CN110437527B - Long-afterglow PE master batch, preparation method thereof, PE plastic product and preparation method thereof - Google Patents

Long-afterglow PE master batch, preparation method thereof, PE plastic product and preparation method thereof Download PDF

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CN110437527B
CN110437527B CN201910763778.0A CN201910763778A CN110437527B CN 110437527 B CN110437527 B CN 110437527B CN 201910763778 A CN201910763778 A CN 201910763778A CN 110437527 B CN110437527 B CN 110437527B
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afterglow
long
master batch
resin
luminance
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CN110437527A (en
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杨锐
孔振兴
戴子林
倪海勇
丁建红
傅汉清
区菊花
李桂英
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Guangdong Institute of Rare Metals
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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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • 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
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention relates to the technical field of composite materials, in particular to a long-afterglow PE master batch, a preparation method thereof, a PE plastic product and a preparation method thereof. The long afterglow PE master batch comprises, by weight, 28-68.5 parts of PE resin, 0.3-1 part of dispersing agent, 0.5-5 parts of heat stabilizer and 30-70 parts of noctilucent powder, wherein the noctilucent powder in the long afterglow PE master batch is bonded with the PE resin. The content of the noctilucent powder in the long-afterglow PE master batch can reach 30-70%, the noctilucent powder is uniformly dispersed, and the long-afterglow PE master batch has bright color, long luminescence time and high brightness.

Description

Long-afterglow PE master batch, preparation method thereof, PE plastic product and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a long-afterglow PE master batch, a preparation method thereof, a PE plastic product and a preparation method thereof.
Background
The luminous powder is aluminate activated by various rare earth ions and can continuously emit light for a long time in a dark place after being irradiated and heated by light. Polyethylene (PE) is a thermoplastic PE resin prepared by polymerizing ethylene, is odorless and nontoxic, has excellent low-temperature resistance (the lowest use temperature can reach-100 to-70 ℃), has good chemical stability, can resist corrosion of most of acid and alkali, is insoluble in common solvents at normal temperature, and has small water absorption and excellent electrical insulation. The noctilucent material prepared by adding the noctilucent powder into the PE resin plastic can be widely applied to the fields of toys, decorations, clothes, outdoor marks and the like. When the noctilucent PE resin is processed and prepared at the present stage, noctilucent powder and the used PE resin are directly and uniformly mixed and then blow-molded or injection-molded, the mass fraction of the noctilucent powder in the obtained product is 5-15%, but the PE noctilucent master batch on the market has the problems of uneven dispersion of the noctilucent powder, low noctilucent powder content, black master batch color, small brightness, short luminescence time, reduced mechanical property of a product formed by adding the master batch and the like.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a long-afterglow PE master batch, which aims to provide a long-afterglow PE master batch with the noctilucent powder content of more than 30 percent, high luminous brightness, long luminous duration and bright color.
The invention also aims to provide a preparation method of the long-afterglow PE master batch, which is simple to operate, mild in condition and convenient to implement.
Another object of the present invention is to provide a PE plastic part having good tensile strength and bending strength.
The invention also aims to provide a preparation method of the PE plastic part, which is simple to operate and beneficial to process implementation.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a long afterglow PE masterbatch, which comprises, by weight, 28 to 68.5 parts of PE resin, 0.3 to 1 part of a dispersant, 0.5 to 5 parts of a heat stabilizer, and 30 to 70 parts of a luminescent powder, wherein the luminescent powder in the long afterglow PE masterbatch is bonded to the PE resin;
preferably, the bonding between the noctilucent powder in the long-afterglow PE master batch and the PE resin is formed through hydrogen bonds and Van der Waals forces.
In an optional embodiment, the raw materials comprise, by weight, 28.5 to 34 parts of PE resin, 0.5 to 1 part of dispersant, 1 to 5 parts of heat stabilizer, and 60 to 70 parts of noctilucent powder.
In an alternative embodiment, the PE resin is a graft polymer;
preferably, the grafting rate is 0.1-2%; more preferably, from 0.5% to 1.0%;
preferably, the graft polymer is PE-MAH.
In alternative embodiments, the dispersant is a hyperbranched polymer;
the heat stabilizer is zinc stearate or calcium stearate;
the noctilucent powder is rare earth aluminate oxide.
In an alternative embodiment, when the long afterglow luminance test emits light for 1 minute, the afterglow luminance of the long afterglow PE master batch is more than 1900mcd/m2Preferably 1968.32-2485.36mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 510mcd/m when the luminescence lasts for 5 minutes2Preferably 515.69-685.57mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 250mcd/m when the light is emitted for 10 minutes2Preferably 257.92-358.46mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 80mcd/m when the luminescence lasts for 30 minutes2Preferably 80.77-113.28mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 35mcd/m when the luminescence lasts for 60 minutes2Preferably, it is 36.25-53.55mcd/m2。
In a second aspect, an embodiment of the present invention provides a method for preparing a long-afterglow PE masterbatch, as defined in any one of the preceding embodiments, comprising the steps of: and mixing the PE resin, the dispersing agent, the heat stabilizer and the noctilucent powder, and then extruding and molding.
In an alternative embodiment, the process conditions for hot melt extrusion are: the temperature is 140-;
preferably, the temperature is 160 ℃, and the rotating speed is 500r/min;
preferably, the mixing process conditions are: the rotating speed is 20-200r/min, and the time is 2-20 minutes;
more preferably, the rotation speed is 200r/min for 10 minutes.
In a third aspect, an embodiment of the present invention provides a PE plastic part, which is prepared from the long-afterglow PE masterbatch of any one of the foregoing embodiments.
In an optional embodiment, the raw materials include a base material and the long afterglow PE master batch, and the mass ratio of the base material to the long afterglow PE master batch is (2-6): 1;
preferably, the mass content of the noctilucent powder in the PE plastic part is 5-20%, preferably 5-10%;
preferably, the tensile strength of the PE plastic part is 14.36-18.25MPa, and the bending strength is 13.88-16.39 MPa.
In a fourth aspect, an embodiment of the present invention provides a method for preparing a PE plastic part, where the long afterglow PE masterbatch is mixed with a base material and then injection molded.
Preferably, the substrate is polyethylene, more preferably high density polyethylene;
preferably, the temperature of injection molding is from 200 ℃ to 240 ℃.
The invention has the following beneficial effects: the bonding effect is generated between the PE resin and the noctilucent powder, so that the compatibility of the PE resin base material and the noctilucent powder is improved, the damage to the structure of the noctilucent powder, the generation of scrap iron and the like in the process of preparing the long-afterglow PE master batch are reduced, the noctilucent powder is uniformly dispersed, the content of the noctilucent powder can be improved, the brightness, the duration and the color of the long-afterglow PE master batch are ensured, and the mechanical property of a PE plastic part prepared from the long-afterglow PE master batch is also ensured. The dispersing agent can effectively increase the dispersibility of the noctilucent powder in the base material, avoid the agglomeration of the noctilucent powder, facilitate the increase of the content of the luminescent powder in the long-afterglow PE master batch, and ensure the luminescent brightness, duration and bright color of the long-afterglow PE master batch. The heat stabilizer can improve the thermal stability of the base material, can reduce the darkening of the color of the master batch caused by aging degradation in the processing process, and ensures the bright color of the long-afterglow PE master batch. The interaction of the substances enables the content of the noctilucent powder in the long-afterglow PE master batch to reach 30-70%, the noctilucent powder is uniformly dispersed, and the long-afterglow PE master batch has bright color, long luminescence time and high brightness.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
The long afterglow PE master batch in the prior art has the problems of uneven dispersion of noctilucent powder, blackened color, small brightness, short luminescence time, reduced mechanical property of a product formed by adding the master batch and the like, the inventor researches and discovers that the problems can be caused by larger noctilucent powder particles and poor compatibility with a PE resin base material, so that the noctilucent powder particles and the PE resin base material rub metal components such as a screw rod and the inner wall of an extruder in the melt extrusion process, meanwhile, under the action of shearing force, the structure of the noctilucent powder is damaged, the luminescence efficiency is reduced, in addition, metal on the surfaces of the screw rod and the inner wall is scraped off to form scrap iron, and the color of the master batch is darkened. For the reasons, the mass percent dosage of the long-afterglow PE master batch, namely the noctilucent powder in the long-afterglow PE master batch needs to be controlled within 30 percent. The low-concentration and low-brightness noctilucent master batch cannot meet the application requirements of high-end markets.
In view of the above, the present invention provides a long afterglow PE master batch, which comprises, by weight, 28 to 68.5 parts of PE resin, 0.3 to 1 part of dispersant, 0.5 to 5 parts of heat stabilizer, and 30 to 70 parts of noctilucent powder. Preferably, the raw materials comprise, by weight, 28.5-34 parts of PE resin, 0.5-1 part of dispersing agent, 1-5 parts of heat stabilizer and 60-70 parts of noctilucent powder. Compared with the prior art, the long-afterglow PE master batch has the advantages that the mass percentage of the noctilucent powder is high, the mass percentage of the noctilucent powder can reach 30-70%, and the noctilucent powder is uniformly dispersed in the long-afterglow PE master batch, so that the long-afterglow PE master batch has the advantages of no blackening, bright color, long luminescence time, high luminescence brightness and the like.
Specifically, the PE resin in the long-afterglow PE master batch is bonded with the noctilucent powder, and the bonding is the bonding effect of hydrogen bonds and Van der Waals force, so that the compatibility of the PE resin and the noctilucent powder is improved, the friction between the noctilucent powder and a machine in the blending and extruding process is reduced, the structure of the noctilucent powder is better protected, the interface acting force of the PE resin and the noctilucent powder in a subsequent injection molding product is improved, the mechanical strength of the composite material is increased, the content of the noctilucent powder in the long-afterglow PE master batch is improved, and the luminous brightness and the luminous duration are further improved.
The dispersing agent is added, so that the dispersibility of the noctilucent powder in the PE resin can be effectively improved, the noctilucent powder can better enter a PE resin matrix, the noctilucent powder is prevented from agglomerating, and the friction between the noctilucent powder and a machine is reduced, so that the damage to the structure of the noctilucent powder is reduced, the color of the long-afterglow PE master batches is ensured to be bright, meanwhile, the hot melting extrusion temperature can be reduced, the aging degradation degree of the PE resin is reduced, and the light-emitting effect of the long afterglow PE master batches is ensured.
The thermal stability of the PE resin can be enhanced by adding the thermal stabilizer, the darkening of the color of the master batch caused by aging degradation in the processing process is reduced, and the bright color of the long-afterglow PE master batch is ensured. And the proportion of each material is further controlled, so that the noctilucent powder can be further ensured to be well compatible with the PE resin, and the complete structure of the noctilucent powder in the preparation process ensures that the long-afterglow PE master batches have long luminescence time, high luminescence brightness and bright color.
Further, the PE resin is a graft polymer;
preferably, the grafting rate is 0.1-2%; more preferably, from 0.5% to 1.0%;
preferably, the grafted polymer is PE-MAH, i.e. maleic anhydride grafted PE;
the maleic anhydride is adopted to graft the PE, so that the bonding effect of the noctilucent powder in the long-afterglow PE master batches and the PE resin is better promoted, the luminous effect of the long-afterglow PE master batches is further ensured, and the mechanical property of a PE plastic part prepared from the subsequent long-afterglow PE master batches is also promoted.
The preparation of the graft polymers is routine experimentation by those skilled in the art and the present invention will not be described in detail.
Further, the dispersant is a hyperbranched polymer. For example, at least one of C100, C181, HyPerC10, HyPerC20, HyPerC30 and HyPerC40 manufactured by guangdong jiang chemical agents ltd may be used. The dispersing agent can further promote the uniform mixing of the noctilucent powder and the PE resin, prevent the noctilucent powder from gathering, reduce the aging of the PE resin and further ensure the luminous effect of the long-afterglow PE master batch.
Further, the heat stabilizer is a stearic acid compound, preferably stearate, more preferably zinc stearate or calcium stearate, and the heat stabilizer can further reduce the aging of the PE resin in the preparation process, so that the bright light-emitting color, the long-afterglow PE master batch and the high brightness are ensured.
Furthermore, the noctilucent powder is rare earth aluminate oxide. For example, at least one of GL-4A, GL-8C, BL-2A, HL-730 and HL-825 developed by the research institute of rare metals in Guangdong province or other existing noctilucent powder can be adopted. Adopt above-mentioned night light powder can further guarantee that night light powder and PE resin form the bonding of hydrogen bond and van der Waals's power, then more be favorable to the two to be compatible, help the night light powder to disperse evenly to can effectively reduce the destruction degree of the structure of night light powder in processing technology, and can promote the content of night light powder, then promote the luminance, duration and the colour bright and bright of long afterglow PE master batch.
Furthermore, the raw materials and the proportion can ensure that the afterglow luminance of the long afterglow PE master batch is more than 1900mcd/m when the prepared long afterglow PE master batch emits light for 1 minute in the afterglow luminance test2Preferably 1968.32-2485.36mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 510mcd/m when the luminescence lasts for 5 minutes2Preferably 515.69-685.57mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 250mcd/m when the light is emitted for 10 minutes2Preferably 257.92-358.46mcd/m2；
The afterglow brightness of the long afterglow PE master batch is 30 minutes after the luminescenceGreater than 80mcd/m2Preferably 80.77-113.28mcd/m2；
The afterglow luminance of the long afterglow PE master batch is more than 35mcd/m when the luminescence lasts for 60 minutes2Preferably, it is 36.25-53.55mcd/m2。
Further, the invention also provides a preparation method of the long afterglow PE master batch, which comprises the following steps: and mixing the PE resin, the dispersing agent, the heat stabilizer and the noctilucent powder, and then extruding and molding.
Specifically, the materials are put into a mixer, mixed for 2-20 minutes in the mixer at the rotating speed of 20r/min-200r/min, added into a double-screw extruder at the rotating speed of 200r/min-500r/min after being uniformly mixed, and subjected to melt blending extrusion at the temperature of 140-160 ℃ and then sequentially granulated and dried. The raw materials and the raw material proportion of the long-afterglow PE master batch are adjusted, so that the hot-melting extrusion temperature can be properly reduced, the PE resin aging is reduced, and the luminous effect of the prepared long-afterglow PE master batch is further improved. By adopting the processing conditions, the aging degree of the PE resin can be reduced, the noctilucent powder can be uniformly dispersed, and the luminescence property of the long-afterglow PE master batch prepared subsequently can be ensured.
Preferably, the process conditions of hot-melt extrusion are: the temperature is 160 ℃, the rotating speed is 300r/min, and the mixing process conditions are as follows: the rotating speed is 200r/min, and the time is 10 minutes. And the luminous effect of the long-afterglow PE master batch can be further ensured by adopting more optimized operating conditions.
The invention also provides a PE plastic part which is prepared from the long-afterglow PE master batch of any one of the embodiments. The material comprises a base material and the long afterglow PE master batch, wherein the mass ratio of the base material to the long afterglow PE master batch is (2-6): 1; preferably, the mass content of the noctilucent powder in the PE plastic part is 5-20%, preferably 5-10%. The PE plastic part prepared from the long-afterglow PE master batch has good mechanical properties, wherein the tensile strength of the PE plastic part is 14.36-18.25MPa, and the bending strength is 13.88-16.39 MPa.
The invention also provides a preparation method of the PE plastic product, wherein the long-afterglow PE master batch is mixed with the base material and then is subjected to injection molding;
preferably, the substrate is polyethylene, more preferably high density polyethylene;
preferably, the temperature of injection molding is from 200 ℃ to 240 ℃.
Example 1
This example provides a long afterglow PE masterbatch, which comprises the following raw materials, 68.5g of PE-MAH (maleic anhydride modified polyethylene, graft ratio of 0.5%), 0.5g of C100 dispersant, 1g of zinc stearate, and 30g of BL-2A luminous powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps:
adding the components into a mixer, mixing for 3 minutes in a mixer at the rotating speed of 100r/min, adding the mixture into a double-screw extruder at the rotating speed of 200r/min after uniform mixing, performing melt blending extrusion at the temperature of 140 ℃, granulating, drying and packaging to obtain the long-afterglow PE master batch.
Example 2
This example provides a long persistence PE masterbatch, which comprises the following raw materials, 64g of PE-MAH (grafting ratio of 0.5%), 1g of C181 hyper-dispersant, 5g of calcium stearate, and 30g of GL-8C noctilucent powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps:
adding the components into a mixer, mixing for 10 minutes in a mixer at the rotating speed of 200r/min, adding the mixture into a double-screw extruder at the rotating speed of 500r/min after uniform mixing, performing melt blending extrusion at the temperature of 150 ℃, granulating, drying and packaging to obtain the long-afterglow PE master batch.
Example 3
This example provides a long persistence PE masterbatch, which comprises the following raw materials, 58.5g PE-MAH (grafting ratio of 0.3%), 0.5g C181 dispersant, 1g zinc stearate, and 40g GL-4A noctilucent powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps: adding the components into a mixer, mixing for 3 minutes in a mixer at the rotating speed of 100r/min, adding the mixture into a double-screw extruder at the rotating speed of 300r/min after uniform mixing, performing melt blending extrusion at the temperature of 160 ℃, granulating, drying and packaging to obtain the long-afterglow PE master batch.
Example 4
This example provides a long afterglow PE masterbatch, which comprises the following raw materials, 46.5g PE-MAH (grafting rate of 2.0%), 0.5g HyPerC20 dispersant, 3g zinc stearate, and 50g HL-730 fluorescent powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps: adding the components into a mixer, mixing for 3 minutes in a mixer at the rotating speed of 20r/min, adding the mixture into a double-screw extruder at the rotating speed of 200r/min after uniform mixing, performing melt blending extrusion at the temperature of 160 ℃, granulating, drying and packaging to obtain the long-afterglow PE master batch.
Example 5
This example provides a long persistence PE masterbatch, which comprises the following raw materials, 34g of PE-MAH (grafting ratio of 0.5%), 1g of HyPerC30 dispersant, 5g of calcium stearate, and 60g of BL-2A noctilucent powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps:
adding the components into a mixer, mixing for 20 minutes in a mixer at the rotating speed of 100r/min, adding the mixture into a double-screw extruder at the rotating speed of 300r/min after uniform mixing, performing melt blending extrusion at the temperature of 160 ℃, granulating, drying and packaging to obtain the long-afterglow PE master batch.
Example 6
This example provides a long persistence PE masterbatch, which comprises 28g of PE-MAH (grafting rate of 0.1%), 1g of C181 dispersant, 1g of calcium stearate, and 70g of HL-825 luminous powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps:
the components are added into a mixer, mixed for 5 minutes in a mixer with the rotating speed of 80r/min, added into a twin-screw extruder with the rotating speed of 500r/min after being mixed evenly, granulated after being melted, blended and extruded at the temperature of 140 ℃, dried and packaged, and the long-afterglow PE master batch is obtained.
Example 7
This example provides a long persistence PE masterbatch, which comprises the following raw materials, 28.5g PE-MAH (grafting ratio of 0.5%), 0.5g C100 dispersant, 1g zinc stearate, and 70g GL-8C luminous powder.
The embodiment also provides a preparation method of the long-afterglow PE master batch, which comprises the following steps:
adding the components into a mixer, mixing for 3 minutes in a mixer at the rotating speed of 200r/min, adding the mixture into a double-screw extruder at the rotating speed of 300r/min after uniform mixing, performing melt blending extrusion at the temperature of 160 ℃, granulating, drying and packaging to obtain the long-afterglow PE master batch.
Example 8
This example provides a PE plastic part having a long persistence, which is the PE masterbatch prepared in example 7, wherein the noctilucent powder is present in an amount of 5% by weight.
This example also provides a method for preparing a PE plastic part by uniformly mixing 100g of the long afterglow PE masterbatch prepared in example 7 with 1300g of hdpe (high density polyethylene), adding to an injection molding machine, and injection molding at 200 ℃.
Example 9
This example provides a PE plastic part, which includes the long persistence PE masterbatch prepared in example 5, wherein the noctilucent powder is present in an amount of 10% by weight.
This example also provides a method for preparing a PE plastic part by uniformly mixing 200g of the long persistence PE masterbatch prepared in example 5 with 1000g of hdpe, adding to an injection molding machine, and injection molding at 220 ℃.
Example 10
This example provides a PE plastic part, which includes the long persistence PE masterbatch prepared in example 5, wherein the noctilucent powder is present in an amount of 20% by weight.
This example also provides a method for preparing a PE plastic part by mixing 400g of the long persistence PE masterbatch prepared in example 5 with 800g of hdpe, adding to an injection molding machine, and injection molding at 240 ℃.
Comparative example 1: the preparation method provided by reference to example 1 is used for preparing the long-afterglow PE master batch, and the difference is that the raw materials are as follows: 68.5g of PE, 30g of BL-2A noctilucent powder, 0.5g of C100 dispersant and 1 part of zinc stearate.
Comparative example 2: the preparation method provided by reference to example 2 is used for preparing the long-afterglow PE master batch, and the difference is that the raw materials are as follows: 65 g of PE-MAH, 30g of GL-8C noctilucent powder and 5g of zinc stearate.
Comparative example 3: the preparation method provided by reference to example 3 is used for preparing the long-afterglow PE master batch, and the difference is that the raw materials are as follows: 50g of PE-MAH, 40g of GL-4A noctilucent powder and 0.5g of C180 dispersing agent.
Comparative example 4: the preparation method provided by reference to example 5 is used for preparing the long-afterglow PE master batch, and the difference is that the raw materials are as follows: 40g of PE and 60g of BL-2A noctilucent powder.
Comparative example 5: the preparation method provided in reference to example 7 is used for preparing the long-afterglow PE masterbatch, and the differences are that the raw material ratio is as follows: 30g of PE and 70g of GL-8C noctilucent powder.
Comparative example 6: 100g of comparative example 5 and 1300g of HDPE were mixed uniformly and then introduced into an injection molding machine, and injection molding was carried out at 200 ℃ to obtain an HDPE part with a GL-8C content of 5%.
Comparative example 7: 200g of comparative example 4 and 1000g of HDPE were mixed uniformly and then introduced into an injection molding machine, and injection molding was carried out at 220 ℃ to obtain 10% BL-2A content HDPE parts.
Comparative example 8: 400g of comparative example 4 and 800g of HDPE were mixed homogeneously and introduced into an injection molding machine, and the resulting mixture was injection molded at 240 ℃ to give 20% BL-2A HDPE parts.
Experimental example 1
The long-afterglow PE concentrates of examples 1 to 7 and comparative examples 1 to 5 were subjected to afterglow luminance tests according to the test method referred to GB/T24981.2-2010. The results are shown in Table 1.
TABLE 1 test results
Figure BDA0002171239870000111
As can be seen from Table 1, the afterglow luminance of the long afterglow PE masterbatch prepared in example 1 is significantly higher than that of comparative example 1 at 1min, 5min, 10min, 30min and 60min, which indicates that the compatibility of the noctilucent powder and PE can be increased and the afterglow luminance of the long afterglow PE masterbatch can be improved after introducing the MAH group into the PE. The afterglow luminance of the long afterglow PE master batches of the embodiment 2 and the embodiment 3 is respectively higher than that of the comparative example 2 and the comparative example 3 in 1min, 5min, 10min, 30min and 60min, which shows that the afterglow luminance of the long afterglow PE master batches can be effectively improved by adding the dispersant and the heat stabilizer. As can be seen from examples 3-7 and comparative examples 3-5, regardless of the change of the concentration of the luminescent powder, the introduction of MAH group, the addition of dispersant or heat stabilizer on PE can effectively improve the afterglow brightness of PE luminescent master batches containing the same content of luminescent powder.
Experimental example 2
The tensile strength and flexural strength of the PE plastic parts of examples 8-10 and comparative examples 6-8 were tested, wherein the tensile strength and flexural strength were tested as described in GB/T1040.1-2006. The results are shown in Table 2.
TABLE 2 test results
Tensile strength (Mpa) Flexural Strength (MPa)
Example 8 18.25 16.39
Example 9 16.32 15.94
Example 10 14.36 13.88
Comparative example 6 16.11 15.12
Comparative example 7 13.19 12.91
Comparative example 8 11.89 11.05
Comparing example 8 with comparative example 6, it can be seen that the tensile strength and bending strength of the PE plastic part prepared by adding the long-afterglow PE master batch prepared by the invention are obviously improved compared with the tensile strength of the part prepared by adding the common long-afterglow PE master batch; comparing example 9 with comparative example 7 and example 10 with comparative example 8, it can be seen that when the content of the noctilucent powder is increased to 10 parts or 20 parts, the tensile strength and bending strength of the PE plastic parts prepared by adding the long afterglow PE master batch prepared by the invention are still obviously higher than those of the parts prepared by the common long afterglow PE master batch.
In summary, the long afterglow PE masterbatch provided in the embodiments of the present invention improves the compatibility between the luminescent powder and the PE resin by bonding the PE resin and the luminescent powder, especially by bonding the PE resin with hydrogen bonds and van der waals forces, and reduces the friction between the luminescent powder and the machine, thereby reducing the damage to the structure of the luminescent powder. After the dispersing agent is added, the noctilucent powder can be better dispersed in the PE resin, the agglomeration of the noctilucent powder is avoided, the preparation temperature can be reduced, and the aging degradation degree of the polymer is reduced; ensuring the luminous effect of the long-afterglow PE master batch. The added heat stabilizer can also enhance the heat stability of the PE resin and reduce aging, degradation and discoloration in the processing process. Compared with the prior art, the mass percent of the noctilucent powder in the long-afterglow PE master batch can reach 30-70%, and the long-afterglow PE master batch has the advantages of no blackening, uniform dispersion, bright color, long luminescence time and the like. The PE plastic part prepared from the long-afterglow PE master batch has better mechanical property than the PE plastic part prepared from the common long-afterglow PE master batch.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. The long-afterglow PE master batch is characterized by comprising, by weight, 28-68.5 parts of PE resin, 0.3-1 part of dispersing agent, 0.5-5 parts of heat stabilizer and 30-70 parts of noctilucent powder, wherein bonding between the noctilucent powder in the long-afterglow PE master batch and the PE resin is formed through hydrogen bonds and Van der Waals forces, and the PE resin is PE-MAH.
2. The long-afterglow PE masterbatch according to claim 1, wherein the raw materials comprise, by weight, 28.5 to 34 parts of PE resin, 0.5 to 1 part of dispersant, 1 to 5 parts of heat stabilizer, and 60 to 70 parts of noctilucent powder.
3. The long-afterglow PE masterbatch according to claim 1 or 2, wherein the graft ratio of the PE resin is 0.1 to 2%.
4. The long-afterglow PE masterbatch of claim 1 or 2 wherein the grafting ratio of the PE resin is 0.5 to 1.0%.
5. The long-afterglow PE masterbatch according to claim 1 or 2, wherein the dispersant is a hyperbranched polymer;
the heat stabilizer is zinc stearate or calcium stearate;
the noctilucent powder is rare earth aluminate oxide.
6. The long-afterglow PE masterbatch of claim 1 or 2, wherein the afterglow luminance of the long-afterglow PE masterbatch is more than 1900mcd/m when the afterglow luminance tests show that the afterglow luminance lasts for 1 minute2The afterglow luminance of the long afterglow PE master batch is more than 510mcd/m when the afterglow luminance is 5 minutes2The afterglow luminance of the long afterglow PE master batch is more than 250mcd/m when the light is emitted for 10 minutes2The afterglow luminance of the long afterglow PE master batch is more than 80mcd/m when the luminescence lasts for 30 minutes2The afterglow luminance of the long afterglow PE master batch is more than 35mcd/m when the afterglow luminance emits light for 60 minutes2。
7. The long-afterglow PE masterbatch of claim 1 or 2 having an afterglow luminance of 1968.32-2485.36mcd/m when emitting light for 1 minute in the afterglow luminance test2；
The afterglow luminance of the long afterglow PE master batch is 515.69-685.57mcd/m when the luminescence lasts for 5 minutes2；
The afterglow luminance of the long afterglow PE master batch is 257.92-358.46mcd/m when the light is emitted for 10 minutes2；
The afterglow luminance of the long afterglow PE master batch is 80.77-113.28mcd/m when the luminescence lasts for 30 minutes2；
The afterglow luminance of the long afterglow PE master batch is 36.25 to 53.55mcd/m when the luminescence lasts for 60 minutes2。
8. The process for preparing a long persistence PE masterbatch according to any one of claims 1 to 7, comprising the steps of: and mixing the PE resin, the dispersing agent, the heat stabilizer and the noctilucent powder, and then extruding and molding.
9. The preparation method according to claim 8, wherein the process conditions of the hot-melt extrusion are as follows: the temperature is 140-; the mixing process conditions are as follows: the rotating speed is 20-200r/min, and the time is 2-20 minutes.
10. The preparation method according to claim 8, wherein the process conditions of the hot-melt extrusion are as follows: the temperature is 160 ℃, the rotating speed is 500r/min, and the mixing process conditions are as follows: the rotating speed is 200r/min, and the time is 10 minutes.
11. PE plastic part, characterized in that it is prepared from the long-afterglow PE masterbatch according to any one of claims 1 to 7.
12. The PE plastic part according to claim 11, wherein the raw materials comprise a base material and the long-afterglow PE master batch, and the mass ratio of the base material to the long-afterglow PE master batch is (2-6): 1; the mass content of the noctilucent powder in the PE plastic part is 5-20%; the tensile strength of the PE plastic part is 14.36-18.25MPa, and the bending strength is 13.88-16.39 MPa.
13. The PE plastic part according to claim 11, wherein the content of the noctilucent powder in the PE plastic part is 5-10% by mass.
14. The process for preparing PE plastic parts according to any one of claims 11 to 13, wherein the long-afterglow PE master batch is mixed with the PE base material and then injection molded,
wherein the base material is high-density polyethylene; the temperature for injection molding is from 200 ℃ to 240 ℃.
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