WO2022152182A1 - 一种改性交联聚乙烯及其制备方法、再生制品及其制备方法 - Google Patents

一种改性交联聚乙烯及其制备方法、再生制品及其制备方法 Download PDF

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WO2022152182A1
WO2022152182A1 PCT/CN2022/071671 CN2022071671W WO2022152182A1 WO 2022152182 A1 WO2022152182 A1 WO 2022152182A1 CN 2022071671 W CN2022071671 W CN 2022071671W WO 2022152182 A1 WO2022152182 A1 WO 2022152182A1
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linked polyethylene
cross
waste
preparation
modified cross
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PCT/CN2022/071671
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English (en)
French (fr)
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白时兵
廖益
段文锋
赖双鑫
杨双桥
丁红梅
谭宁
王迎春
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北京东方雨虹防水技术股份有限公司
四川大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention belongs to the technical field of waste cross-linked polyethylene recycling, and particularly relates to a modified cross-linked polyethylene and a preparation method thereof, a recycled product and a preparation method thereof.
  • Cross-linked polyethylene is a three-dimensional network structure formed by intermolecular covalent bonding of polyethylene through irradiation cross-linking, peroxide cross-linking and silane cross-linking. It has the characteristics of insoluble and infusible. Polyethylene has obtained excellent heat resistance, stress crack resistance, chemical corrosion resistance, wear resistance, creep resistance and excellent mechanical properties, and is widely used in chemical industry, construction, automobile, machinery, electric power, packaging , agriculture and other industries, especially for the preparation of pipes and insulated wires and cables.
  • waste cross-linked polyethylene comes from the above technical fields.
  • the first one is the waste materials in the synthesis and production process. Due to the particularity of cable production, in the process During the debugging process, waste will inevitably be generated, which is about 5% of the product production; the second is the used cable material, which is the old cable replaced after the service life is reached. This part is a very large amount of waste that cannot be reduced at all. . And because the three-dimensional network structure of cross-linked polyethylene cannot be processed again by thermoplastic, it is very difficult to recycle the waste.
  • Waste cross-linked polyethylene should be a resource with great recycling value. According to estimates, recycling 1 ton of waste cross-linked polyethylene is equivalent to using 3-5 tons of oil less. Statistics from the Bureau of Statistics show that in 2019, China's crude oil imports were 505.72 million tons, a year-on-year increase of 9.5%, which is undoubtedly of great significance to my country's national economy.
  • the main methods for disposing of waste cross-linked polyethylene include landfill, incineration and cracking.
  • Landfill method It covers a large area, and the conflict with urban construction is prominent, and the cost of landfill is high. It is often landfilled with other urban solid waste. The organic matter exuded from the landfill will pollute the water source and affect the underground ecological environment.
  • Incineration method It is often incinerated with other urban waste solid waste, and the toxic gas produced will pollute the atmosphere, and the non-toxic treatment equipment using incineration is expensive and costly (more than 2 billion yuan to build a large incineration plant).
  • Cracking method refers to the recovery of monomers, oligomers and other raw materials from waste cross-linked polyethylene through chemical reactions such as pyrolysis or hydrolysis.
  • the establishment of such a raw material recycling plant not only requires large investment and heavy pollution, but also can only process clean waste materials. Therefore, the collection, transportation, separation/sorting and pre-treatment of waste XLPE have high costs, high energy consumption and low efficiency.
  • the total operating cost of the recycling process exceeds the value of the output, and the value of recycling is not large.
  • most of the waste cross-linked polyethylene in my country is recycled by pyrolysis method, which has great pollution to the environment. Therefore, this method is not worth promoting and has been banned.
  • Waste polymer materials can be recycled through solvent separation and recovery, melt processing recovery and solid phase processing recovery.
  • waste polymer materials can be recycled through solvent separation and recovery, melt processing recovery and solid phase processing recovery.
  • the three-dimensional network structure of waste cross-linked polyethylene materials the It can neither be dissolved nor melted, so it is difficult to use solvent separation and recovery or melt processing recovery, so it can only be recovered by solid-phase processing.
  • a waste cross-linked polyethylene recycling material and its recycling method discloses a waste cross-linked polyethylene recycling material and a recycling method thereof.
  • the method is to first pulverize the waste cross-linked polyethylene into 0.5-2 cm pellets, and then place them in a solid-phase mechanical chemical reactor to carry out During the grinding process, the cooling water temperature is controlled to be 5-30°C, the grinding pressure is 10-50MPa, the grinding speed is 10-1000rpm, and the grinding times are 5-30 times.
  • the material is ground into powder, Its particle size is 100-500 mesh, and the gel content tested by the Soxhlet extraction device is ⁇ 60%.
  • the method provided by the invention can selectively cut off the C—O bond and Si—O bond in the waste cross-linked polyethylene, cut off the cross-linked bond of the three-dimensional cross-linked structure, and change its original insoluble and infusible characteristics , improve the thermoplasticity and melt fluidity of the material, and re-endow the waste cross-linked polyethylene recycled material with thermoplastic processability, so that the obtained recycled material can be prepared by conventional thermoplastic processing methods such as extrusion and calendering. Recycled materials and products.
  • the inventor of the present invention found in the actual implementation process of the above-mentioned patented technology that although the waste cross-linked polyethylene was ground by using a solid-phase mechanical chemical reactor, the de-crosslinking of the waste cross-linked polyethylene was achieved to a certain extent. However, the powder obtained by grinding shows de-cross-linking on the surface of the particles, and the interior is still in a cross-linking state, resulting in a state of particle flow during the thermoplastic processing of the powder.
  • the present invention provides a modified cross-linked polyethylene and a preparation method thereof, a regenerated product and a preparation method thereof.
  • the waste cross-linked polyethylene is ground by using a solid-phase mechanochemical reactor, and then the modified cross-linked polyethylene is obtained by plasticizing the asphalt as a plasticizer.
  • the waste cross-linked polyethylene/asphalt material has excellent processing fluidity, and is suitable for various thermoplastic processing processes to prepare high-performance recycled products.
  • the present invention is realized by adopting the technical solutions in four aspects consisting of the following technical measures.
  • the present invention provides a method for preparing a modified cross-linked polyethylene, comprising the following steps:
  • step (2) adding the natural liquid asphalt and the cross-linked polyethylene ultrafine powder obtained in step (1) into an internal mixer, mixing and internal mixing to obtain the modified cross-linked polyethylene.
  • step (1) is as follows: adding the cross-linked polyethylene powder into the grinding disc-type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, collecting the cross-linked polyethylene ultrafine powder .
  • the process parameters of the grinding disc-type solid-phase mechanochemical reactor in step (1) are: the grinding pressure is 2-3 MPa, the temperature of the grinding disc surface is controlled to be 25-35° C. by introducing a circulating cooling liquid, and the circulating grinding 13 ⁇ 15 times, the grinding disc speed is 30 ⁇ 50 rpm.
  • the grinding disc-type solid-phase mechanochemical reactor is the mechanochemical reactor disclosed in the patent ZL95111258.9 previously granted by the applicant of the present invention.
  • the actual operation of the above-mentioned cyclic milling process is to grind the mixed material in a disc-shaped mechanochemical reactor, collect the discharge end product, and place it in the disc-shaped mechanochemical reactor for grinding again.
  • the above process depends on Grind 1 time for the cycle.
  • the temperature of the surface of the grinding disc is controlled to be 25-35° C. by introducing a circulating cooling liquid, and the cooling liquid is water, ethylene glycol or glycerin.
  • the process parameters of the internal mixer in step (2) are: the internal mixing temperature is controlled at 180-200 ° C, the rotational speed is controlled at 30-50 rpm, the time is controlled at 10-30 min, the natural liquid asphalt and the cross-linked polyethylene ultrafine
  • the mass ratio of the powder is (0.1-0.3):(0.9-0.7).
  • the natural liquid asphalt in step (2) is selected to have a penetration of 50-120 (0.1mm), a softening point of 42-49°C, a flash point of 240-260°C, and a ductility of 120-180cm. Natural liquid asphalt.
  • the natural liquid asphalt in step (2) is commercially available 90# liquid asphalt.
  • the cross-linked polyethylene powder is waste cross-linked polyethylene powder
  • the preparation method of the waste cross-linked polyethylene powder is as follows: selecting waste cross-linked polyethylene with a cross-linked polyethylene ratio of not less than 98% Ethylene materials or products, after pretreatment including washing, are processed and pulverized to waste cross-linked polyethylene powder with an average particle size of not more than 1 mm.
  • waste cross-linked polyethylene materials or products include waste materials in the synthesis and production process of cables, waste cables, liquid transportation pipes, refrigeration system pipes, pipes for floor heating systems, etc.
  • those skilled in the art can inquire about the specifications of the waste cross-linked polyethylene material or product to determine whether it conforms to the selection of the raw material of the present invention.
  • the cleaning and pretreatment of waste cross-linked polyethylene materials or products is mainly to remove impurities on the surface of waste cross-linked polyethylene materials or products, and if necessary, the part of non-cross-linked polyethylene needs to be removed.
  • Those skilled in the art can perform specific treatment according to the prior art according to the actual conditions of the waste cross-linked polyethylene materials or products that need to be recycled.
  • the waste cross-linked polyethylene powder crushed to an average particle size of not more than 1 mm can be processed by existing conventional crushing equipment such as jaw crusher, planetary ball mill, and refrigerated ball mill.
  • the treatment is pulverized to waste cross-linked polyethylene powder with an average particle size not higher than 500um.
  • the present invention provides a modified cross-linked polyethylene, which is prepared from natural liquid asphalt and cross-linked polyethylene ultrafine powder as raw materials.
  • the mass ratio of the natural liquid asphalt to the cross-linked polyethylene ultrafine powder is (0.1-0.3):(0.9-0.7).
  • the method for preparing modified cross-linked polyethylene from natural liquid asphalt and cross-linked polyethylene ultrafine powder as raw materials is the preparation method of modified cross-linked polyethylene provided above.
  • the present invention provides a method for preparing a recycled product, comprising the following steps:
  • the modified cross-linked polyethylene is pulverized to obtain composite granules, and the composite granules are prepared by thermoplastic processing to obtain recycled products;
  • the modified cross-linked polyethylene is prepared by the above-mentioned preparation method of modified cross-linked polyethylene.
  • the modified cross-linked polyethylene is pulverized into composite particles with an average particle size of 0.5-1 cm.
  • the pulverization can be carried out by existing conventional pulverizing equipment such as jaw crusher, planetary ball mill, and refrigerated ball mill. deal with.
  • thermoplastic processing includes extrusion molding, injection molding, and calendering.
  • thermoplastic processing specifically:
  • the composite pellets are processed by single-screw extruding.
  • the process parameters of extruding are as follows: the temperature of the three zones is 150 °C in the first zone, 175 °C in the second zone, 180 °C in the third zone, 175 °C in the machine head, and the speed is controlled at 50 ⁇ 100rpm, the die width is 10cm;
  • the composite pellets are extruded by twin-screw.
  • the process parameters of extrusion are as follows: the die width is 30cm, the first zone is 150°C, the second zone is 175°C, the third zone is 180°C, the die head is 175°C, and the rotational speed is controlled at 50 ⁇ 100rpm;
  • the composite pellets are processed by vulcanization platen, and the process parameters are: temperature 180°C, pressure 10MPa, exhaust 5 times, hot pressing for 5 minutes, and cold pressing to room temperature under pressure of 10MPa;
  • the composite pellets are processed by injection molding, and the process parameters are: the temperature of the first zone is 160°C, the temperature of the second zone is 190°C, the temperature of the third zone is 190°C, and the temperature of the fourth zone is 190°C.
  • the present invention provides a recycled product, which is obtained by the above-mentioned preparation method of the recycled product.
  • the inventors of the present invention have found that the waste cross-linked polyethylene ultrafine powder obtained after being milled in a disc-type solid-phase mechanochemical reactor can be plasticized by using asphalt, so that it has excellent processing properties. fluidity.
  • the asphalt containing a variety of small organic molecules acts as a plasticizer, and the small molecules are inserted between the molten particles, weakening the attraction between molecular chains and increasing the distance between them. , plays a role in lubrication, reduces the melt viscosity and increases the possibility of particle movement.
  • the waste cross-linked polyethylene ultrafine powder plasticized by asphalt can not only be molded in a compression force field with high pressure, but also suitable for thermoplastic extrusion processing in a low shear force field. Good mechanical properties. Moreover, continuous large-scale sheets can be obtained by thermoplastic processing, because the waste cross-linked polyethylene ultrafine powder plasticized by asphalt forms a particle flow with lubricating effect, and the interaction between particles The force enables the smallest moving units to move with each other under the condition of heating, and can be closely arranged to form large sheets. Unlike unlubricated powder, the flow is jerky, and it is difficult to have good fluidity under the action of shearing, so it is difficult to continue. forming. This allows the waste powder to undergo secondary processing, and endows this worthless material with the ability to be processed into high-value products, which not only solves the environmental problems of waste on a large scale, but also increases the value of the product and obtains unexpected results. profit.
  • the inventors of the present invention have found through comparative experiments that when the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is limited to (0.1-0.3): (0.9-0.7), the final thermoplastic processing The overall performance of the product is better.
  • the mass ratio of natural liquid asphalt and waste XLPE ultrafine powder is lower than 0.1:0.9, a high shear force field is still required for smooth processing; when natural liquid asphalt and waste XLPE ultrafine powder are When the mass ratio of the powder is higher than 0.3:0.7, the asphalt cannot be well mixed with the powder and the mechanical properties of the material decrease significantly after processing.
  • the obtained recycled board after being processed by single-screw extruding sheet, the obtained recycled board has a tensile strength of up to 20.3 MPa and an elongation at break of up to 610% after testing.
  • the technical solution of the present invention is to use a solid-phase force chemical reactor to grind the waste cross-linked polyethylene, and then use asphalt as a plasticizer to plasticize, so that the partially de-cross-linked waste obtained after grinding
  • the cross-linked polyethylene/asphalt material has excellent processing fluidity and is suitable for various thermoplastic processing processes to prepare high-performance recycled products;
  • waste cross-linked polyethylene as the main raw material, which is different from the existing recycling technology, where waste cross-linked polyethylene is pulverized and then added as a filler in a small amount to prepare recycled products, which can be more efficient.
  • Waste cross-linked polyethylene for recycling
  • the technical scheme of the present invention is not only easy to operate, low in recovery cost, easy for large-scale production, and free from any waste and secondary pollution during the recovery process, but also provides a new recycling route for waste cross-linked polyethylene. .
  • Fig. 1 is the SEM image of the regenerated product prepared in Example 1 of the present invention after being etched by cyclohexane. It can be clearly seen that the waste XLPE ultrafine powder in the recycled products has good compatibility with the natural liquid asphalt, and the asphalt can be uniformly dispersed in the waste XLPE ultrafine powder, which plays a role in plasticizing and lubricating. effect.
  • Figure 2 is a photo of the regenerated product prepared in Example 1 of the present invention. It is obvious that the present invention can produce a sheet with smooth surface and continuously extruded after the single-screw extruding sheet processing under the condition of low shear force field.
  • FIG. 3 is a comparison diagram of torque flow curves of regenerated products prepared in Examples 1, 3 and 5 of the present invention and Comparative Examples 1 and 2.
  • FIG. 3 It can be clearly seen that compared with Comparative Example 1 without asphalt added, the technical solution of the present invention adds asphalt to toughen, firstly, it makes the processing fluidity better, and the torque during banburying decreases from 30Nm to 6Nm with the addition of asphalt. Under the condition of a certain internal mixing speed, the torque reflects the ease of thermoplastic processing. The lower the torque, the lower the shear force required for internal mixing, the easier the powder is to process, and the interaction between the particle flows. The smaller the force, the better the plasticizing effect of asphalt in the material, where 0%, 10%, 20%, 30%, and 40% refer to the added amount of asphalt.
  • FIG. 4 is a high-pressure capillary rheological comparison diagram of the regenerated products prepared in Examples 1, 3 and 5 of the present invention and Comparative Examples 1 and 2.
  • FIG. 4 It can be clearly seen that with the increase of asphalt, the apparent viscosity of the composite material gradually decreases at the first shear rate, the flow property increases, and the thermoplastic processing can be better. It also shows that the asphalt has a good toughening effect on the waste cross-linked polyethylene powder, wherein 0%, 10%, 20%, 30% and 40% refer to the addition amount of asphalt.
  • the experimental sample is subjected to a conventional tensile test according to the test standard as ASTM D638 to obtain its tensile strength and elongation at break.
  • the tensile speed was 50mm/min when testing tensile strength.
  • 90# liquid asphalt is purchased from Liaoning Hualu Special Asphalt Co., Ltd.;
  • the waste cross-linked polyethylene comes from samples provided by TBEA (Deyang) Cable Co., Ltd., and the cross-linked polyethylene accounts for 98%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • waste cross-linked polyethylene material and after pretreatment including washing, pulverize it to waste cross-linked polyethylene powder with an average particle size of not more than 1 mm;
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, the rotating speed of the grinding disc is 50 rpm, and the cooling liquid is water, ethylene glycol alcohol or glycerin. ;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene; wherein, the process parameters of the internal mixer are: internal mixing
  • the temperature is controlled at 180°C
  • the rotation speed is controlled at 50rpm
  • the time is controlled at 10min.
  • the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.2:0.8;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5-1 cm;
  • step (4) The composite pellets obtained in step (4) are subjected to single-screw extrusion processing to prepare a regenerated product in the form of a sheet.
  • the process parameters of the extrusion processing are: the temperature of the three zones is 150 ° C in the first zone and 175 ° C in the second zone. °C, the three zones are 180°C, the machine head is 175°C, the speed is controlled at 100rpm, and the die width is 10cm.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 20.3 MPa, and the elongation at break was 610%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene; wherein, the process parameters of the internal mixer are: internal mixing
  • the temperature is controlled at 180°C
  • the rotation speed is controlled at 50rpm
  • the time is controlled at 10min.
  • the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.2:0.8;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5-1 cm;
  • step (4) the composite pellet obtained in step (4) is processed by vulcanization pressing plate, and the regenerated product in sheet form is prepared, and the technical parameters of vulcanizing pressing plate are: temperature 180 ° C, pressure 10 MPa, exhaust 5 times, hot pressing for 5 minutes, Cold-pressed to room temperature under pressure of 10MPa.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 19.2 MPa, and the elongation at break was 560%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene; wherein, the process parameters of the internal mixer are: internal mixing
  • the temperature is controlled at 180°C
  • the rotation speed is controlled at 50rpm
  • the time is controlled at 10min.
  • the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.1:0.9;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5 to 1 cm;
  • step (4) The composite pellets obtained in step (4) are subjected to single-screw extrusion processing to prepare a regenerated product in the form of a sheet.
  • the process parameters of the extrusion processing are: the temperature of the three zones is 150 ° C in the first zone and 175 ° C in the second zone. °C, the three zones are 180°C, the machine head is 175°C, the speed is controlled at 100rpm, and the die width is 10cm.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 18.7 MPa, and the elongation at break was 540%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • waste cross-linked polyethylene material after the pretreatment including cleaning, it is processed and pulverized to the waste cross-linked polyethylene powder with an average particle size not higher than 1mm;
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene; wherein, the process parameters of the internal mixer are: internal mixing
  • the temperature is controlled at 180°C
  • the rotation speed is controlled at 50rpm
  • the time is controlled at 10min.
  • the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.1:0.9;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5 to 1 cm;
  • step (4) the composite pellet obtained in step (4) is processed by vulcanization pressing plate, and the regenerated product in sheet form is prepared, and the technical parameters of vulcanizing pressing plate are: temperature 180 ° C, pressure 10 MPa, exhaust 5 times, hot pressing for 5 minutes, Cold-pressed to room temperature under pressure of 10MPa.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 18.2 MPa, and the elongation at break was 527%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene;
  • the process parameters of the internal mixer are: internal mixing The temperature is controlled at 180°C, the rotation speed is controlled at 50rpm, and the time is controlled at 10min, and the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.3:0.7;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5-1 cm;
  • step (4) The composite pellets obtained in step (4) are subjected to single-screw extrusion processing to prepare a regenerated product in the form of a sheet.
  • the process parameters of the extrusion processing are: the temperature of the three zones is 150 ° C in the first zone and 175 ° C in the second zone. °C, the three zones are 180°C, the machine head is 175°C, the speed is controlled at 100rpm, and the die width is 10cm.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 17.2 MPa, and the elongation at break was 460%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene;
  • the process parameters of the internal mixer are: internal mixing The temperature is controlled at 180°C, the rotation speed is controlled at 50rpm, and the time is controlled at 10min, and the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.3:0.7;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5 to 1 cm;
  • step (4) the composite pellet obtained in step (4) is processed by vulcanization pressing plate, and the regenerated product in sheet form is prepared, and the technical parameters of vulcanizing pressing plate are: temperature 180 ° C, pressure 10 MPa, exhaust 5 times, hot pressing for 5 minutes, Cold-pressed to room temperature under pressure of 10MPa.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 17.1 MPa, and the elongation at break was 435%.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • waste cross-linked polyethylene material after the pretreatment including cleaning, it is processed and pulverized to the waste cross-linked polyethylene powder with an average particle size not higher than 1mm;
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 2MPa, the temperature of the surface of the grinding disc is controlled to be 35 °C by introducing a circulating cooling liquid, the circular grinding is performed 13 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene; wherein, the process parameters of the internal mixer are: internal mixing
  • the temperature is controlled at 200°C
  • the rotation speed is controlled at 30rpm
  • the time is controlled at 30min.
  • the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.2:0.8;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5 to 1 cm;
  • twin-screw extrusion processing is performed on the composite pellets obtained in step (4) to prepare a regenerated product in the form of a sheet. 175°C, three zones 180°C, machine head 175°C, speed controlled at 50rpm.
  • the present embodiment utilizes waste cross-linked polyethylene and asphalt to prepare the method for modified cross-linked polyethylene and recycled products, comprising the following steps:
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the grinding disc surface is controlled to be 25 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the grinding disc speed is 30 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer and mixing and mixing to obtain the modified cross-linked polyethylene; wherein, the process parameters of the internal mixer are: internal mixing
  • the temperature is controlled at 190°C
  • the rotation speed is controlled at 40rpm
  • the time is controlled at 20min.
  • the mass ratio of natural liquid asphalt and waste cross-linked polyethylene ultrafine powder is 0.2:0.8;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5 to 1 cm;
  • the composite pellets obtained in the step (4) are subjected to injection molding to prepare recycled products in the form of sheets.
  • the process parameters of the extrusion process are: the temperature of the first zone is 160°C, the temperature of the second zone is 190°C, and the temperature of the third zone is 190°C. °C, the temperature of the four zones is 190°C.
  • This comparative example utilizes waste cross-linked polyethylene to prepare the method for recycled products, including the following steps:
  • the grinding disc-type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc-type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer for mixing and mixing; wherein, the process parameters of the internal mixer are: the internal mixing temperature is controlled at 180 ° C, and the rotating speed is controlled at 50 rpm , the time is controlled at 10min;
  • step (3) (4) pulverizing the cross-linked polyethylene material obtained after banburying in step (3) to obtain cross-linked polyethylene pellets with an average particle size of 0.5 to 1 cm;
  • step (4) The cross-linked polyethylene pellets obtained in step (4) are subjected to single-screw extrusion processing to prepare a regenerated product in the form of a sheet.
  • the process parameters of the extrusion processing are: the temperature of the three zones is The second zone is 175°C, the third zone is 180°C, the machine head is 175°C, the speed is controlled at 100rpm, and the die width is 10cm.
  • the powder melted incompletely, the particle flow connection was not tight, and the fluid at the die was unstable, resulting in intermittent extrudates, unable to form a continuous and smooth sheet.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 15.2 MPa, and the elongation at break was 376%.
  • This comparative example utilizes waste cross-linked polyethylene and bitumen to prepare the method for recycled products, including the following steps:
  • the grinding disc type solid-phase mechanical chemical reactor for grinding and pulverizing, and after the grinding is completed, the waste cross-linked polyethylene ultrafine powder is collected; wherein, the grinding disc type solid phase
  • the technological parameters of the mechanochemical reactor are as follows: the grinding pressure is 3MPa, the temperature of the surface of the grinding disc is controlled to be 28 °C by feeding the circulating cooling liquid, the circular grinding is performed 15 times, and the rotating speed of the grinding disc is 50 rpm;
  • step (3) adding the natural liquid asphalt and the waste cross-linked polyethylene ultrafine powder obtained in step (2) into the internal mixer for mixing and mixing; wherein, the process parameters of the internal mixer are: the internal mixing temperature is controlled at 180 °C, The rotation speed is controlled at 50rpm, the time is controlled at 10min, and the mass ratio of natural liquid asphalt to waste XLPE ultrafine powder is 0.4:0.6;
  • step (3) (4) pulverizing the modified cross-linked polyethylene obtained after banburying in step (3) into composite pellets with an average particle size of 0.5 to 1 cm;
  • step (4) The composite pellets obtained in step (4) are subjected to single-screw extrusion processing to prepare a regenerated product in the form of a sheet.
  • the process parameters of the extrusion processing are: the temperature of the three zones is 150 ° C in the first zone and 175 ° C in the second zone. °C, the three zones are 180°C, the machine head is 175°C, the speed is controlled at 100rpm, and the die width is 10cm.
  • the regenerated product obtained by the above final preparation was used as a sample for mechanical property test, and its tensile strength was 14.5 MPa, and the elongation at break was 350%.

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Abstract

本发明提供一种改性交联聚乙烯及其制备方法、再生制品及其制备方法，改性交联聚乙烯的制备方法是通过利用固相力化学反应器对废弃交联聚乙烯进行碾磨处理，再利用沥青作为增塑剂进行增塑得到改性交联聚乙烯，增塑处理使得经碾磨后所得部分解交联的废弃交联聚乙烯/沥青材料具备优良的加工流动性，适用于各类热塑加工工艺制备具备高性能的再生制品。经过沥青增塑后的废弃交联聚乙烯超细粉体，不仅可以在具有高压力的压缩力场中成型，也可适用于低剪切力场的热塑性挤出加工，制备所得再生制品都具备良好的力学性能。

Description

一种改性交联聚乙烯及其制备方法、再生制品及其制备方法 技术领域
本发明属于废弃交联聚乙烯回收利用技术领域，具体涉及一种改性交联聚乙烯及其制备方法、再生制品及其制备方法。
背景技术
交联聚乙烯是聚乙烯通过辐照交联、过氧化物交联和硅烷交联等方法，利用分子间共价键作用形成了三维网状结构，具有不溶不熔的特点，交联过后的聚乙烯获得了优异的耐热性、耐应力开裂性、耐化学腐蚀性、耐磨损性、抗蠕变性能及出色的力学等性能，广泛应用于化工、建筑、汽车、机械、电力、包装、农业等行业，尤其被用于制备管道和绝缘电线电缆。
显然，废弃交联聚乙烯的产生来自于上述技术领域，例如在电缆料领域中的来源主要有两个，第一个就是合成和生产过程中废弃料，由于电缆线生产的特殊性，在工艺调试过程中不可避免的会产生废料，约有产品生产的5％；第二个就是使用过后的电缆料，在达到使用年限后替换下的旧电缆，这一部分是非常大量且完全无法减少的废料。并且由于交联聚乙烯的三维网状结构更是无法再次热塑加工，致使废料十分难以进行回收利用。
废弃交联聚乙烯应是极具回收利用价值的资源，根据测算，回收利用1吨废弃交联聚乙烯相当于少用3-5吨石油，这对缺乏原生资源，原油大量依赖进口，据国家统计局数据显示，2019年，中国原油进口量为50572万吨，同比增长9.5％，对于我国国民经济无疑具有十分重要的意义。
目前，处理废弃交联聚乙烯的方法主要有填埋、焚烧和裂解等。
填埋法：占地面积大，与城市建设争地矛盾突出，填埋费用高，多与其他城市固体垃圾一同填埋，填埋渗出的有机物会污染水源，影响地下生态环境。
焚烧法：常与其他城市废弃固体垃圾一起焚烧，产生的有毒气体，会污染大气，而使用焚烧的无毒化处理设备又投资大，成本高(建一座大型焚烧厂需20多亿元)。
裂解法：是指通过热解或水解等化学反应从废弃交联聚乙烯中回收单体、低聚物等原料。但建立这种原料回收工厂不仅投资大、污染重，还只能处理清洁的废弃料，因而废弃交联聚乙烯的收集、运输、分离/分类和前处理费用高、能耗 高，效率低，使得回收过程的运行总费用超过产出物的价值，回收利用的价值不大。现今我国大部分废弃交联聚乙烯都是裂解法回收，对于环境具有极大污染，因此该方法不值得推广，已开始被禁止。
回收利用(Reuse，Recycle)虽是废弃交联聚乙烯最有效、最有前景的处理方法。但从目前来说，对于通常废弃高分子材料可以通过溶剂分离回收、熔体加工回收和固相加工回收这三种方法进行回收利用，但由于废弃交联聚乙烯材料的三维网状结构使其既不能溶解，也不能熔融，因此难以采用溶剂分离回收或熔体加工回收方式，从而只能通过固相加工方式进行回收。
为了提供一种更为清洁、高效、易于实施的废弃交联聚乙烯固相加工回收利用新技术，本发明申请人在先申请专利“一种废弃交联聚乙烯回收材料及其回收方法”(CN104385485A)中，公开了一种废弃交联聚乙烯回收材料及其回收方法，该方法是先将废弃交联聚乙烯粉碎成0.5-2cm的粒料，然后置于固相力化学反应器中进行碾磨，碾磨过程中控制冷却循环水温为5～30℃，碾磨压力为10～50MPa，碾磨转速10～1000rpm，碾磨次数为5-30次，其材料被碾磨成粉体，其粒度为100-500目，且通过索氏提取装置测试的凝胶含量<60％。
该发明提供的方法能够选择性地切断废弃交联聚乙烯中的C—O键和Si—O键，将其三维交联结构的交联键断开，改变其原有的不溶不熔的特性，提高材料的热塑性和熔融流动性，重新赋予了废弃交联聚乙烯回收材料热塑加工性，使其获得的回收材料能够通过挤出、压延等常规的热塑加工方法制备性能优异的高值化回收材料及制品。
但是，本发明的发明人在对上述专利技术实际实施过程中发现，虽然利用固相力化学反应器对废弃交联聚乙烯进行了碾磨，实现了一定程度上废弃交联聚乙烯的解交联，但是经过碾磨所得粉体呈现出颗粒外表解交联，内部仍为交联状态，导致在粉体热塑加工时呈现颗粒流的状态。因此虽然其具有一定的热塑加工性，但是其流动性通常只有在高剪切力场的作用下才能勉强进行加工，而对于低剪切力场的单螺杆直接挤出成型以及无剪切力场的硫化压板技术，都表现出了较差的力学性能，因此在其应用例中也并未谈及直接挤出成型为片材的应用方式及产品性能。
并且上述专利技术在实施过程中还发现，即便按照其应用例公开先通过高剪切力场的双螺杆挤出机挤出造粒再热压成型，但是其加工的产品只能是不连续的 小块片材，无法在实际生产中大量连续加工，极大的限制了其应用范围。
发明内容
本发明针对上述现有技术中的问题，提供一种改性交联聚乙烯及其制备方法、再生制品及其制备方法。该方法通过利用固相力化学反应器对废弃交联聚乙烯进行碾磨处理，再利用沥青作为增塑剂进行增塑得到改性交联聚乙烯，增塑处理使得经碾磨后所得部分解交联的废弃交联聚乙烯/沥青材料具备优良的加工流动性，适用于各类热塑性加工工艺制备具备高性能的再生制品。
为实现上述目的，本发明是采用由以下技术措施构成的四个方面的技术方案来实现的。
第一方面，本发明提供一种改性交联聚乙烯的制备方法，包括以下步骤：
(1)获取交联聚乙烯超细粉体；
(2)将天然液体沥青与步骤(1)所得交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯。
优选地，步骤(1)的具体过程如下：将交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得到交联聚乙烯超细粉体。
优选地，步骤(1)中磨盘型固相力化学反应器的工艺参数为：碾磨压力为2～3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为25～35℃，循环碾磨13～15次，磨盘转速30～50转/分。
具体地，所述磨盘型固相力化学反应器为本发明申请人在先授权专利ZL95111258.9所公开的力化学反应器。通常地，上述循环碾磨的工艺实际操作为将混合物料经磨盘形力化学反应器碾磨后，收集出料端产物后再次置于磨盘形力化学反应器中进行碾磨处理，上述过程视为循环碾磨1次。
优选地，步骤(1)中所述磨盘盘面温度通过通入循环冷却液体控制温度为25～35℃，所述冷却液体为水、乙二醇或甘油。
优选地，步骤(2)中密炼机的工艺参数为：密炼温度控制在180～200℃，转速控制在30～50rpm，时间控制在10～30min，天然液体沥青与交联聚乙烯超细粉体的质量比为(0.1～0.3)：(0.9～0.7)。
优选地，步骤(2)中所述天然液体沥青选择为针入度50～120(0.1mm)，软化点42～49℃，闪点在240℃～260℃之间，延度120～180cm的天然液体沥青。
优选地，步骤(2)中所述天然液体沥青选择市售90#液体沥青。
优选地，所述交联聚乙烯粉体为废弃交联聚乙烯粉体，所述废弃交联聚乙烯粉体制备方法如下：选取交联聚乙烯占比不低于98％的废弃交联聚乙烯材料或制品，经过包括洗净的预处理后，将其处理粉碎至平均粒径不高于1mm的废弃交联聚乙烯粉体。
具体地，废弃交联聚乙烯材料或制品包括电缆在合成和生产过程中废弃料、废旧电缆、液体输送管道、制冷系统管道、地暖系统用管等产生的废料等废弃量较大的工业废弃物，本领域技术人员可查询废弃交联聚乙烯材料或制品的规格确定是否符合将其作为本发明的原料选择。
具体地，对废弃交联聚乙烯材料或制品进行洗净预处理主要是将废弃交联聚乙烯材料或制品表面杂质进行清除，如有必要，还需将非交联聚乙烯的部分除去，本领域技术人员可根据其需要回收利用的废弃交联聚乙烯材料或制品的实际状况，根据现有技术进行具体的处理。
具体地，所述处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体，可通过颚式破碎机，行星球磨机，冷冻球磨机等现有的常规粉碎设备进行处理。
优选地，所述处理粉碎至平均粒径不高于500um的废弃交联聚乙烯粉体。
第二方面，本发明提供一种改性交联聚乙烯，由天然液体沥青与交联聚乙烯超细粉体为原料制备而成。
优选地，所述天然液体沥青与交联聚乙烯超细粉体的质量比为(0.1～0.3)：(0.9～0.7)。
优选地，由天然液体沥青与交联聚乙烯超细粉体为原料制备改性交联聚乙烯的方法为上述提供的改性交联聚乙烯的制备方法。
第三方面，本发明提供一种再生制品的制备方法，包括以下步骤：
将改性交联聚乙烯进行粉碎处理得到复合粒料，将复合粒料通过热塑性加工制备得到再生制品；
其中，所述改性交联聚乙烯采用上述提供的改性交联聚乙烯的制备方法制得。
优选地，所述改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料，具体地，粉碎处理可通过颚式破碎机，行星球磨机，冷冻球磨机等现有的常规粉碎设备进行处理。
优选地，所述热塑性加工，包括挤塑型材加工、注塑加工、压延成型。
优选地，所述热塑性加工，具体为：
将复合粒料进行单螺杆挤片加工，挤片加工的工艺参数为：三区温度分别是为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在50～100rpm，口模宽度为10cm；
或为，
将复合粒料进行双螺杆挤出加工，挤出加工的工艺参数为：口模宽度为30cm，一区150℃、二区175℃、三区180℃，机头175℃，转速控制在50～100rpm；
或为，
将复合粒料进行硫化压板加工，工艺参数为：温度180℃、压力10MPa、排气5次，热压5分钟，压力10MPa下冷压至室温；
或为，
将复合粒料进行注塑加工，工艺参数为：一区温度160℃、二区温度190℃、三区温度190℃、四区温度190℃。
第四方面，本发明提供一种再生制品，采用上述再生制品的制备方法制得。
值得说明的是，经本发明的发明人研究发现，经磨盘型固相力化学反应器碾磨处理后所得废弃交联聚乙烯超细粉体，通过利用沥青增塑，使其具备优秀的加工流动性。在表面熔融的颗粒流中，含有多种有机小分子的沥青充当了增塑剂的作用，小分子插人到熔融颗粒之间，削弱了分子链间的引力，增大了它们之间的距离，起到了润滑的作用，降低了熔体黏度，增加了颗粒移动的可能性。
经过沥青增塑后的废弃交联聚乙烯超细粉体，不仅可以在具有高压力的压缩力场中成型，也可适用于低剪切力场的热塑性挤出加工，制备所得再生制品都具备良好的力学性能。并且，经热塑性加工可制得具有连续性的大规格片材，是因为经过沥青增塑后的废弃交联聚乙烯超细粉体形成一种带有润滑效果的颗粒流，颗粒之间的作用力使得最小运动单元既可以在升温条件下相互运动，又可以紧密排列形成大型片材，不像未经润滑的粉体，流动生涩，难以在剪切作用下具有良好的流动性从而很难连续成型。这就使得废弃的粉体可以进行二次加工，并且赋予这种毫无价值的材料一种可加工成高值产品的能力，既大规模解决了废料的环境问题也可以提升产品价值获得意想不到的利润。
值得重点说明的是，天然液体沥青与废弃交联聚乙烯超细粉体的质量比对于 热塑加工的容易程度及加工所得再生制品性能具有重要影响，虽然随着天然液体沥青添加量的增加，密炼时转矩随之下降，颗粒流之间的作用力越小，越容易加工，但是沥青添加量过高时会出现以下弊端：第一可以明显观察到在密炼混合时存在沥青与粉体混合不完全，多余未进入粉体间隙的沥青留在了密炼腔体壁上；第二由于沥青含量太多，颗粒之间作用力太小，导致黏度太低，最后片材力学性能较差，成为了强度不高，韧性低的材料，没有利用价值。因此本发明的发明人经过对照实验发现，限定天然液体沥青与废弃交联聚乙烯超细粉体的质量比为(0.1～0.3)：(0.9～0.7)时，最终热塑加工所制得再生制品综合性能更佳。当天然液体沥青与废弃交联聚乙烯超细粉体的质量比低于0.1：0.9时，仍需要较高的剪切力场才可以顺利加工；当天然液体沥青与废弃交联聚乙烯超细粉体的质量比高于0.3：0.7时，沥青不能很好的与粉体混合均匀且加工成型后材料力学性能下降非常明显。
利用上述优选的技术方案，在通过单螺杆挤片加工后，所制得的再生板材经测试，其拉伸强度可达20.3MPa，断裂伸长率可达610％。
本发明具有如下的有益效果：
(1)本发明技术方案通过利用固相力化学反应器对废弃交联聚乙烯进行碾磨处理，再利用沥青作为增塑剂进行增塑，从而使得经碾磨后所得部分解交联的废弃交联聚乙烯/沥青材料具备优良的加工流动性，适用于各类热塑加工工艺制备具备高性能的再生制品；
(2)本发明技术方案以废弃交联聚乙烯作为主要原料，区别于现有回收利用技术中多将废弃交联聚乙烯粉碎后作为填料少量添加制备再生制品的方式，能够更为效率的对废弃交联聚乙烯进行回收利用；
(3)本发明技术方案限定选择极低成本的沥青作为增塑剂，并具有良好的技术效果，进一步降低了回收利用废弃交联聚乙烯的整体成本，并为将来回收利用废弃交联聚乙烯提供了启迪；
(4)本发明技术方案不仅操作简便，回收成本低廉，易于规模化生产，且回收过程中无任何废弃物产生，无二次污染，同时也为废弃交联聚乙烯提供了一条新的回收途径。
附图说明
图1为本发明实施例1制备所得再生制品在经环己烷刻蚀过的SEM图。可明 显看出，再生制品中废弃交联聚乙烯超细粉体与天然液体沥青具有良好的相容性，沥青可以均匀分散在废弃交联聚乙烯超细粉体中，起到增塑润滑的作用。
图2为本发明实施例1制备所得再生制品的照片。明显看出，本发明在低剪切力场条件下的单螺杆挤片加工后可以制成表面平滑且连续挤出的片材。
图3为本发明实施例1、3、5，对比例1、2制备所得再生制品的转矩流变曲线对比图。可明显看出，相比未添加沥青的对比例1，本发明技术方案中加入沥青增韧，第一使得加工流动性更好，密炼时转矩随着沥青的加入从30Nm降到了6Nm。在密炼加工转速一定的条件下，转矩反应了热塑加工的容易程度，转矩越低说明密炼混合所需要的剪切力越低，粉体越容易加工，颗粒流之间的作用力越小，充分体现了沥青在材料中的增塑作用，其中，0％、10％、20％、30％、40％指的是沥青的添加量。
图4为本发明实施例1、3、5，对比例1、2制备所得再生制品的高压毛细管流变对比图。可以明显的看出随着沥青的增加在第剪切速率下复合材料的表观黏度逐渐下降，流动性能增加，可以更好的进行热塑加工。也说明了沥青对于废弃的交联聚乙烯粉体起到了良好的增韧作用，其中，0％、10％、20％、30％、40％指的是沥青的添加量。
具体实施方式
下面通过实施例并结合附图对本发明作进一步说明。值得指出的是，给出的实施例不能理解为对本发明保护范围的限制，该领域的技术人员根据本发明的内容对本发明作出的一些非本质的改进和调整仍应属于本发明保护范围。
下述实施例中，对实验样品按照测试标准为ASTM D638进行常规的拉伸实验测试，得到其拉伸强度、断裂伸长率。测试拉伸强度时拉伸速度50mm/min。
下述实施例中，90#液体沥青选购自辽宁华路特种沥青有限公司；
废弃交联聚乙烯来源于自特变电工(德阳)电缆股份有限公司所提供样品，交联聚乙烯占比为98％。
实施例1
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至平均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分，冷却液体为水、乙二醇或甘油。；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.2：0.8；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为平均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行单螺杆挤片加工，制备得到为片材形式的再生制品，挤片加工的工艺参数为：三区温度分别为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在100rpm，口模宽度为10cm。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为20.3MPa，断裂伸长率为610％。
实施例2
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.2：0.8；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm 的复合粒料；
(5)将步骤(4)所得复合粒料进行硫化压板加工，制备得到为片材形式的再生制品，硫化压板工艺参数为：温度180℃、压力10MPa、排气5次，热压5分钟，压力10MPa下冷压至室温。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为19.2MPa，断裂伸长率为560％。
实施例3
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.1：0.9；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行单螺杆挤片加工，制备得到为片材形式的再生制品，挤片加工的工艺参数为：三区温度分别为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在100rpm，口模宽度为10cm。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为18.7MPa，断裂伸长率为540％。
实施例4
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎 至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.1：0.9；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行硫化压板加工，制备得到为片材形式的再生制品，硫化压板工艺参数为：温度180℃、压力10MPa、排气5次，热压5分钟，压力10MPa下冷压至室温。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为18.2MPa，断裂伸长率为527％。
实施例5
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.3：0.7；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm 的复合粒料；
(5)将步骤(4)所得复合粒料进行单螺杆挤片加工，制备得到为片材形式的再生制品，挤片加工的工艺参数为：三区温度分别为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在100rpm，口模宽度为10cm。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为17.2MPa，断裂伸长率为460％。
实施例6
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.3：0.7；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行硫化压板加工，制备得到为片材形式的再生制品，硫化压板工艺参数为：温度180℃、压力10MPa、排气5次，热压5分钟，压力10MPa下冷压至室温。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为17.1MPa，断裂伸长率为435％。
实施例7
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎 至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为2MPa，磨盘盘面温度通过通入循环冷却液体控制温度为35℃，循环碾磨13次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在200℃，转速控制在30rpm，时间控制在30min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.2：0.8；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行双螺杆挤出加工，制备得到为片材形式的再生制品，挤出加工的工艺参数为：口模宽度为30cm，一区150℃、二区175℃、三区180℃，机头175℃，转速控制在50rpm。
实施例8
本实施例利用废弃交联聚乙烯和沥青制备改性交联聚乙烯和再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为25℃，循环碾磨15次，磨盘转速30转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯；其中，密炼机的工艺参数为：密炼温度控制在190℃，转速控制在40rpm，时间控制在20min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.2：0.8；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行注塑加工，制备得到为片材形式的再生 制品，挤出加工的工艺参数为：一区温度160℃、二区温度190℃、三区温度190℃、四区温度190℃。
对比例1
本对比例利用废弃交联聚乙烯制备再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min；
(4)将步骤(3)密炼后所得交联聚乙烯材料进行粉碎处理为均粒径0.5～1cm的交联聚乙烯粒料；
(5)将步骤(4)所得交联聚乙烯粒料进行单螺杆挤片加工，制备得到为片材形式的再生制品，挤片加工的工艺参数为：三区温度分别为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在100rpm，口模宽度为10cm。
制备过程中出现粉料熔融不完全，颗粒流连接不紧密，在口模处流体不稳定，导致挤出物断断续续，无法形成连续且表面光滑的片材。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为15.2MPa，断裂伸长率为376％。
对比例2
本对比例利用废弃交联聚乙烯和沥青制备再生制品的方法，包括以下步骤：
(1)选取废弃交联聚乙烯材料，经过包括洗净的预处理后，将其处理粉碎至均粒径不高于1mm的废弃交联聚乙烯粉体；
(2)将废弃交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得废弃交联聚乙烯超细粉体；其中，磨盘型固相力化学反应器的工艺参数为：碾磨压力为3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为28℃，循环碾磨15次，磨盘转速50转/分；
(3)将天然液体沥青与步骤(2)所得废弃交联聚乙烯超细粉体加入到密炼机中混合密炼；其中，密炼机的工艺参数为：密炼温度控制在180℃，转速控制在50rpm，时间控制在10min，天然液体沥青与废弃交联聚乙烯超细粉体的质量比为0.4：0.6；
(4)将步骤(3)密炼后所得改性交联聚乙烯进行粉碎处理为均粒径0.5～1cm的复合粒料；
(5)将步骤(4)所得复合粒料进行单螺杆挤片加工，制备得到为片材形式的再生制品，挤片加工的工艺参数为：三区温度分别为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在100rpm，口模宽度为10cm。
制备过程中在挤片加工时，颗粒流间沥青在外力作用下向表面迁移，可以明显观察到螺杆上残留的沥青，以及由于黏度太小，造成严重的粘辊现象，对加工造成困难。
将上述最终制备所得再生制品作为样品进行力学性能测试，其拉伸强度为14.5MPa，断裂伸长率为350％。

Claims (17)

  1. 一种改性交联聚乙烯的制备方法，其特征在于：包括以下步骤：
    (1)获取交联聚乙烯超细粉体；
    (2)将天然液体沥青与步骤(1)所得交联聚乙烯超细粉体加入到密炼机中混合密炼得到改性交联聚乙烯。
  2. 根据权利要求1所述的改性交联聚乙烯的制备方法，其特征在于：步骤(1)的具体过程如下：将交联聚乙烯粉体加入磨盘型固相力化学反应器中进行碾磨粉碎，待碾磨完成后，收集得到交联聚乙烯超细粉体。
  3. 根据权利要求2所述的改性交联聚乙烯的制备方法，其特征在于：步骤(1)中磨盘型固相力化学反应器的工艺参数为：碾磨压力为2～3MPa，磨盘盘面温度通过通入循环冷却液体控制温度为25～35℃，循环碾磨13～15次，磨盘转速30～50rpm。
  4. 根据权利要求3所述的改性交联聚乙烯的制备方法，其特征在于：步骤(1)中所述磨盘盘面温度通过通入循环冷却液体控制温度为25～35℃，所述冷却液体为水、乙二醇或甘油。
  5. 根据权利要求1所述的改性交联聚乙烯的制备方法，其特征在于：步骤(2)中密炼机的工艺参数为：密炼温度控制在180～200℃，转速控制在30～50rpm，时间控制在10～30min，天然液体沥青与交联聚乙烯超细粉体的质量比为(0.1～0.3)：(0.9～0.7)。
  6. 根据权利要求1所述的改性交联聚乙烯的制备方法，其特征在于：步骤(2)中所述天然液体沥青选择为针入度50～120(0.1mm)，软化点42～49℃，闪点在240℃～260℃之间，延度120～180cm的天然液体沥青。
  7. 根据权利要求1所述的改性交联聚乙烯的制备方法，其特征在于：步骤(2)中所述天然液体沥青选择市售90#液体沥青。
  8. 根据权利要求2所述的改性交联聚乙烯的制备方法，其特征在于：所述交联聚乙烯粉体为废弃交联聚乙烯粉体，所述废弃交联聚乙烯粉体制备方法如下：选取交联聚乙烯占比不低于98％的废弃交联聚乙烯材料或制品，经过包括洗净的预处理后，将其处理粉碎至平均粒径不高于1mm的废弃交联聚乙烯粉体。
  9. 根据权利要求8所述的改性交联聚乙烯的制备方法，其特征在于：所述处理粉碎至平均粒径不高于500um的废弃交联聚乙烯粉体。
  10. 一种改性交联聚乙烯，其特征在于：由天然液体沥青与交联聚乙烯超细粉体为原料制备而成。
  11. 根据权利要求10所述的改性交联聚乙烯，其特征在于：所述天然液体沥青与交联聚乙烯超细粉体的质量比为(0.1～0.3)：(0.9～0.7)。
  12. 根据权利要求10所述的改性交联聚乙烯，其特征在于：由天然液体沥青与交联聚乙烯超细粉体为原料制备改性交联聚乙烯的方法为权利要求1-9任意一项所述的方法。
  13. 一种再生制品的制备方法，其特征在于：包括以下步骤：
    将改性交联聚乙烯进行粉碎处理得到复合粒料，将复合粒料通过热塑性加工制备得到再生制品；
    其中，所述改性交联聚乙烯采用如权利要求1-9任意一项制备方法制得。
  14. 根据权利要求13所述的再生制品的制备方法，其特征在于：所述改性交联聚乙烯进行粉碎处理为平均粒径0.5～1cm的复合粒料。
  15. 根据权利要求13所述的再生制品的制备方法，其特征在于：所述热塑性加工，包括挤塑型材加工、注塑加工、压延成型。
  16. 根据权利要求13所述的再生制品的制备方法，其特征在于：
    所述热塑性加工，具体为：
    将复合粒料进行单螺杆挤片加工，挤片加工的工艺参数为：三区温度分别为一区150℃、二区175℃、三区180℃，机头175℃，转速控制在50～100rpm，口模宽度为10cm；
    或为，
    将复合粒料进行双螺杆挤出加工，挤出加工的工艺参数为：口模宽度为30cm，一区150℃、二区175℃、三区180℃，机头175℃，转速控制在50～100rpm；
    或为，
    将复合粒料进行硫化压板加工，工艺参数为：温度180℃、压力10MPa、排气5次，热压5分钟，压力10MPa下冷压至室温；
    或为，
    将复合粒料进行注塑加工，工艺参数为：一区温度160℃、二区温度190℃、三区温度190℃、四区温度190℃。
  17. 一种再生制品，其特征在于：采用如权利要求13-16任意一项制备方法制得。
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