone releasing device and the at least one carbon tetrachloride spraying device respectively spray ozone and carbon tetrachloride on the polytetrafluoroethylene powder, and spray
  • the weight ratio of ozone to the polytetrafluoroethylene powder was 0.3%, and the weight ratio of the sprayed carbon tetrachloride to the polytetrafluoroethylene powder in the tray was 5%.
  • the at least one cobalt 60 irradiation device may be a single grid cobalt source or a double grid cobalt source.
  • the step (4) further includes the automatic assembly being joined to the holder containing the Teflon powder, and at the outlet end of the automatic assembly line The irradiated polytetrafluoroethylene powder is poured into the feed port of the jet mill described in step (5).
  • the jet mill comprises a gas flow nozzle and a pulverizing chamber, and the compressed air is jetted into the pulverizing chamber through the nozzle at a high speed, at the intersection of the plurality of high-pressure air streams, irradiated
  • the polytetrafluoroethylene fine powder particles are repeatedly crushed, rubbed, sheared and pulverized.
  • the jet mill further includes a cyclone, a dust remover and an induced draft fan; the jet mill includes a classification zone, and the polytetrafluoroethylene after the crushing chamber is pulverized The fan moves to the classification zone. Under the action of the classification wheel, the fine particles of polytetrafluoroethylene are separated according to the particle size. The fine particles that meet the particle size requirements are collected by the classification wheel into the cyclone or the dust collector, which does not meet the particle size requirements. The coarse particles are dropped to the pulverizing chamber to continue pulverization.
  • the airflow nozzle of the jet mill is a Laval nozzle.
  • the jet mill has a dry filter device, and the dry filter device is located in front of the nozzle.
  • the automatic line may be a bucket conveyor or a suspended chain conveyor system, and has an automatic reversing device.
  • the degradation rate of the polytetrafluoroethylene can be increased or the irradiation time can be reduced to achieve the same degradation rate, thereby improving the production.
  • Efficiency to ensure the acquisition of low-molecular PTFE ultrafine powder with the required size, and the manufacturing process can be strictly controlled to ensure the production quality.
  • PTFE has poor radiation resistance (1000Gy) and is degraded by high-energy radiation.
  • the present invention utilizes the characteristics of polytetrafluoroethylene to perform radiation degradation treatment of polytetrafluoroethylene by high-frequency high-voltage electron accelerator, and then uses airflow.
  • the pulverizer is subjected to dispersion treatment to obtain a polytetrafluoroethylene ultrafine powder material.
  • Co Cobalt-60
  • the gamma ray also known as the y particle stream, is an electromagnetic wave with a wave length shorter than 0.2 angstrom and has a strong penetrating power.
  • Cobalt-60 radioactive sources are widely used in almost all walks of life. In agriculture, they are often used for radiation breeding, stimulation of yield increase, radiation control of pests and food irradiation preservation and preservation, etc. It is often used for non-destructive testing, radiation disinfection, radiation processing, radiation treatment of waste, as well as for thickness, density, level measurement and online automatic control; in medicine, it is commonly used for radiation therapy of cancer and tumor.
  • the polytetrafluoroethylene ruthenium becomes a low molecule through the polymer, and the low molecular weight polytetrafluoroethylene is still agglomerated together, and the ultrafine powder is not dispersed into small molecules, in order to obtain the ultrafine powder,
  • the low molecular weight polytetrafluoroethylene after irradiation degradation must be pulverized and pulverized by air flow.
  • the jet mill used in the following embodiments of the present invention includes a gas flow nozzle and a pulverizing chamber, and the compressed air is jetted into the pulverizing chamber at a high speed through the nozzle, and the irradiated PTFE fine at the intersection of the plurality of high-pressure air streams
  • the powder particles are repeatedly crushed, rubbed, sheared and pulverized.
  • the airflow nozzle of the jet mill is a Laval nozzle.
  • the air flow pulverizer also has a dry filter unit located in front of the nozzle.
  • the jet mill further comprises a cyclone separator, a dust collector and an induced draft fan; the jet mill further comprises a classification zone, wherein the PTFE pulverized in the crushing chamber is moved to the classification zone by the induced draft fan, and under the action of the classifying wheel, The PTFE particles are separated according to the particle size.
  • the fine particles meeting the particle size requirements are collected by the grading wheel into the cyclone or the dust collector.
  • the coarse particles that do not meet the particle size requirements are lowered to the pulverizing chamber to continue pulverization.
  • a method for preparing PTFE ultrafine powder by combining Y-ray with ozone and carbon tetrachloride comprising the following steps:
  • the dried polytetrafluoroethylene raw material is subjected to low temperature cold treatment with liquid nitrogen; the low temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 ⁇ ;
  • the cobalt 60 irradiation chamber comprising a single grid cobalt source located in the middle of the irradiation chamber, a bucket conveyor passing through the single grid cobalt source, located at the Said automatic pipeline and adjacent to said cobalt 60 irradiation device of at least one ozone release device and at least one carbon tetrachloride shower device, radiation partition wall and control room;
  • the polytetrafluoroethylene powder enters the irradiation chamber at a uniform speed with the open bucket conveyor, the at least one ozone releasing device and at least one carbon tetrachloride spraying device in the polytetrafluoroethylene
  • the ethylene powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.1%, and the sprayed carbon tetrachloride is The weight ratio of the polytetrafluoroethylene powder is 8%;
  • gamma rays generated by the single grid cobalt source are irradiated to the polytetrafluoroethylene powder at a dose of 40 KGy while passing through the single grid cobalt source, the bucket conveyor
  • the velocity is determined by the amount of radioactivity of the single grid cobalt source and is controlled by the control chamber;
  • a method for preparing PTFE ultrafine powder by combining X-ray with ozone and carbon tetrachloride comprising the following steps:
  • the dried polytetrafluoroethylene raw material is subjected to low temperature cold treatment with liquid nitrogen; the low temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 ⁇ ;
  • the polytetrafluoroethylene powder enters the irradiation chamber at a uniform speed with the open bucket conveyor, the 1 ozone release device and 2 carbon tetrachloride shower devices in the PTFE powder
  • the material is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.1%, and the sprayed carbon tetrachloride and the polytetra
  • the weight ratio of the vinyl fluoride powder is 8%;
  • the polytetrafluoroethylene powder continues to advance with the bucket conveyor after spraying ozone and carbon tetrachloride, and the single grid cobalt source is generated when passing through the single grid cobalt source
  • the gamma ray irradiates the polytetrafluoroethylene powder at an irradiation dose of 60 KGy, the speed of the bucket conveyor is determined by the radioactivity of the single grid cobalt source, and is controlled by the control chamber;
  • the cargo tank containing the irradiated PTFE powder is transported out of the irradiation chamber by the bucket conveyor, and the irradiated PTFE powder is directly discharged into the feed of the jet mill. mouth;
  • the irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 ⁇ m or less.
  • the above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
  • the jet mill has a gas flow nozzle, a pulverizing chamber, and a grading zone, and the compressed air is sprayed to the pulverizing chamber at a high speed through the nozzle, and the PTFE raw material irradiated at the intersection of the plurality of high-pressure air streams is repeatedly collided , rubbing, shearing and pulverizing, the pulverized PTFE moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the coarse and fine polytetrafluoroethylene particles are made under the strong centrifugal force generated by the high-speed rotating classification turbine. Separation, fine particles meeting the particle size requirements are collected into a cyclone or a dust collector. The cyclone collects coarser particles in the fine particles. A small portion of the ultrafine particles are collected by the dust collector, and the coarse particles are lowered to the crushing zone to continue to be crushed.
  • Embodiment 3 Embodiment 3:
  • a method for preparing PTFE ultrafine powder by combining X-ray with ozone and carbon tetrachloride comprising the following steps:
  • the dried polytetrafluoroethylene raw material is subjected to low temperature cold treatment with liquid nitrogen; the low temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 ⁇ ;
  • the polytetrafluoroethylene powder enters the irradiation chamber at a constant speed with the open hanging chain conveyor system, and the two ozone releasing devices and one carbon tetrachloride spraying device are in the polytetrafluoroethylene
  • the powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.5%, and the sprayed carbon tetrachloride and the poly The weight ratio of the tetrafluoroethylene powder is 3%;
  • the polytetrafluoroethylene powder continues to advance with the suspension chain conveyor system, and the gamma ray generated by the double grid cobalt source is PTFE when passing through the double grid cobalt source
  • the powder is irradiated, the irradiation dose is 50KGy, and the speed of the suspension chain conveyor system is determined by the radioactivity of the double grid cobalt source, and is controlled by the control room;
  • the cargo tank containing the irradiated Teflon powder is transported out of the irradiation room by the hanging chain conveyor system, and the irradiated PTFE powder is directly discharged into the jet mill. Feed opening
  • the irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 ⁇ m or less.
  • the above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
  • the jet mill has a gas flow nozzle, a pulverizing chamber, and a grading zone, and the compressed air is sprayed to the pulverizing chamber at a high speed through the nozzle, and the PTFE raw material irradiated at the intersection of the plurality of high-pressure air streams is repeatedly collided , rubbing, shearing and pulverizing, the pulverized PTFE moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the coarse and fine polytetrafluoroethylene particles are made under the strong centrifugal force generated by the high-speed rotating classification turbine. Separation, fine particles meeting the particle size requirements are collected into a cyclone or a dust collector. The cyclone collects coarser particles in the fine particles. A small portion of the ultrafine particles are collected by the dust collector, and the coarse particles are lowered to the crushing zone to continue to be crushed.
  • Embodiment 4 Embodiment 4:
  • a preparation method of a polytetrafluoroethylene ultrafine powder comprising the following steps:
  • the dried polytetrafluoroethylene raw material is subjected to low-temperature cold treatment with liquid nitrogen; the low-temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 ⁇ m;
  • the polytetrafluoroethylene powder enters the irradiation chamber at a constant speed with the open suspension chain conveyor system, the two ozone release devices and two carbon tetrachloride shower devices in the polytetrafluoroethylene
  • the powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.5%, and the sprayed carbon tetrachloride and the poly The weight ratio of the tetrafluoroethylene powder is 5%;
  • the PTFE powder continues along with the suspension chain conveyor system, and the gamma ray generated by the single grid cobalt source passes through the double grid cobalt source
  • the fluoroethylene powder is irradiated, the irradiation dose is 60KGy, and the speed of the suspension chain conveyor system is determined by the radioactivity of the single grid cobalt source, and is controlled by the control room;
  • the cargo tank containing the irradiated Teflon powder is transported out of the irradiation room by the hanging chain conveyor system, and the irradiated PTFE powder is directly discharged into the jet mill. Feed opening
  • the irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 ⁇ m or less.
  • the above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
  • the jet mill has a gas flow nozzle, a pulverizing chamber, a grading zone, and the compressed air enters the nozzle through a filter drying device in front of the nozzle, and then is injected into the pulverizing chamber at a high speed, and is irradiated at a meeting point of the plurality of high-pressure air streams.
  • the PTFE raw material is repeatedly crushed, rubbed, sheared and pulverized.
  • the pulverized polytetrafluoroethylene moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the powerful centrifugal force generated by the high-speed rotating classification turbine
  • the fine PTFE particles are separated, the fine particles meeting the particle size requirements are collected into a cyclone or a dust collector, the cyclone collects coarser particles in the fine particles, and a small portion of the ultrafine particles are collected by the dust collector, coarse particles Drop to the crushing zone and continue to smash.
  • a method for preparing PTFE ultrafine powder by combining X-ray with ozone and carbon tetrachloride comprising the following steps:
  • the dried polytetrafluoroethylene raw material is subjected to low-temperature cold treatment with liquid nitrogen; the low-temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 ⁇ m;
  • the polytetrafluoroethylene powder enters the irradiation chamber at a constant speed with the open suspension chain conveyor system, the two ozone release devices and three carbon tetrachloride shower devices in the polytetrafluoroethylene
  • the powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.3%, and the sprayed carbon tetrachloride and the poly The weight ratio of the tetrafluoroethylene powder is 8%;
  • the polytetrafluoroethylene powder continues along with the suspension chain conveyor system, and the gamma ray generated by the double grid cobalt source passes through the double grid cobalt source
  • the fluoroethylene powder is irradiated, the irradiation dose is 60KGy, and the speed of the suspension chain conveyor system is determined by the radioactivity of the double grid cobalt source, and is controlled by the control room;
  • the cargo tank containing the irradiated Teflon powder is transported out of the irradiation room by the hanging chain conveyor system, and the irradiated PTFE powder is directly discharged into the jet mill. Feed opening
  • the irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the fine polytetrafluoroethylene powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 ⁇ or less.
  • the above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
  • the jet mill has a gas flow nozzle, a pulverizing chamber, a grading zone, and the compressed air enters the nozzle through a filter drying device in front of the nozzle, and then is injected into the pulverizing chamber at a high speed, and is irradiated at a meeting point of the plurality of high-pressure air streams.
  • the PTFE raw material is repeatedly crushed, rubbed, sheared and pulverized.
  • the pulverized polytetrafluoroethylene moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the powerful centrifugal force generated by the high-speed rotating classification turbine
  • the fine PTFE particles are separated, the fine particles meeting the particle size requirements are collected into a cyclone or a dust collector, the cyclone collects coarser particles in the fine particles, and a small portion of the ultrafine particles are collected by the dust collector, coarse particles Drop to the crushing zone and continue to smash.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Disclosed is a method for preparing a PTFE superfine powder by combining γ rays with ozone and carbon tetrachloride. The method comprises: quenching a dry polytetrafluoroethylene raw material in liquid nitrogen; crushing same into a polytetrafluoroethylene powder having a grain size of 100-1000 μm with a pulverizer; then placing same into a container on an automatic production line of a cobalt 60 device; first spraying ozone and carbon tetrachloride on the automatic production line, and then irradiating when passing through the cobalt 60 device, wherein the irradiation dose is 40-60 KGy, and the radiation time is determined according to the radioactivity of the cobalt 60 device; conveying the radiated polytetrafluoroethylene powder out of the radiation chamber via the automatic production line; and placing same into an airflow crushing system for sufficient crushing, so as to obtain a polytetrafluoroethylene superfine powder with a grain size of 0.2-5 μm. According to the method provided by the present invention, using the automatic production line can further improve the production efficiency while the degradation rate of polytetrafluoroethylene can be increased.

Description

Y射线结合臭氧和四氯化碳制备 PTFE超细粉的方法 技术领域 本发明涉及化工技术领域， 特别涉及一种利用钴 60装置辐照聚四氟乙烯 超细粉的方法。 背景技术  TECHNICAL FIELD The present invention relates to the field of chemical engineering, and in particular to a method for irradiating a polytetrafluoroethylene ultrafine powder by using a cobalt 60 device. Background technique
聚四氟乙烯 （PTFE)俗称塑料王， 是由四氟乙烯单体聚合而成的聚合物， 有很强的凝聚性， 树脂很容易附在一起， 不易分散。 PTFE超细粉 （微粉） 是 低分子量的聚四氟乙烯，达到超细程度的 PTFE超细粉，分子量低于 1万以下， 粒径在 0.5-15μηι的 PTFE微粉系列，不仅保持着聚四氟乙烯原有的所有优良性 能， 还具有许多独特的性能： 如无自凝聚性、 无静电效应、 相溶性好、 分子量 低、 分散性好、 自润滑性高、 摩擦系数降低， 不结团， 容易与油或有机液体相 混，与其它固体微粒也可均匀混合明显等等。 PTFE超细粉平均粒径小于 5μηι， 比表面大于 10m2/g， 摩擦系数 0.06〜0.07， 润滑性好， 能很好地分散在许多材 料中。可用作塑料、橡胶、 油墨、涂料、润滑油脂的防黏、减摩、 阻燃添加剂， 也可作干性润滑剂制成气溶胶等。 PTFE超细粉可以单独作固体润滑剂使用， 也可以作为塑料、 橡胶、 涂料、 油墨、 润滑油、 润滑脂等的添加剂。 与塑料或 橡胶混合时可用各种典型的粉末加工方法， 如共混等， 在油和油脂中添加聚四 氟乙烯超细粉， 可降低摩擦系数， 只要加百分之几， 就可提高润滑油的寿命。 其有机溶剂分散液还可作脱模剂。 Polytetrafluoroethylene (PTFE), commonly known as plastic king, is a polymer made of tetrafluoroethylene monomer. It has strong cohesiveness, and the resin is easily attached and difficult to disperse. PTFE ultrafine powder (micronized powder) is a low molecular weight polytetrafluoroethylene, which has an ultrafine PTFE ultrafine powder, a molecular weight of less than 10,000, and a PTFE micropowder series with a particle size of 0.5-15μηι, which not only maintains polytetrafluoroethylene. All the excellent properties of ethylene, also have many unique properties: such as no self-cohesion, no static effect, good compatibility, low molecular weight, good dispersion, high self-lubricity, reduced friction coefficient, no agglomeration, easy It is mixed with oil or organic liquid, and it can be uniformly mixed with other solid particles. The average particle size of PTFE ultrafine powder is less than 5μηι, the specific surface is larger than 10m 2 /g, the friction coefficient is 0.06~0.07, the lubricity is good, and it can be well dispersed in many materials. It can be used as anti-sticking, anti-friction and flame retardant additives for plastics, rubber, inks, coatings and lubricating greases. It can also be used as a dry lubricant to make aerosols. PTFE ultrafine powder can be used as a solid lubricant alone or as an additive for plastics, rubber, paints, inks, lubricants, greases, etc. When mixing with plastic or rubber, various typical powder processing methods, such as blending, can be added. Adding PTFE ultrafine powder to oil and grease can reduce the friction coefficient, and increase the lubrication by adding a few percent. The life of the oil. The organic solvent dispersion can also be used as a release agent.
四氯化碳（化学式： CC14)， 也称四氯甲烷或氯垸， 是一种无色、 易挥发、 不易燃的液体， 沸点 76.8°C， 蒸气压 15.26kPa(25 °C)， 蒸气密度 5.3gZL。 由于 其化学性质稳定， 在 Y射线辐照下降解产生负氧离子， 负氧离子不稳定， 进一 歩产生臭氧。 Carbon tetrachloride (chemical formula: CC1 4 ), also known as tetrachloromethane or chloranil, is a colorless, volatile, non-flammable liquid with a boiling point of 76.8 ° C and a vapor pressure of 15.26 kPa (25 ° C). The density is 5.3 g ZL. Due to its stable chemical properties, it degrades under γ-ray irradiation to produce negative oxygen ions, which are unstable and generate ozone.
臭氧是氧的同素异形体， 在常温下， 它是一种有特殊臭味的蓝色气体， 不 溶于四氯化碳。臭氧具有很强的氧化性， 易分解， 在分解过程中产生的羟基自 由基（.OH) 具有极强的氧化能力。 制备 PTFE超细粉的方法， 决定了 PTFE超细粉的结构性能、 分子量及其 分布。 PTFE超细粉的制备方法主要有两种： 1、 直接用 TFE调节聚合， 经一 定时间后终止聚合反应， 产物再进行适当加工； 2、 用高分子量 PTFE降解， 再粉碎。 裂解反应制备 PTFE超细粉的方法主要有热裂解和辐照裂解。 辐照裂 解过程中， PTFE降解受辐照条件的影响， 辐照剂量， 辐照所采用的能量来源 以及氧化条件的不同， 对 PTFE超细粉的物理性能和化学性能均有较大影响， 因此需要对 PTFE辐照裂解过程中的设备和工艺条件进行优化并严格控制。 发明内容 针对上述现有技术中存在的问题，本发明的目的在于提供一种 Y射线结合 臭氧和四氯化碳制备 PTFE超细粉的方法。 Ozone is an allotrope of oxygen. At normal temperature, it is a blue gas with a special odor and is insoluble in carbon tetrachloride. Ozone is highly oxidizing and easily decomposed, and the hydroxyl radical (.OH) produced during the decomposition process has a strong oxidizing power. The method for preparing PTFE ultrafine powder determines the structural properties, molecular weight and distribution of the PTFE ultrafine powder. There are two main preparation methods for PTFE ultrafine powder: 1. The polymerization is directly regulated by TFE. After a certain period of time, the polymerization reaction is terminated, and the product is further processed; 2. Degraded with high molecular weight PTFE, and then pulverized. The pyrolysis reaction to prepare PTFE ultrafine powder mainly includes thermal cracking and irradiation cracking. During the irradiation cracking process, the degradation of PTFE is affected by the irradiation conditions, the irradiation dose, the energy source used for the irradiation, and the oxidation conditions have a great influence on the physical properties and chemical properties of the PTFE ultrafine powder. Equipment and process conditions in the PTFE irradiation cracking process need to be optimized and tightly controlled. SUMMARY OF THE INVENTION In view of the problems in the prior art described above, it is an object of the present invention to provide a method of preparing PTFE ultrafine powder by combining Y-rays with ozone and carbon tetrachloride.
为了实现上述发明目的， 本发明采用的技术方案如下：  In order to achieve the above object, the technical solution adopted by the present invention is as follows:
一种 Y射线结合臭氧和四氯化碳制备 PTFE超细粉的方法，包括以下步骤: A method for preparing PTFE ultrafine powder by combining Y-ray with ozone and carbon tetrachloride, comprising the following steps:
( 1 )将干燥的聚四氟乙烯原料用液氮进行急冷处理； 将急冷处理后的聚 四氟乙烯原料粉碎成粒径为 100-1000 μηι的粉料； (1) quenching the dried polytetrafluoroethylene raw material with liquid nitrogen; pulverizing the quenched polytetrafluoroethylene raw material into a powder having a particle diameter of 100-1000 μηι;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具位于贯穿钴 60辐照室 的自动流水线上， 且所述盛具密封， 其内设置有至少 1个四氯化碳喷淋装置和 至少 1个臭氧释放装置， 所述钴 60辐照室包括位于所述辐照室中间的至少 1 个钴 60辐照装置、经过所述钴 60辐照装置的自动流水线、辐射隔离墙以及控 制室；  (2) placing the polytetrafluoroethylene powder into a holder, the holder is located on an automatic assembly line running through the cobalt 60 irradiation chamber, and the holder is sealed, and at least one tetrachlorine is disposed therein a carbon shower device and at least one ozone release device, the cobalt 60 irradiation chamber comprising at least one cobalt 60 irradiation device in the middle of the irradiation chamber, an automatic assembly line passing through the cobalt 60 irradiation device, Radiation barrier and control room;
( 3 )所述聚四氟乙烯粉料随着开启的自动流水线匀速进入辐照室， 在所 述聚四氟乙烯粉料经过至少 1个钴 60辐照装置时， 所述至少 1个四氯化碳喷 淋装置向所述聚四氟乙烯粉料喷淋四氯化碳，所述至少 1个臭氧释放装置向密 封的盛具中通入臭氧， 所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.1%-0.5%， 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 3%-8%； (3) the polytetrafluoroethylene powder enters the irradiation chamber at a constant rate with the open automatic line, and the at least one tetrachloride is used when the polytetrafluoroethylene powder passes through at least one cobalt 60 irradiation device. The carbon shower device sprays carbon tetrachloride on the polytetrafluoroethylene powder, and the at least one ozone releasing device introduces ozone into the sealed vessel, and the sprayed ozone and the polytetracycline The weight ratio of the vinyl fluoride powder is 0.1% to 0.5%, and the weight ratio of the sprayed carbon tetrachloride to the polytetrafluoroethylene powder is 3% to 8%;
(4)在经过所述至少 1个钴 60辐照装置时， 所述至少 1个钴 60辐照装 置产生的伽马射线对聚四氟乙烯粉料进行辐照， 辐照剂量为 40-60KGy; (4) gamma rays generated by the at least one cobalt 60 irradiation device irradiate the polytetrafluoroethylene powder at a dose of 40-60 KGy when passing through the at least one cobalt 60 irradiation device. ;
( 5 ) 装有经过辐照的聚四氟乙烯粉料的盛具由所述自动流水线运出所述 辐照室；  (5) a holder containing the irradiated polytetrafluoroethylene powder is transported out of the irradiation chamber by the automatic assembly line;
( 6)用气流粉碎机将所述经过辐照的聚四氟乙烯粉料进行再粉碎、分级， 聚四氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。 进一歩地， 在上述方法中， 所述至少 1个个臭氧释放装置和至少 1个四氯 化碳喷淋装置分别向所述聚四氟乙烯粉料喷淋臭氧和四氯化碳，喷淋的臭氧与 所述聚四氟乙烯粉料的重量比为 0.3%， 所述喷淋的四氯化碳与所述托盘中聚 四氟乙烯粉料的重量比为 5%。 (6) re-pulverizing and classifying the irradiated polytetrafluoroethylene powder by a jet mill. The fine polytetrafluoroethylene powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μm or less. Further, in the above method, the at least one ozone releasing device and the at least one carbon tetrachloride spraying device respectively spray ozone and carbon tetrachloride on the polytetrafluoroethylene powder, and spray The weight ratio of ozone to the polytetrafluoroethylene powder was 0.3%, and the weight ratio of the sprayed carbon tetrachloride to the polytetrafluoroethylene powder in the tray was 5%.
进一歩地， 在上述方法中， 所述至少 1个钴 60辐照装置可以为单栅板钴 源或双栅板钴源。  Further, in the above method, the at least one cobalt 60 irradiation device may be a single grid cobalt source or a double grid cobalt source.
进一歩地， 在上述任一种方法中， 在歩骤 （4) 还包括所述自动流水线与 所述装有聚四氟乙烯粉料的盛具接合在一起，并在自动流水线的出口端将所述 经过辐照的聚四氟乙烯粉料倒入歩骤 （5 ) 所述的气流粉碎机的进料口。  Further, in any of the above methods, the step (4) further includes the automatic assembly being joined to the holder containing the Teflon powder, and at the outlet end of the automatic assembly line The irradiated polytetrafluoroethylene powder is poured into the feed port of the jet mill described in step (5).
进一歩地，在上述任一种方法中，所述气流粉碎机包括气流喷嘴、粉碎腔， 压縮空气通过喷嘴高速喷射入粉碎腔， 在多股高压气流的交汇点处， 经辐照过 的聚四氟乙烯细粉颗粒被反复碰撞、 磨擦、 剪切而粉碎。  Further, in any of the above methods, the jet mill comprises a gas flow nozzle and a pulverizing chamber, and the compressed air is jetted into the pulverizing chamber through the nozzle at a high speed, at the intersection of the plurality of high-pressure air streams, irradiated The polytetrafluoroethylene fine powder particles are repeatedly crushed, rubbed, sheared and pulverized.
进一歩地， 在上述任一种方法中， 所述气流粉碎机还包括旋风分离器、 除 尘器和引风机； 所述气流粉碎机包括分级区， 在粉碎腔粉碎后的聚四氟乙烯在 引风机作用下运动至分级区， 在分级轮作用下， 使聚四氟乙烯细粉颗粒按粒度 大小分离，符合粒度要求的细颗粒通过分级轮进入旋风分离器或除尘器进行收 集， 不符合粒度要求的粗颗粒下降至粉碎腔继续粉碎。  Further, in any one of the above methods, the jet mill further includes a cyclone, a dust remover and an induced draft fan; the jet mill includes a classification zone, and the polytetrafluoroethylene after the crushing chamber is pulverized The fan moves to the classification zone. Under the action of the classification wheel, the fine particles of polytetrafluoroethylene are separated according to the particle size. The fine particles that meet the particle size requirements are collected by the classification wheel into the cyclone or the dust collector, which does not meet the particle size requirements. The coarse particles are dropped to the pulverizing chamber to continue pulverization.
进一歩地， 在上述任一种方法中， 所述气流粉碎机的气流喷嘴为拉瓦尔喷 嘴。  Further, in any of the above methods, the airflow nozzle of the jet mill is a Laval nozzle.
进一歩地， 在上述任一种方法中， 所述气流粉碎机具有干燥过滤装置， 所 述干燥过滤装置位于喷嘴前。  Further, in any of the above methods, the jet mill has a dry filter device, and the dry filter device is located in front of the nozzle.
进一歩地， 在上述任一种方法中， 所述自动流水线可以是斗式输送机或悬 挂链式输送***， 并具有自动倒车装置。  Further, in any of the above methods, the automatic line may be a bucket conveyor or a suspended chain conveyor system, and has an automatic reversing device.
根据本发明提供的聚四氟乙烯超细粉的制备方法， 在相同的辐照条件下， 可增加聚四氟乙烯的降解率或者降低辐照时间也能达到相同的降解率， 因此提 高了生产效率， 保证获得尺寸符合要求的低分子的聚四氟乙烯超细粉， 且制造 过程可严格进行控制， 保证生产质量。 具体实施方式 为了使本发明的目的、 技术方案及优点更加清楚明白， 下面结合实施例， 对本发明进行进一歩详细说明。应当理解， 此处所描述的具体实施例仅用以解 释本发明， 并不用于限定本发明。 According to the preparation method of the polytetrafluoroethylene ultrafine powder provided by the invention, under the same irradiation condition, the degradation rate of the polytetrafluoroethylene can be increased or the irradiation time can be reduced to achieve the same degradation rate, thereby improving the production. Efficiency, to ensure the acquisition of low-molecular PTFE ultrafine powder with the required size, and the manufacturing process can be strictly controlled to ensure the production quality. detailed description In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be described in detail below in conjunction with the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
聚四氟乙烯的耐辐射性能较差 （1000Gy)， 受高能辐射后引起降解， 本发 明利用聚四氟乙烯的这个特性采用高频高压电子加速器对聚四氟乙烯进行辐 射降解处理， 再用气流粉碎机进行分散处理可得到聚四氟乙烯超细粉材料。  PTFE has poor radiation resistance (1000Gy) and is degraded by high-energy radiation. The present invention utilizes the characteristics of polytetrafluoroethylene to perform radiation degradation treatment of polytetrafluoroethylene by high-frequency high-voltage electron accelerator, and then uses airflow. The pulverizer is subjected to dispersion treatment to obtain a polytetrafluoroethylene ultrafine powder material.
钴 -60 (Co) 是金属元素钴的放射性同位素之一， 其半衰期为 5.27年。 它 会透过 衰变放出能量高达 315 keV的高速电子成为镍 -60， 同时会放出两束 伽马射线， 其能量分别为 1.17及 1.33 MeV。 γ射线， 又称 y 粒子流， 是波 长短于 0.2埃的电磁波， 有很强的穿透力。 作为和平利用核能的重要标志， 钴 -60放射源的应用非常广泛， 几乎遍及各行各业， 在农业上， 常用于辐射育种、 刺激增产、辐射防治虫害和食品辐照保藏与保鲜等;在工业上,常用于无损探伤、 辐射消毒、 辐射加工、 辐射处理废物， 以及用于厚度、 密度、 物位的测定和在 线自动控制等； 在医学上， 常用于癌和肿瘤的放射治疗。  Cobalt-60 (Co) is one of the radioisotopes of metallic cobalt and has a half-life of 5.27 years. It emits high-speed electrons with energy up to 315 keV through decay to become nickel-60, and emits two gamma rays with energies of 1.17 and 1.33 MeV, respectively. The gamma ray, also known as the y particle stream, is an electromagnetic wave with a wave length shorter than 0.2 angstrom and has a strong penetrating power. As an important symbol of the peaceful use of nuclear energy, Cobalt-60 radioactive sources are widely used in almost all walks of life. In agriculture, they are often used for radiation breeding, stimulation of yield increase, radiation control of pests and food irradiation preservation and preservation, etc. It is often used for non-destructive testing, radiation disinfection, radiation processing, radiation treatment of waste, as well as for thickness, density, level measurement and online automatic control; in medicine, it is commonly used for radiation therapy of cancer and tumor.
经过辐照降解后的聚四氟乙烯巳经由高分子变成低分子了，可低分子的聚 四氟乙烯还是团聚在一起， 没有分散成小分子的超细粉， 为了能得到超细粉， 必须把辐照降解后的低分子的聚四氟乙烯经过气流粉碎及粉碎。本发明下述实 施例中所使用的气流粉碎机包括气流喷嘴、粉碎腔， 压缩空气通过喷嘴高速喷 射入粉碎腔， 在多股高压气流的交汇点处， 经辐照过的聚四氟乙烯细粉颗粒被 反复碰撞、 磨擦、 剪切而粉碎。气流粉碎机的气流喷嘴为拉瓦尔喷嘴。 气流粉 碎机还具有干燥过滤装置， 位于喷嘴前。气流粉碎机还包括旋风分离器、 除尘 器和引风机； 气流粉碎机还包括分级区， 在粉碎腔粉碎后的聚四氟乙烯在引风 机作用下运动至分级区，在分级轮作用下，使聚四氟乙烯颗粒按粒度大小分离， 符合粒度要求的细颗粒通过分级轮进入旋风分离器或除尘器进行收集，不符合 粒度要求的粗颗粒下降至粉碎腔继续粉碎。 实施例一  After the radiation degradation, the polytetrafluoroethylene ruthenium becomes a low molecule through the polymer, and the low molecular weight polytetrafluoroethylene is still agglomerated together, and the ultrafine powder is not dispersed into small molecules, in order to obtain the ultrafine powder, The low molecular weight polytetrafluoroethylene after irradiation degradation must be pulverized and pulverized by air flow. The jet mill used in the following embodiments of the present invention includes a gas flow nozzle and a pulverizing chamber, and the compressed air is jetted into the pulverizing chamber at a high speed through the nozzle, and the irradiated PTFE fine at the intersection of the plurality of high-pressure air streams The powder particles are repeatedly crushed, rubbed, sheared and pulverized. The airflow nozzle of the jet mill is a Laval nozzle. The air flow pulverizer also has a dry filter unit located in front of the nozzle. The jet mill further comprises a cyclone separator, a dust collector and an induced draft fan; the jet mill further comprises a classification zone, wherein the PTFE pulverized in the crushing chamber is moved to the classification zone by the induced draft fan, and under the action of the classifying wheel, The PTFE particles are separated according to the particle size. The fine particles meeting the particle size requirements are collected by the grading wheel into the cyclone or the dust collector. The coarse particles that do not meet the particle size requirements are lowered to the pulverizing chamber to continue pulverization. Embodiment 1
一种 Y射线结合臭氧和四氯化碳制备 PTFE超细粉的方法，包括如下步骤: A method for preparing PTFE ultrafine powder by combining Y-ray with ozone and carbon tetrachloride, comprising the following steps:
( 1 )将干燥的聚四氟乙烯原料用液氮进行低温冷处理； 将低温处理后的 聚四氟乙烯原料粉碎成粒径为 100-1000 μηι的粉料； (1) the dried polytetrafluoroethylene raw material is subjected to low temperature cold treatment with liquid nitrogen; the low temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 μηι;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具是位于贯穿钴 60辐照 室的斗式输送机上的货斗， 所述钴 60辐照室包括位于所述辐照室中间的 1个 单栅板钴源， 经过所述单栅板钴源的斗式输送机， 位于所述自动流水线并邻近 所述钴 60辐照装置的至少 1个臭氧释放装置和至少 1个四氯化碳喷淋装置， 辐射隔离墙和控制室； (2) placing the polytetrafluoroethylene powder into a holder, the holder being located in the cobalt 60 irradiation a cargo bucket on a bucket conveyor of the chamber, the cobalt 60 irradiation chamber comprising a single grid cobalt source located in the middle of the irradiation chamber, a bucket conveyor passing through the single grid cobalt source, located at the Said automatic pipeline and adjacent to said cobalt 60 irradiation device of at least one ozone release device and at least one carbon tetrachloride shower device, radiation partition wall and control room;
( 3 ) 所述聚四氟乙烯粉料随着开启的斗式输送机匀速进入辐照室， 所述 至少 1个臭氧释放装置和至少 1个四氯化碳喷淋装置在所述聚四氟乙烯粉料经 过时向其喷淋臭氧和四氯化碳，所述喷淋的臭氧与所述聚四氟乙烯粉料的重量 比为 0.1%， 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 8%;  (3) the polytetrafluoroethylene powder enters the irradiation chamber at a uniform speed with the open bucket conveyor, the at least one ozone releasing device and at least one carbon tetrachloride spraying device in the polytetrafluoroethylene The ethylene powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.1%, and the sprayed carbon tetrachloride is The weight ratio of the polytetrafluoroethylene powder is 8%;
(4) 在经过所述单栅板钴源时， 所述单栅板钴源产生的伽马射线对聚四 氟乙烯粉料进行辐照，辐照剂量为 40KGy，所述斗式输送机的速度由所述单栅 板钴源的放射性大小决定， 并由所述控制室控制；  (4) gamma rays generated by the single grid cobalt source are irradiated to the polytetrafluoroethylene powder at a dose of 40 KGy while passing through the single grid cobalt source, the bucket conveyor The velocity is determined by the amount of radioactivity of the single grid cobalt source and is controlled by the control chamber;
( 5 ) 装有经过辐照的聚四氟乙烯粉料的货斗由斗式输送机运出辐照室， 并将经辐照的聚四氟乙烯粉料卸在气流粉碎原料区；  (5) The cargo bucket containing the irradiated PTFE powder is transported out of the irradiation chamber by the bucket conveyor, and the irradiated PTFE powder is discharged into the airflow pulverizing raw material zone;
( 6) 用气流粉碎机对经辐照的聚四氟乙烯细粉进行再粉碎、 分级， 聚四 氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。 实施例二：  (6) The irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μm or less. Embodiment 2:
一种 Υ射线结合臭氧和四氯化碳制备 PTFE超细粉的方法，包括如下步骤: A method for preparing PTFE ultrafine powder by combining X-ray with ozone and carbon tetrachloride, comprising the following steps:
( 1 ) 将干燥的聚四氟乙烯原料用液氮进行低温冷处理； 将低温处理后的 聚四氟乙烯原料粉碎成粒径为 100-1000 μηι的粉料； (1) The dried polytetrafluoroethylene raw material is subjected to low temperature cold treatment with liquid nitrogen; the low temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 μηι;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具是位于贯穿钴 60辐照 室的斗式输送机上的货斗， 所述钴 60辐照室包括位于所述辐照室中间的 2个 单栅板钴源， 经过所述单栅板钴源的斗式输送机， 辐射隔离墙和控制室；  (2) placing the polytetrafluoroethylene powder into a holder, the holder being a bucket on a bucket conveyor penetrating the cobalt 60 irradiation chamber, the cobalt 60 irradiation chamber being included Two single grid cobalt sources in the middle of the irradiation chamber, a bucket conveyor passing through the single grid cobalt source, a radiation partition wall and a control room;
( 3 )所述聚四氟乙烯粉料随着开启的斗式输送机匀速进入辐照室，所述 1 个臭氧释放装置和 2个四氯化碳喷淋装置在所述聚四氟乙烯粉料经过时向其喷 淋臭氧和四氯化碳， 所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.1%, 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 8%;  (3) the polytetrafluoroethylene powder enters the irradiation chamber at a uniform speed with the open bucket conveyor, the 1 ozone release device and 2 carbon tetrachloride shower devices in the PTFE powder The material is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.1%, and the sprayed carbon tetrachloride and the polytetra The weight ratio of the vinyl fluoride powder is 8%;
( 4 )所述聚四氟乙烯粉料在喷淋臭氧和四氯化碳之后继续随所述斗式输 送机前进， 在经过所述单栅板钴源时， 所述单栅板钴源产生的伽马射线对聚四 氟乙烯粉料进行辐照，辐照剂量为 60KGy，所述斗式输送机的速度由所述单栅 板钴源的放射性大小决定， 并由所述控制室控制； ( 5 ) 装有经过辐照的聚四氟乙烯粉料的货斗由斗式输送机运出辐照室， 并将经辐照的聚四氟乙烯粉料直接卸在气流粉碎机的进料口； (4) the polytetrafluoroethylene powder continues to advance with the bucket conveyor after spraying ozone and carbon tetrachloride, and the single grid cobalt source is generated when passing through the single grid cobalt source The gamma ray irradiates the polytetrafluoroethylene powder at an irradiation dose of 60 KGy, the speed of the bucket conveyor is determined by the radioactivity of the single grid cobalt source, and is controlled by the control chamber; (5) The cargo tank containing the irradiated PTFE powder is transported out of the irradiation chamber by the bucket conveyor, and the irradiated PTFE powder is directly discharged into the feed of the jet mill. mouth;
( 6) 用气流粉碎机对经辐照的聚四氟乙烯细粉进行再粉碎、 分级， 聚四 氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。 上述气流粉碎***包含气流粉碎机、 旋风分离器、 除尘器和引风机。  (6) The irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μm or less. The above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
所述气流粉碎机具有气流喷嘴、 粉碎腔、 分级区， 压縮空气通过喷嘴高速 喷射到粉碎腔，在多股高压气流的交汇点处经辐照过的所述聚四氟乙烯原料被 反复碰撞、 磨擦、 剪切而粉碎， 粉碎后的聚四氟乙烯在引风机抽力作用下随上 升气流运动至分级区， 在高速旋转的分级涡轮产生的强大离心力作用下， 使粗 细聚四氟乙烯颗粒分离， 符合粒度要求的细颗粒进入旋风分离器或除尘器收 集， 旋风分离器收集细颗粒中的较粗颗粒， 少部分超细颗粒由除尘器收集， 粗 颗粒下降至粉碎区继续粉碎。 实施例三：  The jet mill has a gas flow nozzle, a pulverizing chamber, and a grading zone, and the compressed air is sprayed to the pulverizing chamber at a high speed through the nozzle, and the PTFE raw material irradiated at the intersection of the plurality of high-pressure air streams is repeatedly collided , rubbing, shearing and pulverizing, the pulverized PTFE moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the coarse and fine polytetrafluoroethylene particles are made under the strong centrifugal force generated by the high-speed rotating classification turbine. Separation, fine particles meeting the particle size requirements are collected into a cyclone or a dust collector. The cyclone collects coarser particles in the fine particles. A small portion of the ultrafine particles are collected by the dust collector, and the coarse particles are lowered to the crushing zone to continue to be crushed. Embodiment 3:
一种 Υ射线结合臭氧和四氯化碳制备 PTFE超细粉的方法，包括如下步骤: A method for preparing PTFE ultrafine powder by combining X-ray with ozone and carbon tetrachloride, comprising the following steps:
( 1 ) 将干燥的聚四氟乙烯原料用液氮进行低温冷处理； 将低温处理后的 聚四氟乙烯原料粉碎成粒径为 100-1000 μηι的粉料； (1) The dried polytetrafluoroethylene raw material is subjected to low temperature cold treatment with liquid nitrogen; the low temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 μηι;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具是位于贯穿钴 60辐照 室的悬挂链式输送***上的货斗， 所述钴 60辐照室包括位于所述辐照室中间 的 1个双栅板钴源， 经过所述双栅板钴源的悬挂链式输送***， 位于所述悬挂 链式输送***并邻近所述双栅板钴源的 2个臭氧释放装置和 1个四氯化碳喷淋 装置， 辐射隔离墙和控制室；  (2) placing the polytetrafluoroethylene powder into a holder, the holder being a cargo bucket on a suspension chain conveyor system penetrating the cobalt 60 irradiation chamber, the cobalt 60 irradiation chamber being included a double grid cobalt source in the middle of the irradiation chamber, through the suspension chain conveyor system of the double grid cobalt source, located in the hanging chain conveyor system and adjacent to the double grid cobalt source An ozone release device and a carbon tetrachloride shower device, a radiation barrier and a control room;
( 3 )所述聚四氟乙烯粉料随着开启的悬挂链式输送***匀速进入辐照室， 所述 2个臭氧释放装置和 1个四氯化碳喷淋装置在所述聚四氟乙烯粉料经过时 向其喷淋臭氧和四氯化碳，所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.5%, 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 3%;  (3) the polytetrafluoroethylene powder enters the irradiation chamber at a constant speed with the open hanging chain conveyor system, and the two ozone releasing devices and one carbon tetrachloride spraying device are in the polytetrafluoroethylene The powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.5%, and the sprayed carbon tetrachloride and the poly The weight ratio of the tetrafluoroethylene powder is 3%;
(4) 所述聚四氟乙烯粉料随所述悬挂链式输送***继续前进， 在经过所 述双栅板钴源时， 所述双栅板钴源产生的伽马射线对聚四氟乙烯粉料进行辐 照，辐照剂量为 50KGy，所述悬挂链式输送***的速度由所述双栅板钴源的放 射性大小决定， 并由所述控制室控制； ( 5 ) 装有经过辐照的聚四氟乙烯粉料的货斗由悬挂链式输送***运出辐 照室， 并将经辐照的聚四氟乙烯粉料直接卸在气流粉碎机的进料口； (4) the polytetrafluoroethylene powder continues to advance with the suspension chain conveyor system, and the gamma ray generated by the double grid cobalt source is PTFE when passing through the double grid cobalt source The powder is irradiated, the irradiation dose is 50KGy, and the speed of the suspension chain conveyor system is determined by the radioactivity of the double grid cobalt source, and is controlled by the control room; (5) The cargo tank containing the irradiated Teflon powder is transported out of the irradiation room by the hanging chain conveyor system, and the irradiated PTFE powder is directly discharged into the jet mill. Feed opening
( 6) 用气流粉碎机对经辐照的聚四氟乙烯细粉进行再粉碎、 分级， 聚四 氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。  (6) The irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μm or less.
上述气流粉碎***包含气流粉碎机、 旋风分离器、 除尘器和引风机。  The above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
所述气流粉碎机具有气流喷嘴、 粉碎腔、 分级区， 压縮空气通过喷嘴高速 喷射到粉碎腔，在多股高压气流的交汇点处经辐照过的所述聚四氟乙烯原料被 反复碰撞、 磨擦、 剪切而粉碎， 粉碎后的聚四氟乙烯在引风机抽力作用下随上 升气流运动至分级区， 在高速旋转的分级涡轮产生的强大离心力作用下， 使粗 细聚四氟乙烯颗粒分离， 符合粒度要求的细颗粒进入旋风分离器或除尘器收 集， 旋风分离器收集细颗粒中的较粗颗粒， 少部分超细颗粒由除尘器收集， 粗 颗粒下降至粉碎区继续粉碎。 实施例四：  The jet mill has a gas flow nozzle, a pulverizing chamber, and a grading zone, and the compressed air is sprayed to the pulverizing chamber at a high speed through the nozzle, and the PTFE raw material irradiated at the intersection of the plurality of high-pressure air streams is repeatedly collided , rubbing, shearing and pulverizing, the pulverized PTFE moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the coarse and fine polytetrafluoroethylene particles are made under the strong centrifugal force generated by the high-speed rotating classification turbine. Separation, fine particles meeting the particle size requirements are collected into a cyclone or a dust collector. The cyclone collects coarser particles in the fine particles. A small portion of the ultrafine particles are collected by the dust collector, and the coarse particles are lowered to the crushing zone to continue to be crushed. Embodiment 4:
一种聚四氟乙烯超细粉的制备方法， 包括如下歩骤：  A preparation method of a polytetrafluoroethylene ultrafine powder, comprising the following steps:
( 1 ) 将干燥的聚四氟乙烯原料用液氮进行低温冷处理； 将低温处理后的 聚四氟乙烯原料粉碎成粒径为 100-1000 μιη的粉料；  (1) The dried polytetrafluoroethylene raw material is subjected to low-temperature cold treatment with liquid nitrogen; the low-temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 μm;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具是位于贯穿钴 60辐照 室的悬挂链式输送***上的货斗， 所述钴 60辐照室包括位于所述辐照室中间 的 3个单栅板钴源， 经过所述单栅板钴源的悬挂链式输送***， 位于所述悬挂 链式输送***上方并邻近所述单栅板钴源的 2个臭氧释放装置和 2个四氯化碳 喷淋装置， 辐射隔离墙和控制室；  (2) placing the polytetrafluoroethylene powder into a holder, the holder being a cargo bucket on a suspension chain conveyor system penetrating the cobalt 60 irradiation chamber, the cobalt 60 irradiation chamber being included 3 single grid cobalt sources in the middle of the irradiation chamber, through the suspension chain conveyor system of the single grid cobalt source, located above the suspension chain conveyor system and adjacent to the single grid cobalt source 2 An ozone release device and two carbon tetrachloride showers, a radiation barrier and a control room;
(3 )所述聚四氟乙烯粉料随着开启的悬挂链式输送***匀速进入辐照室， 所述 2个臭氧释放装置和 2个四氯化碳喷淋装置在所述聚四氟乙烯粉料经过时 向其喷淋臭氧和四氯化碳，所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.5%, 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 5%;  (3) the polytetrafluoroethylene powder enters the irradiation chamber at a constant speed with the open suspension chain conveyor system, the two ozone release devices and two carbon tetrachloride shower devices in the polytetrafluoroethylene The powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.5%, and the sprayed carbon tetrachloride and the poly The weight ratio of the tetrafluoroethylene powder is 5%;
(4) 所述聚四氟乙烯粉料随着所述悬挂链式输送***继续前行， 在经过 所述双栅板钴源时，所述单栅板钴源产生的伽马射线对聚四氟乙烯粉料进行辐 照，辐照剂量为 60KGy，所述悬挂链式输送***的速度由所述单栅板钴源的放 射性大小决定， 并由所述控制室控制； ( 5 ) 装有经过辐照的聚四氟乙烯粉料的货斗由悬挂链式输送***运出辐 照室， 并将经辐照的聚四氟乙烯粉料直接卸在气流粉碎机的进料口； (4) the PTFE powder continues along with the suspension chain conveyor system, and the gamma ray generated by the single grid cobalt source passes through the double grid cobalt source The fluoroethylene powder is irradiated, the irradiation dose is 60KGy, and the speed of the suspension chain conveyor system is determined by the radioactivity of the single grid cobalt source, and is controlled by the control room; (5) The cargo tank containing the irradiated Teflon powder is transported out of the irradiation room by the hanging chain conveyor system, and the irradiated PTFE powder is directly discharged into the jet mill. Feed opening
( 6) 用气流粉碎机对经辐照的聚四氟乙烯细粉进行再粉碎、 分级， 聚四 氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。 上述气流粉碎***包含气流粉碎机、 旋风分离器、 除尘器和引风机。  (6) The irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μm or less. The above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan.
所述气流粉碎机具有气流喷嘴、 粉碎腔、 分级区， 压縮空气通过喷嘴前的 过滤干燥装置进入喷嘴， 然后高速喷射入粉碎腔， 在多股高压气流的交汇点处 经辐照过的所述聚四氟乙烯原料被反复碰撞、 磨擦、 剪切而粉碎， 粉碎后的聚 四氟乙烯在引风机抽力作用下随上升气流运动至分级区，在高速旋转的分级涡 轮产生的强大离心力作用下， 使粗细聚四氟乙烯颗粒分离， 符合粒度要求的细 颗粒进入旋风分离器或除尘器收集， 旋风分离器收集细颗粒中的较粗颗粒， 少 部分超细颗粒由除尘器收集， 粗颗粒下降至粉碎区继续粉碎。 实施例五：  The jet mill has a gas flow nozzle, a pulverizing chamber, a grading zone, and the compressed air enters the nozzle through a filter drying device in front of the nozzle, and then is injected into the pulverizing chamber at a high speed, and is irradiated at a meeting point of the plurality of high-pressure air streams. The PTFE raw material is repeatedly crushed, rubbed, sheared and pulverized. The pulverized polytetrafluoroethylene moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the powerful centrifugal force generated by the high-speed rotating classification turbine Next, the fine PTFE particles are separated, the fine particles meeting the particle size requirements are collected into a cyclone or a dust collector, the cyclone collects coarser particles in the fine particles, and a small portion of the ultrafine particles are collected by the dust collector, coarse particles Drop to the crushing zone and continue to smash. Embodiment 5:
一种 Υ射线结合臭氧和四氯化碳制备 PTFE超细粉的方法，包括如下歩骤： A method for preparing PTFE ultrafine powder by combining X-ray with ozone and carbon tetrachloride, comprising the following steps:
( 1 ) 将干燥的聚四氟乙烯原料用液氮进行低温冷处理； 将低温处理后的 聚四氟乙烯原料粉碎成粒径为 100-1000 μιη的粉料； (1) The dried polytetrafluoroethylene raw material is subjected to low-temperature cold treatment with liquid nitrogen; the low-temperature treated polytetrafluoroethylene raw material is pulverized into a powder having a particle diameter of 100-1000 μm;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具是位于贯穿钴 60辐照 室的悬挂链式输送***上的货斗， 所述钴 60辐照室包括位于所述辐照室中间 的 2个双栅板钴源， 经过所述双栅板钴源的悬挂链式输送***， 位于所述自动 流水线并邻近所述双栅板钴源的 2个臭氧释放装置和 3个四氯化碳喷淋装置， 辐射隔离墙和控制室；  (2) placing the polytetrafluoroethylene powder into a holder, the holder being a cargo bucket on a suspension chain conveyor system penetrating the cobalt 60 irradiation chamber, the cobalt 60 irradiation chamber being included Two double grid cobalt sources in the middle of the irradiation chamber, through the suspension chain conveyor system of the double grid cobalt source, two ozone release devices located in the automatic pipeline adjacent to the double grid cobalt source And three carbon tetrachloride sprinklers, a radiation barrier and a control room;
(3 )所述聚四氟乙烯粉料随着开启的悬挂链式输送***匀速进入辐照室， 所述 2个臭氧释放装置和 3个四氯化碳喷淋装置在所述聚四氟乙烯粉料经过时 向其喷淋臭氧和四氯化碳，所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.3%, 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 8%;  (3) the polytetrafluoroethylene powder enters the irradiation chamber at a constant speed with the open suspension chain conveyor system, the two ozone release devices and three carbon tetrachloride shower devices in the polytetrafluoroethylene The powder is sprayed with ozone and carbon tetrachloride, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.3%, and the sprayed carbon tetrachloride and the poly The weight ratio of the tetrafluoroethylene powder is 8%;
(4) 所述聚四氟乙烯粉料随着所述悬挂链式输送***继续前行， 在经过 所述双栅板钴源时，所述双栅板钴源产生的伽马射线对聚四氟乙烯粉料进行辐 照，辐照剂量为 60KGy，所述悬挂链式输送***的速度由所述双栅板钴源的放 射性大小决定， 并由所述控制室控制； ( 5 ) 装有经过辐照的聚四氟乙烯粉料的货斗由悬挂链式输送***运出辐 照室， 并将经辐照的聚四氟乙烯粉料直接卸在气流粉碎机的进料口； (4) the polytetrafluoroethylene powder continues along with the suspension chain conveyor system, and the gamma ray generated by the double grid cobalt source passes through the double grid cobalt source The fluoroethylene powder is irradiated, the irradiation dose is 60KGy, and the speed of the suspension chain conveyor system is determined by the radioactivity of the double grid cobalt source, and is controlled by the control room; (5) The cargo tank containing the irradiated Teflon powder is transported out of the irradiation room by the hanging chain conveyor system, and the irradiated PTFE powder is directly discharged into the jet mill. Feed opening
( 6 ) 用气流粉碎机对经辐照的聚四氟乙烯细粉进行再粉碎、 分级， 聚四 氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。  (6) The irradiated polytetrafluoroethylene fine powder is repulverized and classified by a jet mill, and the fine polytetrafluoroethylene powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μηη or less.
上述气流粉碎***包含气流粉碎机、 旋风分离器、 除尘器和引风机。 所述气流粉碎机具有气流喷嘴、 粉碎腔、 分级区， 压縮空气通过喷嘴前的 过滤干燥装置进入喷嘴， 然后高速喷射入粉碎腔， 在多股高压气流的交汇点处 经辐照过的所述聚四氟乙烯原料被反复碰撞、 磨擦、 剪切而粉碎， 粉碎后的聚 四氟乙烯在引风机抽力作用下随上升气流运动至分级区，在高速旋转的分级涡 轮产生的强大离心力作用下， 使粗细聚四氟乙烯颗粒分离， 符合粒度要求的细 颗粒进入旋风分离器或除尘器收集， 旋风分离器收集细颗粒中的较粗颗粒， 少 部分超细颗粒由除尘器收集， 粗颗粒下降至粉碎区继续粉碎。  The above airflow pulverizing system comprises a jet mill, a cyclone, a dust collector and an induced draft fan. The jet mill has a gas flow nozzle, a pulverizing chamber, a grading zone, and the compressed air enters the nozzle through a filter drying device in front of the nozzle, and then is injected into the pulverizing chamber at a high speed, and is irradiated at a meeting point of the plurality of high-pressure air streams. The PTFE raw material is repeatedly crushed, rubbed, sheared and pulverized. The pulverized polytetrafluoroethylene moves with the ascending airflow to the classification zone under the action of the induced draft fan, and the powerful centrifugal force generated by the high-speed rotating classification turbine Next, the fine PTFE particles are separated, the fine particles meeting the particle size requirements are collected into a cyclone or a dust collector, the cyclone collects coarser particles in the fine particles, and a small portion of the ultrafine particles are collected by the dust collector, coarse particles Drop to the crushing zone and continue to smash.
以上所述实施例仅表达了本发明的实施方式， 其描述较为具体和详细， 但 并不能因此而理解为对本发明专利范围的限制。应当指出的是， 对于本领域的 普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和改 进， 这些都属于本发明的保护范围。 因此， 本发明专利的保护范围应以所附权 利要求为准。  The above-mentioned embodiments are merely illustrative of the embodiments of the present invention, and the description thereof is not to be construed as limiting the scope of the invention. It should be noted that various modifications and improvements can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the invention should be subject to the appended claims.

Claims

权 利 要 求 书 Claim
1. 一种 Y射线结合臭氧和四氯化碳制备 PTFE超细粉的方法， 其特征在 于， 包括如下歩骤： A method for preparing a PTFE ultrafine powder by combining Y-rays with ozone and carbon tetrachloride, which is characterized by comprising the following steps:
( 1 ) 将干燥的聚四氟乙烯原料用液氮进行急冷处理； 将急冷处理后的聚 四氟乙烯原料粉碎成粒径为 100-1000 μιη的粉料；  (1) quenching the dried polytetrafluoroethylene raw material with liquid nitrogen; pulverizing the quenched polytetrafluoroethylene raw material into a powder having a particle diameter of 100-1000 μm;
(2)将所述聚四氟乙烯粉料放入盛具中， 所述盛具位于贯穿钴 60辐照室 的自动流水线上， 且所述盛具密封， 且设置有至少 1个四氯化碳喷淋装置接口 和至少 1个臭氧释放装置接口， 所述钴 60辐照室包括位于所述辐照室中间的 至少 1个钴 60辐照装置、 经过所述钴 60辐照装置的自动流水线、 与所述盛具 上的至少 1个臭氧释放装置接口和至少 1个四氯化碳喷淋装置接口配合设置的 至少 1个臭氧释放装置和至少 1个四氯化碳喷淋装置、辐射隔离墙以及控制室;  (2) placing the polytetrafluoroethylene powder into a holder, the holder being located on an automatic line running through the cobalt 60 irradiation chamber, and the holder is sealed and provided with at least one tetrachlorination a carbon shower device interface and at least one ozone release device, the cobalt 60 irradiation chamber comprising at least one cobalt 60 irradiation device located in the middle of the irradiation chamber, and an automatic assembly line passing through the cobalt 60 irradiation device At least one ozone release device and at least one carbon tetrachloride shower device disposed in interface with at least one ozone release device interface on the holder and at least one carbon tetrachloride shower device, and radiation isolation Wall and control room;
(3 ) 所述聚四氟乙烯粉料随着开启的自动流水线匀速进入辐照室， 在所 述聚四氟乙烯粉料经过至少 1个钴 60辐照装置时， 所述至少 1个四氯化碳喷 淋装置向所述聚四氟乙烯粉料喷淋四氯化碳，所述至少 1个臭氧释放装置向密 封的盛具中通入臭氧， 所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.1%-0.5%, 所述喷淋的四氯化碳与所述聚四氟乙烯粉料的重量比为 3%-8%； (3) the polytetrafluoroethylene powder enters the irradiation chamber at a constant rate with the open automatic line, and the at least one tetrachloride is used when the polytetrafluoroethylene powder passes through at least one cobalt 60 irradiation device. The carbon shower device sprays carbon tetrachloride on the polytetrafluoroethylene powder, and the at least one ozone releasing device introduces ozone into the sealed vessel, and the sprayed ozone and the polytetracycline The weight ratio of the vinyl fluoride powder is 0.1% to 0.5%, and the weight ratio of the sprayed carbon tetrachloride to the polytetrafluoroethylene powder is 3% to 8%;
(4) 在经过所述至少 1个钴 60辐照装置时， 所述至少 1个钴 60辐照装 置产生的伽马射线对聚四氟乙烯粉料进行辐照， 辐照剂量为 40-60KGy; (4) When passing through the at least one cobalt 60 irradiation device, the gamma ray generated by the at least one cobalt 60 irradiation device irradiates the polytetrafluoroethylene powder to an irradiation dose of 40-60 KGy. ;
( 5) 装有经过辐照的聚四氟乙烯粉料的盛具由所述自动流水线运出所述 辐照室；  (5) a holder containing the irradiated polytetrafluoroethylene powder is transported out of the irradiation chamber by the automatic assembly line;
(6)用气流粉碎机将所述经过辐照的聚四氟乙烯粉料进行再粉碎、 分级， 聚四氟乙烯细粉分散成平均粒径在 5μηι以下的聚四氟乙烯超细粉。  (6) The irradiated polytetrafluoroethylene powder is repulverized and classified by a jet mill, and the polytetrafluoroethylene fine powder is dispersed into a polytetrafluoroethylene ultrafine powder having an average particle diameter of 5 μm or less.
2. 如权利要求 1所述的方法， 其特征在于， 所述至少 1个臭氧释放装置 和至少 1 个四氯化碳喷淋装置分别向所述聚四氟乙烯粉料喷淋臭氧和四氯化 碳， 所述喷淋的臭氧与所述聚四氟乙烯粉料的重量比为 0.3%， 所述喷淋的四 氯化碳与所述托盘中聚四氟乙烯粉料的重量比为 5%。  2. The method according to claim 1, wherein the at least one ozone releasing device and the at least one carbon tetrachloride shower device respectively spray ozone and tetrachloride to the polytetrafluoroethylene powder Carbonized, the weight ratio of the sprayed ozone to the polytetrafluoroethylene powder is 0.3%, and the weight ratio of the sprayed carbon tetrachloride to the polytetrafluoroethylene powder in the tray is 5 %.
3. 如权利要求 1所述的方法， 其特征在于， 所述至少 1个钴 60辐照装置 为单栅板钴源。  3. The method of claim 1 wherein said at least one cobalt 60 irradiation device is a single grid cobalt source.
4. 如权利要求 1所述的方法， 其特征在于， 所述至少 1个钴 60辐照装置 为双栅板钴源。 4. The method of claim 1 wherein said at least one cobalt 60 irradiation device is a dual grid cobalt source.
5. 根据权利要求 1所述的方法， 其特征在于， 歩骤 （4) 还包括所述自动 流水线与所述装有聚四氟乙烯粉料的盛具接合在一起，并在自动流水线的出口 端将所述经过辐照的聚四氟乙烯粉料倒入歩骤 （5 ) 所述的气流粉碎机的进料 □。 5. The method according to claim 1, wherein the step (4) further comprises the automatic assembly being joined to the holder containing the Teflon powder and at the outlet of the automatic assembly line. The end of the irradiated polytetrafluoroethylene powder is poured into the feed □ of the jet mill described in step (5).
6. 根据权利要求 5所述的方法，其特征在于，所述气流粉碎机包括气流喷 嘴、 粉碎腔， 压縮空气通过喷嘴高速喷射入粉碎腔， 在多股高压气流的交汇点 处， 经辐照过的聚四氟乙烯细粉颗粒被反复碰撞、 磨擦、 剪切而粉碎。  6. The method according to claim 5, wherein the jet mill comprises a gas flow nozzle and a pulverizing chamber, and the compressed air is injected into the pulverizing chamber at a high speed through the nozzle, at a meeting point of the plurality of high-pressure air streams, The irradiated fine particles of polytetrafluoroethylene are repeatedly crushed, rubbed, sheared and pulverized.
7. 根据权利要求 6所述的方法，其特征在于：所述气流粉碎机还包括旋风 分离器、 除尘器和引风机； 所述气流粉碎机包括分级区， 在粉碎腔粉碎后的聚 四氟乙烯在引风机作用下运动至分级区， 在分级轮作用下， 使聚四氟乙烯细粉 颗粒按粒度大小分离，符合粒度要求的细颗粒通过分级轮进入旋风分离器或除 尘器进行收集， 不符合粒度要求的粗颗粒下降至粉碎腔继续粉碎。  7. The method according to claim 6, wherein the jet mill further comprises a cyclone, a dust remover and an induced draft fan; the jet mill comprises a classification zone, and the polytetrafluorocarbon after the crushing chamber is pulverized The ethylene moves to the classification zone under the action of the induced draft fan. Under the action of the classification wheel, the fine particles of polytetrafluoroethylene are separated according to the particle size. The fine particles meeting the particle size requirements are collected into the cyclone or the dust collector through the classification wheel. The coarse particles meeting the particle size requirements are lowered to the pulverizing chamber to continue pulverization.
8. 根据权利要求 7所述的方法，其特征在于，所述气流粉碎机的气流喷嘴 为拉瓦尔喷嘴。  8. The method of claim 7 wherein the gas flow nozzle of the jet mill is a Laval nozzle.
9. 根据权利要求 8中所述的方法，其特征在于，所述气流粉碎机具有干燥 过滤装置， 所述干燥过滤装置位于喷嘴前。  9. A method according to claim 8 wherein the jet mill has a dry filter device located in front of the nozzle.
10. 根据权利要求 1-9任一项所述的方法， 其特征在于， 所述自动流水线 为可实现自动倒车的斗式输送机或悬挂链式输送***。  The method according to any one of claims 1 to 9, wherein the automatic pipeline is a bucket conveyor or a hanging chain conveyor system that can realize automatic reverse.
PCT/CN2013/000796 2013-04-03 2013-06-28 METHOD FOR PREPARING PTFE SUPERFINE POWDER BY COMBINING γ RAYS WITH OZONE AND CARBON TETRACHLORIDE WO2014161112A1 (en)

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