CN108504077B - White graphene modified polyphenyl ether composite material and preparation method thereof - Google Patents
White graphene modified polyphenyl ether composite material and preparation method thereof Download PDFInfo
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Abstract
The white graphene modified polyphenyl ether composite material is mainly prepared from the following raw materials in parts by weight: 0.1-20 parts of high polymer modified white graphene, 60-100 parts of polyphenyl ether resin, 0.1-10 parts of white oil and 0.1-20 parts of dispersing agent. The white graphene modified polyphenyl ether composite material has high mechanical strength and thermal conductivity and high processability.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a white graphene modified polyphenyl ether composite material and a preparation method thereof.
Background
Polyphenylene Oxide (PPO) is a high-strength engineering plastic developed in the 60 th century, and has a chemical name of poly (2, 6-dimethyl-1, 4-phenylene oxide, which is also called polyphenylene oxide or polyphenylene ether. PPO is non-toxic, transparent, has small relative density, excellent mechanical strength, stress relaxation resistance, creep resistance, heat resistance, water vapor resistance and dimensional stability, and is mainly used in the fields of electronic appliances, automobiles, household appliances, office equipment, industrial machinery and the like. However, PPO materials have poor melt flowability, are difficult to process and form, and have poor scratch resistance and impact toughness and poor aging resistance.
In order to improve the processability, impact resistance, etc. of PPO, modification of PPO, such as modification of PPO with Polystyrene (PS) or an elastomer, is generally carried out, and although such modification can improve the processability, it results in a significant decrease in scratch resistance, thermal conductivity, etc. of the PPO-modified material. Although some manufacturers modify the PPO by using traditional inorganic nano materials to improve the impact strength, scratch resistance and thermal conductivity of the PPO to a certain extent, the inorganic nano materials have large filling amount, are difficult to uniformly disperse, and are easy to cause the problems of difficult processing and forming and the like. Therefore, a new material which can improve the strength and the thermal conductivity of the PPO material and is easy to process is found, and the aim of continuous pursuit and research of various enterprises is achieved.
Disclosure of Invention
Based on the above, it is necessary to provide a white graphene modified polyphenylene oxide composite material having high processability while ensuring the mechanical strength and thermal conductivity of the PPO material, and a preparation method thereof.
The white graphene modified polyphenyl ether composite material is mainly prepared from the following raw materials in parts by weight: 0.1-20 parts of high polymer modified white graphene, 60-100 parts of polyphenyl ether resin, 0.1-10 parts of white oil and 0.1-20 parts of dispersing agent.
The white graphene modified polyphenyl ether composite material is mainly prepared from high polymer modified white graphene, polyphenyl ether resin, white oil and a dispersing agent. The white graphene modified polyphenyl ether composite material has high mechanical strength and thermal conductivity, and also has high toughness, scratch resistance and thermal oxidation resistance by controlling the raw material ratio, so that the processing performance of the white graphene modified polyphenyl ether composite material is greatly improved.
Specifically, the white graphene modified by the high polymer in the white graphene modified polyphenyl ether composite material has good compatibility with polyphenyl ether resin, the uniform dispersion degree of a system is improved by the aid of the addition of white oil, and the white graphene modified by the high polymer is well dispersed and interpenetrated in a polyphenyl ether matrix to form a net structure by the aid of a dispersing agent, so that the impact resistance and the scratch resistance of the composite material are remarkably improved, and the processability of the composite material is greatly improved. The white graphene modified by the high polymer has high thermal conductivity, oxygen resistance and self-lubricity, so that the toughness and the thermal oxidation resistance of the composite material are obviously improved, and the processing performance of the composite material is further improved.
In one embodiment, the white graphene modified polyphenylene ether composite material is mainly prepared from the following raw materials in parts by weight: 1-15 parts of high polymer modified white graphene, 80-100 parts of polyphenyl ether resin, 0.5-5 parts of white oil and 0.5-10 parts of dispersing agent.
In one embodiment, the white oil is one or more of 1#, 3#, 5#, 7#, 10#, 15#, 26#, 36#, 46# industrial grade white oil or food grade white oil; and/or
The dispersing agent is one or more of paraffin, polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, barium stearate and pentaerythritol stearate.
In one embodiment, the high polymer modified white graphene is mainly prepared from the following raw materials in parts by weight: 0.5-10 parts of white graphene, 0.05-2 parts of polymerized monomer, 0.1-5 parts of stabilizer, 0.5-5 parts of initiator and 90-110 parts of solvent;
the polymerization monomer is one or more of styrene, acrylic acid, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate and glycidyl methacrylate.
In one embodiment, the stabilizer is one or more of polyvinylpyrrolidone, sodium alkyl sulfate, sodium alkyl benzene sulfonate, oleylamine and oleic acid; and/or the presence of a catalyst in the reaction mixture,
the initiator is one or more of ammonium persulfate and azobisisobutyronitrile; and/or the presence of a catalyst in the reaction mixture,
the solvent is one or more of water, ethanol, glycol, glycerol, ethyl acetate and butyl acetate.
In one embodiment, the number of the polymer-modified white graphene layers is 2-10, the particle size is 5-10 μm, and the specific surface area is 300-500m2/g。
In one embodiment, the preparation method of the high polymer modified white graphene comprises the following steps:
placing the white graphene in the solvent for ultrasonic dispersion, and then adding the stabilizer for treatment to obtain oleophylic modified white graphene dispersion liquid;
and (3) uniformly mixing the oleophylic modified white graphene dispersion liquid with the polymerization monomer and the initiator, reacting for 0.5-3h at the temperature of 60-120 ℃, adding a neutralizing agent to adjust the pH value to 7-8, cooling, filtering and drying to obtain the high polymer modified white graphene.
A preparation method of a white graphene modified polyphenyl ether composite material comprises the following steps:
and mixing and dispersing the polyphenyl ether resin, the white graphene modified by the high polymer, the white oil and the dispersing agent, then mixing and melting, and extruding and granulating to obtain the white graphene modified polyphenyl ether composite material.
The method is simple and convenient to operate, does not need complex instruments, can be used for batch production, and can meet industrial application.
In one embodiment, the mixing and dispersing step comprises the following steps:
and (2) placing the polyphenyl ether resin, the white graphene modified by the high polymer, the white oil and the dispersing agent into a high-speed mixer, and mixing for 5-30min at the temperature of 60-120 ℃.
In one embodiment, the mixing, melting, extruding and granulating process includes the following steps:
and adding the mixed and dispersed mixed components into a charging barrel of a double-screw extruder, mixing and extruding under the conditions that the temperature range of each area of the double-screw extruder is 270-320 ℃, the head temperature is 280-330 ℃ and the main machine rotating speed is 180-550r/min, and then cooling, drawing strips and cutting granules to obtain the white graphene modified polyphenyl ether composite material.
The white graphene modified polyphenyl ether composite material has high mechanical strength, high thermal conductivity and high processability.
In addition, the white graphene modified polyphenyl ether composite material is simple in formula, easy in raw material obtaining, capable of being produced in batches without complex equipment and complex operation, and capable of meeting industrial application.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The white graphene modified polyphenyl ether composite material is mainly prepared from the following raw materials in parts by weight: 0.1-20 parts of high polymer modified white graphene, 60-100 parts of polyphenyl ether resin, 0.1-10 parts of white oil and 0.1-20 parts of dispersing agent.
In one embodiment, the white graphene modified polyphenylene ether composite material is mainly prepared from the following raw materials in parts by weight: 1-15 parts of high polymer modified white graphene, 80-100 parts of polyphenyl ether resin, 0.5-5 parts of white oil and 0.5-10 parts of dispersing agent.
In one embodiment, the white graphene modified polyphenylene ether composite material is mainly prepared from the following raw materials in parts by weight: 2-10 parts of high polymer modified white graphene, 80-90 parts of polyphenyl ether resin, 2-5 parts of white oil and 2-10 parts of a dispersing agent.
In one embodiment, the white graphene modified polyphenyl ether composite material is mainly prepared from the following raw materials in parts by weight: 3-8 parts of high polymer modified white graphene, 80-90 parts of polyphenyl ether resin, 3-5 parts of white oil and 3-10 parts of a dispersing agent.
White oils, also known as paraffinic, white and mineral oils, are liquid hydrocarbon mixtures refined from petroleum, mainly saturated mixtures of naphthenic and paraffinic hydrocarbons. The adhesive property of the high polymer modified white graphene and a matrix can be increased, and the overall uniform dispersibility and the processability of the composite material are improved. In one embodiment, the white oil is one or more of 1#, 3#, 5#, 7#, 10#, 15#, 26#, 36#, and 46# industrial grade white oil or food grade white oil.
The dispersing agent can act synergistically with the white graphene modified by the high polymer to improve the compatibility of the white graphene modified by the high polymer and the polyphenyl ether plastic, so that the white graphene modified by the high polymer is uniformly dispersed and interpenetrated in the polyphenyl ether, and the formation of a lamellar network structure of the whole material system is promoted, so that the mechanical properties and toughness of the composite plastic such as impact resistance can be improved, the thermal conductivity and oxidation resistance of the composite plastic can be improved, and the processing performance of the composite material is improved.
In one embodiment, the dispersant is one or more of paraffin, polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, barium stearate, and pentaerythritol stearate.
The high polymer-modified white graphene is white graphene having a high polymer coating layer formed on the surface thereof. In one embodiment, the coating layer is polymethyl methacrylate; in one embodiment, the coating layer is polymethyl acrylate; in one embodiment, the coating layer is poly glycidyl methacrylate; in one embodiment, the coating layer is polystyrene.
In addition, the high polymer modified white graphene may be a single-layer or few-layer modified white graphene. The graphene/graphene composite material has better thermal conductivity and high temperature resistance due to the two-dimensional property of the atomic-scale thickness similar to that of graphene. In one embodiment, the graphene is 2-10 layers of modified white graphene.
In one embodiment, the high polymer modified white graphene is mainly prepared from the following raw materials in parts by weight: 0.5-10 parts of white graphene, 0.05-2 parts of polymerized monomer, 0.1-5 parts of stabilizer, 0.5-5 parts of initiator and 90-110 parts of solvent; wherein the polymerized monomer is one or more of styrene, acrylic acid, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate and glycidyl methacrylate.
In an embodiment, the high polymer modified white graphene is mainly prepared from the following raw materials in parts by weight: 6-10 parts of white graphene, 1-2 parts of polymerized monomer, 0.3-3 parts of stabilizer, 0.5-5 parts of initiator and 90-110 parts of solvent.
In an embodiment, the high polymer modified white graphene is mainly prepared from the following raw materials in parts by weight: 6-10 parts of white graphene, 1-2 parts of polymerized monomer, 0.3-0.8 part of stabilizer, 0.5-5 parts of initiator and 90-110 parts of solvent.
In one embodiment, the polymerized monomer is one or more of styrene, acrylic acid, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate, and glycidyl methacrylate.
In addition, various monomers can be purified by reduced pressure distillation or the like to improve the yield of the polymerization reaction.
The solvent in the raw material for preparing the high polymer modified white graphene can be one or more of water, ethanol, ethylene glycol, glycerol, ethyl acetate, butyl acetate and the like.
The stabilizer can be one or more of polyvinylpyrrolidone, alkyl sodium sulfate, sodium alkyl benzene sulfonate, oleylamine, oleic acid and the like.
The initiator may be one or more of azo type initiators or peroxy type initiators. In one embodiment, the initiator is ammonium persulfate or azobisisobutyronitrile.
In one embodiment, the particle size of the polymer-modified white graphene is 5-10 μm, and the specific surface area is 300-500m2/g。
The high polymer modified white graphene can be prepared by carrying out in-situ polymerization modification on the white graphene.
Specifically, the preparation method of the high polymer modified white graphene comprises the following steps:
s101: and (3) placing the white graphene in a solvent for ultrasonic dispersion, and then adding a stabilizer for treatment to obtain an oleophylic modified white graphene dispersion solution.
It should be noted that, after the step, the oleophylic modified white graphene may be separated from the oleophylic modified white graphene dispersion liquid, and then the oleophylic modified white graphene is dispersed in a new solvent to prepare a new oleophylic modified white graphene dispersion liquid for subsequent reaction, or the oleophylic modified white graphene dispersion liquid may be directly used for subsequent reaction. And the solvent (i.e., the new solvent) in step S102 may be the same as or different from the solvent in step S101, and may be one or more of water, ethanol, ethylene glycol, glycerol, ethyl acetate, butyl acetate, and the like.
S102: and (2) uniformly mixing the oleophylic modified white graphene dispersion liquid with a polymerization monomer and an initiator, reacting at 60-100 ℃ for 0.5-3h, adding a neutralizing agent to adjust the pH value to 7-8, cooling, filtering and drying to obtain the high polymer modified white graphene.
The order of addition of the materials in this step is not particularly limited. In one embodiment, the oleophylic modified white graphene dispersion liquid is heated to the reaction temperature of 60-100 ℃, then the initiator is added, the mixture is stirred for 10-30min to make the solution uniform, then the polymeric monomer is dropwise added, the dropping is completed within 0.5-1h, and after the dropping is completed, the reaction is continued for 0.5-3h at the temperature of 60-100 ℃ to improve the yield.
In addition, the mixing mode in the mixing operation includes one of mechanical stirring, ultrasonic and ultrasonic-mechanical stirring combination. In one embodiment, the mixing is performed using a combination of ultrasonic-mechanical agitation.
After the polymerization reaction is finished, adding a neutralizing agent to adjust the pH value to 7-8 so as to improve the compatibility of the high polymer and the white graphene, wherein the neutralizing agent can be one or more of ammonia water, dimethylethanolamine, triethylamine, sodium hydroxide and potassium hydroxide. In one embodiment, the neutralizing agent is ammonia.
Further, it is preferable to quickly cool to room temperature after adding the neutralizing agent. And then washing and drying, wherein the washing can be carried out by using ethanol so as to reduce the difficulty of subsequent drying. In one embodiment, after washing with ethanol, drying is performed at 50 ℃ to 70 ℃.
The obtained high polymer modified white graphene can be ground to obtain the high polymer modified white graphene with smaller particle size, which is beneficial to subsequent modification of the composite material. In one embodiment, the white graphene modified by the high polymer is ground to obtain a material with a particle size of 5-10 μm and a specific surface area of 300-500m2Per g of high polymer modified white graphene.
The method comprises the steps of firstly, placing white graphene in a dispersion liquid for ultrasonic dispersion; after ultrasonic treatment, a stabilizer is added to modify the surface of the white graphene so as to improve the surface activity of the white graphene, and then the white graphene and a polymerization monomer are subjected to polymerization reaction under the action of an initiator so as to form a coating layer on the surface of the white graphene. The white graphene is uniformly dispersed in the dispersion liquid through ultrasound, so that the coating layer formed on the white graphene is uniform in thickness, and the dispersibility of the high polymer modified white graphene in polyphenyl ether can be effectively improved. In addition, the thickness of the coating layer can be adjusted by adjusting the concentration of the polymerization monomer, and the method is simple and convenient.
The invention also provides a preparation method of the white graphite modified polyphenyl ether composite material, which comprises the following steps:
s201: mixing and dispersing polyphenyl ether resin, high polymer modified white graphene, white oil and a dispersing agent.
The mixing dispersion can be mixed by using a high-speed mixer, and specifically comprises the following steps: placing polyphenyl ether resin, high polymer modified white graphene, white oil and a dispersing agent into a high-speed mixer, and mixing for 5-30min at the temperature of 60-120 ℃.
In one embodiment, the mixing is carried out at 70-100 deg.C for 5-30 min.
S202: and mixing, melting, extruding and granulating to obtain the white graphene modified polyphenyl ether composite material.
The step can be carried out by using a double-screw extruder, and specifically comprises the following steps:
adding the mixed and dispersed mixed components into a charging barrel of a double-screw extruder, mixing and extruding under the conditions that the temperature range of each area of the double-screw extruder is 270-320 ℃, the head temperature is 280-330 ℃ and the main machine rotating speed is 180-550r/min, and then cooling by water, drawing strips and cutting particles to obtain the white graphene modified polyphenyl ether composite material.
The preparation method of the white graphene modified polyphenyl ether composite material is simple and convenient to operate, does not need complex instruments, can realize batch production, and can meet industrial application. The white graphene modified polyphenyl ether composite material prepared by the method has high mechanical strength, high thermal conductivity and high processability.
The present invention will be described with reference to specific examples.
Example 1
Step 1): preparing high polymer modified white graphene: adding 10 parts of 2-10 layers of white graphene powder into a round-bottom flask, adding 100ml of distilled water into the round-bottom flask, performing ultrasonic dispersion, adding 0.2 part of sodium dodecyl sulfate into the round-bottom flask, and performing ultrasonic high-speed stirring to obtain an oleophylic modified white graphene dispersion solution;
heating the oleophylic modified white graphene dispersion liquid to 90 ℃, adding 1.5 parts of initiator ammonium persulfate, stirring for 10min, then beginning to dropwise add 3 parts of styrene, and finishing dropping within 1 h. After the dropwise addition, the temperature is kept for 30min until the reaction is finished. And after the reaction is finished, adjusting the pH value to 7 by using ammonia water, quickly cooling to normal temperature, filtering under reduced pressure, washing the filter cake by using distilled water for 3-4 times, washing by using alcohol for one time, and drying and grinding in vacuum at 60 ℃ to obtain the polystyrene-coated modified white graphene.
Step 2) premixing and dispersing white graphene/PPO resin: after the heating temperature of a high-speed mixer is stabilized at 80 ℃, 92 parts of PPO resin, 3 parts of polystyrene coated and modified white graphene, 2 parts of No. 15 industrial white oil and 3 parts of polyethylene wax are respectively weighed according to parts by weight and premixed and dispersed for 6min by a high-speed stirrer to be discharged;
step 3), preparing white graphene modified PPO master batch: and (3) controlling the temperature of each zone of the double-screw extruder to be stabilized at 270-300 ℃, controlling the temperature of a machine head to be stabilized at 310 ℃, adding 100 parts of the premixed and dispersed mixture obtained in the step 2) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 260r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene modified PPO master batch of the embodiment 1.
Example 2
Step 1): preparing high polymer modified white graphene: adding 10 parts of 2-10 layers of white graphene powder into a round-bottom flask, adding 100ml of distilled water into the round-bottom flask, performing ultrasonic dispersion, adding 0.2 part of sodium dodecyl sulfate into the round-bottom flask, and performing ultrasonic high-speed stirring to obtain an oleophylic modified white graphene dispersion solution;
heating the oleophylic modified white graphene dispersion liquid to 90 ℃, adding 1.5 parts of initiator ammonium persulfate, stirring for 10min, then beginning to dropwise add 3 parts of styrene, and finishing dropping within 1 h. After the dropwise addition, the temperature is kept for 30min until the reaction is finished. And after the reaction is finished, adjusting the pH value to 7 by using ammonia water, quickly cooling to normal temperature, filtering under reduced pressure, washing the filter cake by using distilled water for 3-4 times, washing by using alcohol for one time, and drying and grinding in vacuum at 60 ℃ to obtain the polystyrene-coated modified white graphene.
Step 2) premixing and dispersing white graphene/PPO resin: after the heating temperature of a high-speed mixer is stabilized at 90 ℃, 88 parts of PPO resin, 5 parts of polystyrene coated and modified white graphene, 3 parts of No. 26 industrial white oil and 4 parts of polyethylene wax are respectively weighed according to parts by weight and premixed and dispersed for 10min by a high-speed mixer to be discharged;
step 3), preparing white graphene modified PPO master batch: and (3) controlling the temperature of each zone of the double-screw extruder to be stable at 310 ℃ in 280 plus, controlling the temperature of a machine head to be stable at 320 ℃, adding 100 parts of the premixed and dispersed mixture obtained in the step 2) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 350r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene modified PPO master batch of the embodiment 2.
Example 3
Step 1): preparing high polymer modified white graphene: adding 10 parts of 2-10 layers of white graphene powder into a round-bottom flask, adding 100ml of distilled water into the round-bottom flask, performing ultrasonic dispersion, adding 0.2 part of sodium dodecyl sulfate into the round-bottom flask, and performing ultrasonic high-speed stirring to obtain an oleophylic modified white graphene dispersion solution;
heating the oleophylic modified white graphene dispersion liquid to 90 ℃, adding 1.5 parts of initiator ammonium persulfate, stirring for 10min, then beginning to dropwise add 3 parts of styrene, and finishing dropping within 1 h. After the dropwise addition, the temperature is kept for 30min until the reaction is finished. And after the reaction is finished, adjusting the pH value to 7 by using ammonia water, quickly cooling to normal temperature, filtering under reduced pressure, washing the filter cake by using distilled water for 3-4 times, washing by using alcohol for one time, and drying and grinding in vacuum at 60 ℃ to obtain the polystyrene-coated modified white graphene.
Step 2) premixing and dispersing white graphene/PPO resin: after the heating temperature of the high-speed mixer is stabilized at 90 ℃, 83 parts of PPO resin, 8 parts of modified white graphene, 4 parts of 36# food-grade white oil and 5 parts of oxidized polyethylene wax are respectively weighed according to parts by weight and premixed and dispersed for 15min by a high-speed mixer, and then discharged;
step 3), preparing white graphene modified PPO master batch: and (3) controlling the temperature of each zone of the double-screw extruder to be stabilized at 290-320 ℃, controlling the temperature of a machine head to be stabilized at 330 ℃, adding 100 parts of the premixed and dispersed mixture obtained in the step 2) into a cylinder of the double-screw extruder, controlling the rotating speed of a main machine to be 480r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene modified PPO master batch of the embodiment 3.
Example 4
The method is basically the same as in example 3, except that the polystyrene-coated modified white graphene in step 2) is added in an amount of 15 parts.
Example 5
Essentially the same as example 3, except that the polymerized monomer was glycidyl acrylate.
Example 6
The same as example 3 except that the monomer to be polymerized was methyl acrylate.
Comparative example 1
Step 1) pre-mixing and dispersing polypropylene (PP) resin: after the heating temperature of the high-speed mixer is stabilized at 80 ℃, 85 parts of PPO resin, 10 parts of high impact polystyrene HIPS, 2 parts of phenol antioxidant 1010 and 3 parts of polyethylene wax are respectively weighed according to parts by weight and premixed and dispersed for 6min by a high-speed mixer to be discharged;
step 2) preparation of modified PPO master batch: and (2) controlling the temperature of each zone of the double-screw extruder to be stabilized at 270-300 ℃, controlling the temperature of a machine head to be stabilized at 310 ℃, adding 100 parts of the premixed and dispersed mixture obtained in the step 1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 250r/min, and mixing, extruding, water-cooling, drawing strips and granulating to obtain the HIPS modified PPO master batch.
Comparative example 2
Step 1) premixing and dispersing white graphene/PPO resin: after the heating temperature of a high-speed mixer is stabilized at 80 ℃, 92 parts of PPO resin, 3 parts of unmodified white graphene, 2 parts of No. 15 industrial white oil and 3 parts of polyethylene wax are respectively weighed according to parts by weight and premixed and dispersed for 6min by a high-speed mixer to be discharged;
step 2), preparing white graphene modified PPO master batch: and (3) controlling the temperature of each zone of the double-screw extruder to be stabilized at 270-300 ℃, controlling the temperature of a machine head to be stabilized at 310 ℃, adding 100 parts of the premixed and dispersed mixture obtained in the step 2) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 260r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene modified PPO master batch.
Performance testing
The test method used was as follows:
tensile strength: ISO 527-2: 1993
Notched impact strength: ISO 179-1: 2000
Wear resistance: ASTM D1044-2013
Coefficient of thermal conductivity: ASTM D5470
TABLE 1 white graphene composite PPO master batch performance of each example and comparative example
As can be seen from table 1, the white graphene-modified polyphenylene ether composites of examples 1 to 6 have higher tensile strength and notched impact strength, indicating that they have higher toughness and mechanical properties. The white graphene-modified polyphenylene ether composite materials of the embodiments 1 to 6 have higher thermal conductivity, which indicates that the white graphene-modified polyphenylene ether composite materials have higher thermal conductivity; the white graphene-modified polyphenylene ether composite materials of examples 1 to 6 have high wear resistance, which indicates that the white graphene-modified polyphenylene ether composite materials have high scratch resistance and high processability.
In addition, it can be seen from comparative examples 3, 5 and 6 that the polymerized monomer has a certain effect on the composite material, and styrene is preferred.
The comparative example 1 is the HIPS modified PPO master batch, and as can be seen from Table 1, the tensile strength, the notched impact strength, the wear resistance and the thermal conductivity coefficient of the HIPS modified PPO master batch are obviously lower than those of the examples 1 to 6, which indicates that the HIPS modified PPO master batch has no mechanical strength, heat resistance and processability as the white graphene modified polyphenylene oxide composite material.
The white graphene in comparative example 2 is not modified, and as can be seen from table 1, the tensile strength, the notched impact strength, the wear resistance and the thermal conductivity are all significantly lower than those of example 1, which indicates that the white graphene modified by the high polymer has a great influence on the mechanical properties, the thermal conductivity and the processability of the composite material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The white graphene modified polyphenyl ether composite material is characterized by being mainly prepared from the following raw materials in parts by weight: 0.1-20 parts of high polymer modified white graphene, 60-100 parts of polyphenyl ether resin, 0.1-10 parts of white oil and 0.1-20 parts of dispersant;
the high polymer modified white graphene is mainly prepared from the following raw materials in parts by weight: 0.5-10 parts of white graphene, 0.05-2 parts of polymerized monomer, 0.1-5 parts of stabilizer, 0.5-5 parts of initiator and 90-110 parts of solvent;
the polymerization monomer is one or more of styrene, acrylic acid, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate and glycidyl methacrylate.
2. The white graphene-modified polyphenylene ether composite material according to claim 1, which is prepared from the following raw materials in parts by weight: 1-15 parts of high polymer modified white graphene, 80-100 parts of polyphenyl ether resin, 0.5-5 parts of white oil and 0.5-10 parts of dispersing agent.
3. The white graphene-modified polyphenylene ether composite material according to claim 1 or 2, wherein the white oil is one or more of 1#, 3#, 5#, 7#, 10#, 15#, 26#, 36#, 46# industrial grade white oil or food grade white oil; and/or
The dispersing agent is one or more of paraffin, polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, barium stearate and pentaerythritol stearate.
4. The white graphene-modified polyphenylene ether composite material according to claim 1 or 2, wherein the stabilizer is one or more of polyvinylpyrrolidone, sodium alkyl sulfate, sodium alkyl benzene sulfonate, oleylamine, and oleic acid.
5. The white graphene-modified polyphenylene ether composite material according to claim 1, wherein the initiator is one or more of ammonium persulfate and azobisisobutyronitrile; and/or the presence of a catalyst in the reaction mixture,
the solvent is one or more of water, ethanol, glycol, glycerol, ethyl acetate and butyl acetate.
6. The white graphene-modified polyphenylene ether composite material according to claim 1, wherein the number of the polymer-modified white graphene layers is 2-10, the particle size is 5-10 μm, and the specific surface area is 300-500m2/g。
7. The white graphene-modified polyphenylene ether composite material according to claim 1, wherein the method for preparing the high polymer-modified white graphene comprises the steps of:
placing the white graphene in the solvent for ultrasonic dispersion, and then adding the stabilizer for treatment to obtain oleophylic modified white graphene dispersion liquid;
and (3) uniformly mixing the oleophylic modified white graphene dispersion liquid with the polymerization monomer and the initiator, reacting for 0.5-3h at the temperature of 60-120 ℃, adding a neutralizing agent to adjust the pH value to 7-8, cooling, filtering and drying to obtain the high polymer modified white graphene.
8. A method for preparing the white graphene-modified polyphenylene ether composite material according to any one of claims 1 to 7, comprising the steps of:
and mixing and dispersing the polyphenyl ether resin, the white graphene modified by the high polymer, the white oil and the dispersing agent, then mixing and melting, and extruding and granulating to obtain the white graphene modified polyphenyl ether composite material.
9. The method of claim 8, wherein said mixing and dispersing comprises the steps of:
and (2) placing the polyphenyl ether resin, the white graphene modified by the high polymer, the white oil and the dispersing agent in a high-speed mixer, and mixing and dispersing for 5-30min at the temperature of 60-120 ℃.
10. The method of claim 8, wherein the mixing, melting, extruding and granulating comprises the following steps:
and adding the mixed and dispersed mixed components into a charging barrel of a double-screw extruder, mixing and extruding under the conditions that the temperature range of each area of the double-screw extruder is 270-320 ℃, the head temperature is 280-330 ℃ and the main machine rotating speed is 180-550r/min, and then cooling, drawing strips and cutting granules to obtain the white graphene modified polyphenyl ether composite material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575087A (en) * | 2009-10-21 | 2012-07-11 | 赢创德固赛有限公司 | Film made of polyaryleetherketone |
| CN104927330A (en) * | 2015-06-15 | 2015-09-23 | 四川大学 | High thermal conductive and insulating polymer composite and preparing method and application thereof |
| CN105026312A (en) * | 2013-03-07 | 2015-11-04 | 电气化学工业株式会社 | Boron-nitride powder and resin composition containing same |
| CN105623234A (en) * | 2016-03-24 | 2016-06-01 | 安徽大学 | High-thermal-conductivity engineering plastic and preparation method thereof |
| CN105860315A (en) * | 2016-06-14 | 2016-08-17 | 辽宁大学 | Preparing method of hexagonal boron nitride/polystyrene composite |
-
2018
- 2018-03-08 CN CN201810190938.2A patent/CN108504077B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575087A (en) * | 2009-10-21 | 2012-07-11 | 赢创德固赛有限公司 | Film made of polyaryleetherketone |
| CN105026312A (en) * | 2013-03-07 | 2015-11-04 | 电气化学工业株式会社 | Boron-nitride powder and resin composition containing same |
| CN104927330A (en) * | 2015-06-15 | 2015-09-23 | 四川大学 | High thermal conductive and insulating polymer composite and preparing method and application thereof |
| CN105623234A (en) * | 2016-03-24 | 2016-06-01 | 安徽大学 | High-thermal-conductivity engineering plastic and preparation method thereof |
| CN105860315A (en) * | 2016-06-14 | 2016-08-17 | 辽宁大学 | Preparing method of hexagonal boron nitride/polystyrene composite |
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