CN112063076A - Graphene polyvinyl chloride composite material and preparation method thereof - Google Patents
Graphene polyvinyl chloride composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112063076A CN112063076A CN202010972267.2A CN202010972267A CN112063076A CN 112063076 A CN112063076 A CN 112063076A CN 202010972267 A CN202010972267 A CN 202010972267A CN 112063076 A CN112063076 A CN 112063076A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyvinyl chloride
- composite material
- parts
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- 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)
- Graft Or Block Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a graphene polyvinyl chloride composite material and a preparation method thereof, wherein the graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight: 5-10 parts of maleic anhydride grafted polystyrene resin, 1-3 parts of N-methyl pyrrolidone, 20-30 parts of polyvinyl chloride, 1-5 parts of modified graphene, 1-3 parts of acetylene black, 0.1-3.0 parts of zinc oxide, 4-8 parts of plasticizer, 0.1-3.0 parts of antioxidant, 0.05-0.5 part of initiator and 1-5 parts of filler. According to the invention, the polyvinyl chloride is toughened by the modified graphene, the modified graphene is in a uniformly dispersed state and has strong interface binding force with the composite material, the polymerization reaction kinetics and the heat transfer process of the polyvinyl chloride are not affected, the performance of the polyvinyl chloride can be improved comprehensively, the compatibility of the modified graphene and a polymer matrix can be obviously improved, and the modified graphene is uniformly dispersed in the polyvinyl chloride, so that the composite material with excellent performance is obtained.
Description
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to a graphene polyvinyl chloride composite material and a preparation method thereof.
Background
Polyvinyl chloride (PVC) has excellent comprehensive properties such as good mechanical property, electrical property, corrosion resistance, flame retardance and the like, is low in price and wide in raw material source, and is widely applied to chemical building materials and other fields. PVC is a general-purpose resin with wide application, but the application of PVC is limited to a certain extent due to high melt viscosity, poor impact resistance and poor thermal stability. Therefore, the modification of polyvinyl chloride has attracted the attention of a great number of researchers. The traditional method for modifying polyvinyl chloride is to add elastomers such as acrylic copolymers, thermoplastic polyurethanes, nitrile rubbers, thermoplastic resins. The addition of these elastomers can greatly raise the toughness of the material, but can greatly reduce its rigidity, strength and heat-distortion temperature.
There are some patents reporting that polyvinyl chloride is modified by graphene. However, graphene is difficult to bond with a substrate material in a polymerization process, so that compatibility problems exist between graphene and polyvinyl chloride, environmental pollution is caused, and the popularization and application and performance improvement of the polyvinyl chloride composite material are influenced due to the existing problems and disadvantages.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a graphene polyvinyl chloride composite material, which can obviously improve the compatibility of modified graphene and a polymer matrix and uniformly disperse the modified graphene in polyvinyl chloride, so that the composite material with excellent performance is obtained.
The invention aims to provide a preparation method of a graphene polyvinyl chloride composite material, which is simple to operate, convenient to control, high in production efficiency and low in production cost.
The purpose of the invention is realized by the following technical scheme: the graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight:
the plasticizer is tricresyl phosphate T306 produced by Shandong Ruixing flame retardant science and technology Limited.
The polyvinyl chloride adopted in the invention has good comprehensive properties such as mechanical property, electrical property, corrosion resistance, flame retardance and the like, but the application of the polyvinyl chloride is limited to a certain extent due to large melt viscosity, poor impact resistance and poor thermal stability, so that the polyvinyl chloride is toughened by the modified graphene, and the modified graphene is in a uniformly dispersed state and has strong interface binding force with a composite material, is particularly suitable for a polyvinyl chloride system, has no influence on polymerization reaction kinetics and a heat transfer process, can comprehensively improve the performance of the polyvinyl chloride, can remarkably improve the compatibility of the modified graphene and a polymer matrix, and uniformly disperses the modified graphene in the polyvinyl chloride, thereby obtaining the composite material with excellent performance. The adopted maleic anhydride grafted polystyrene resin PS (PS-35) has good phase interface binding capacity, and can improve the polarity of the surface of polyvinyl chloride and the binding rate of the modified graphene and the polyvinyl chloride in the polymerization process of the modified graphene and the polyvinyl chloride, so that the graphene polyvinyl chloride composite material has higher mechanical strength; the N-methyl pyrrolidone is a polar solvent with good selectivity and high stability, and can well disperse among the maleic anhydride grafted polystyrene resin, the polyvinyl chloride and the modified graphene in a graphene polyvinyl chloride composite material system, so that the problem of compatibility of the graphene polyvinyl chloride can be solved, and the bonding rate of the modified graphene and the polyvinyl chloride is improved; the acetylene black has high thermal decomposition temperature, and is added into a graphene polyvinyl chloride composite material composite system, so that the thermal stability of the system can be obviously improved, the composite material has high thermal deformation temperature, and the performance of the graphene polyvinyl chloride composite material is comprehensively improved; in addition, the zinc oxide can be used as a light stabilizer and a heat stabilizer of the composite material, and further cooperates with the acetylene black to obviously improve the thermal stability of the system, so that the composite material has good thermal deformation temperature, and the performance of the graphene polyvinyl chloride composite material is comprehensively improved.
Preferably, each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a solution with the mass percentage concentration of 60-70%; the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to the weight ratio of 0.8-1.2: 0.6-1.0.
Preferably, the modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 100-120 ℃ water bath for 30-60min, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 80-100 ℃ to obtain modified graphene.
According to the invention, the modified graphene is in a uniformly dispersed state, has strong interface binding force with the composite material, can interact with a polyvinyl chloride molecular chain, has no influence on polymerization reaction kinetics and a heat transfer process, can comprehensively improve the performance of polyvinyl chloride, can remarkably improve the compatibility of the modified graphene and a polymer matrix, and can be uniformly dispersed in the polyvinyl chloride, so that the composite material with excellent performance is obtained. The adopted micron graphene has small and uniform granularity and high surface activity, and the micron graphene and the composite material have strong interface binding force after being modified by the modifier; the adopted tetrahydrofuran is an organic solvent of the micron graphene, so that the micron graphene can be well dissolved and dispersed, and modification by a modifier is facilitated. When the micron graphene is modified, the water bath temperature in the step S1 needs to be strictly controlled to be 100-120 ℃, if the temperature is too high, the mass percentage concentration of the hydroxide solution is too high, part of the sodium hydroxide is crystallized, the activation of the micron graphene is not facilitated, and if the temperature is too low, the optimal activity range of the micron graphene is not reached, and the modification of the micron graphene is not facilitated.
Preferably, each part of the antioxidant is a mixture of the antioxidant DNP, the antioxidant 1010 and the antioxidant 168 according to the weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0.
The antioxidant 1010 adopted by the invention has excellent oxidation resistance on maleic anhydride grafted polystyrene resin and polyvinyl chloride, the antioxidant 1010 can effectively prevent thermal oxidation degradation of the composite material in a long-term aging process, so that the service life of the composite material is prolonged, and in addition, the antioxidant 1010 can be used together with the antioxidant 168 to have a synergistic effect; the antioxidant 168 and the antioxidant DNP auxiliary antioxidant are compounded with the main antioxidant 1010, have good synergistic effect, can effectively prevent thermal degradation of the maleic anhydride grafted polystyrene resin and polyvinyl chloride in basic injection molding, and provide extra long-acting protection for the composite material.
Preferably, each part of the initiator is at least one of bis (2-ethylhexyl) peroxydicarbonate, and azobisisobutyronitrile. Each part of the filler is at least one of silicon lime, gas-phase silicon dioxide, aluminum powder and zinc powder. More preferably, each part of the filler is a mixture of silica fume, fumed silica and zinc powder in a weight ratio of 0.4-0.8:0.8-1.2: 0.6-1.0.
In the invention, the initiator di (2-ethylhexyl) peroxydicarbonate is a free radical type initiator and is an initiator of chloroethylene, and in the process of polymerizing the modified graphene and the polyvinyl chloride, the polarity of the surface of the polyvinyl chloride can be improved, the bonding rate of the modified graphene and the polyvinyl chloride is improved, so that the graphene polyvinyl chloride composite material has higher mechanical strength; the filler can make up the defects that the interaction force between the maleic anhydride grafted polystyrene resin and the polyvinyl chloride molecules is weak and the cohesive energy is low, improve the mechanical property of the prepared composite material and play a role in reinforcing.
The invention also provides a preparation method of the graphene polyvinyl chloride composite material, which comprises the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 40-60 ℃, and stirring for 20-40min to obtain a mixture A for later use;
2) according to the parts by weight, uniformly mixing and stirring the acetylene black, the initiator and the antioxidant, heating to 120-140 ℃, and continuously stirring for 1-2h under the condition of 300-600r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), stirring for 40-50 minutes at the temperature of 80-90 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
The graphene polyvinyl chloride composite material prepared by the method is prepared by adopting the modified graphene to toughen polyvinyl chloride, and the modified graphene is in a uniformly dispersed state and has strong interface bonding force with the composite material, so that the graphene polyvinyl chloride composite material is particularly suitable for a polyvinyl chloride system, has no influence on polymerization reaction kinetics and a heat transfer process, can comprehensively improve the polyvinyl chloride performance, can remarkably improve the compatibility of the modified graphene and a polymer matrix, and uniformly disperses the modified graphene in the polyvinyl chloride, thereby obtaining the composite material with excellent performance. In the process of preparing the composite material, the temperature in the step 2) needs to be strictly controlled to be 120-140 ℃, if the temperature is too high, part of the initiator is deactivated, and if the temperature is too low, the dispersion among the raw materials is not facilitated, so that the comprehensive performance of the graphene polyvinyl chloride composite material is influenced; and the temperature in the step 3) needs to be strictly controlled to be 80-90 ℃, if the temperature is too high, the interface molecules of the modified graphene are too active, and the interface binding force between the modified graphene and the polyvinyl chloride is not facilitated.
The invention has the beneficial effects that: according to the invention, the polyvinyl chloride is toughened by the modified graphene, and the modified graphene is in a uniformly dispersed state and has strong interface binding force with the composite material, so that the polyvinyl chloride composite material is particularly suitable for a polyvinyl chloride system, has no influence on polymerization reaction kinetics and a heat transfer process, can comprehensively improve the performance of polyvinyl chloride, can remarkably improve the compatibility of the modified graphene and a polymer matrix, and can uniformly disperse the modified graphene in the polyvinyl chloride, thereby obtaining the composite material with excellent performance.
The preparation method of the graphene polyvinyl chloride composite material is simple to operate, convenient to control, high in production efficiency and low in production cost.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight:
the plasticizer is tricresyl phosphate T306 produced by Shandong Ruixing flame retardant science and technology Limited; the maleic anhydride grafted polystyrene resin is maleic anhydride grafted polystyrene resin PS (PS-35).
Each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a solution with the mass percentage concentration of 60%; the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to a weight ratio of 0.8: 0.6.
The modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 100 ℃ for 30min in a water bath, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 80 ℃ to obtain modified graphene.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.8:0.4: 0.6.
Each part of the initiator is di (2-ethylhexyl) peroxydicarbonate.
Each part of the filler is a mixture of silica fume, fumed silica and zinc powder according to the weight ratio of 0.4:0.8: 0.6.
The preparation method of the graphene polyvinyl chloride composite material comprises the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 40 ℃, and stirring for 20min to obtain a mixture A for later use;
2) mixing and stirring acetylene black, an initiator and an antioxidant uniformly according to parts by weight, heating to 120 ℃, and continuously stirring for 1h under the condition of 300r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), keeping the temperature and stirring for 40 minutes at 80 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
Example 2
The graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight:
the plasticizer is tricresyl phosphate T306 produced by Shandong Ruixing flame retardant science and technology Limited; the maleic anhydride grafted polystyrene resin is maleic anhydride grafted polystyrene resin PS (PS-35).
Each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a solution with the mass percentage concentration of 63%; the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to a weight ratio of 0.9: 0.7.
The modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 105 ℃ in a water bath for 38min, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 85 ℃ to obtain modified graphene.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.9:0.5: 0.7.
Each part of the initiator is di (2-ethylhexyl) peroxydicarbonate.
Each part of the filler is a mixture of silica fume, fumed silica and zinc powder according to the weight ratio of 0.5:0.9: 0.7.
The preparation method of the graphene polyvinyl chloride composite material comprises the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 45 ℃, and stirring for 25min to obtain a mixture A for later use;
2) mixing and stirring acetylene black, an initiator and an antioxidant uniformly according to parts by weight, heating to 125 ℃, and continuously stirring for 1.25 hours under the condition of 375r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), keeping the temperature and stirring for 43 minutes at 83 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
Example 3
The graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight:
the plasticizer is tricresyl phosphate T306 produced by Shandong Ruixing flame retardant science and technology Limited; the maleic anhydride grafted polystyrene resin is maleic anhydride grafted polystyrene resin PS (PS-35).
Each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a 65% solution in percentage by mass; the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to the weight ratio of 1.0: 0.8.
The modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydrogen hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 110 ℃, performing water bath for 45min, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 90 ℃ to obtain modified graphene.
Each part of the antioxidant is a mixture of antioxidant DNP, antioxidant 1010 and antioxidant 168 according to the weight ratio of 1.0:0.6: 0.8.
Each part of the initiator is azodiisobutyronitrile.
Each part of the filler is a mixture of silica fume, fumed silica and zinc powder according to the weight ratio of 0.6:1.0: 0.8.
The preparation method of the graphene polyvinyl chloride composite material comprises the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 50 ℃, and stirring for 30min to obtain a mixture A for later use;
2) mixing and stirring acetylene black, an initiator and an antioxidant uniformly according to parts by weight, heating to 130 ℃, and continuously stirring for 1.5 hours under the condition of 450r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), keeping the temperature and stirring for 45 minutes at 85 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
Example 4
The graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight:
the plasticizer is tricresyl phosphate T306 produced by Shandong Ruixing flame retardant science and technology Limited; the maleic anhydride grafted polystyrene resin is maleic anhydride grafted polystyrene resin PS (PS-35).
Each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a solution with the mass percentage concentration of 68%; the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to the weight ratio of 1.1: 0.9.
The modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydrogen hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 115 ℃ in a water bath for 52min, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 95 ℃ to obtain modified graphene.
Each part of the antioxidant is a mixture of antioxidant DNP, antioxidant 1010 and antioxidant 168 according to the weight ratio of 1.1:0.7: 0.9.
Each part of the initiator is di (2-ethylhexyl) peroxydicarbonate.
Each part of the filler is a mixture of silica fume, fumed silica and zinc powder according to the weight ratio of 0.7:1.1: 0.9.
The preparation method of the graphene polyvinyl chloride composite material comprises the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 55 ℃, and stirring for 35min to obtain a mixture A for later use;
2) mixing and stirring acetylene black, an initiator and an antioxidant uniformly according to parts by weight, heating to 135 ℃, and continuously stirring for 1.75 hours under the condition of 515r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), keeping the temperature and stirring for 48 minutes at 88 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
Example 5
The graphene polyvinyl chloride composite material comprises the following raw materials in parts by weight:
the plasticizer is tricresyl phosphate T306 produced by Shandong Ruixing flame retardant science and technology Limited; the maleic anhydride grafted polystyrene resin is maleic anhydride grafted polystyrene resin PS (PS-35).
Each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a solution with the mass percentage concentration of 70%; the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to the weight ratio of 1.2: 1.0.
The modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 120 ℃ in a water bath for 60min, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 100 ℃ to obtain modified graphene.
Each part of the antioxidant is a mixture of antioxidant DNP, antioxidant 1010 and antioxidant 168 according to the weight ratio of 1.2:0.8: 1.0.
Each part of the initiator is di (2-ethylhexyl) peroxydicarbonate.
Each part of the filler is a mixture of silica fume, fumed silica and zinc powder according to the weight ratio of 0.8:1.2: 1.0.
The preparation method of the graphene polyvinyl chloride composite material comprises the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 60 ℃, and stirring for 40min to obtain a mixture A for later use;
2) mixing and stirring acetylene black, an initiator and an antioxidant uniformly according to parts by weight, heating to 140 ℃, and continuously stirring for 2 hours under the condition of 600r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), keeping the temperature and stirring for 50 minutes at 90 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
Comparative example 1
This comparative example differs from example 1 above in that: no modification of graphene was performed in this comparative example. The remainder of this comparative example is the same as example 1 and will not be described again here.
Comparative example 2
This comparative example differs from example 3 above in that: in this comparative example, diethylene triamine was used instead of the modifier in the preparation of the modified graphene, and the other raw materials were mixed in the same ratio as in example 3. The remainder of this comparative example is the same as example 3 and will not be described again here.
Comparative example 3
This comparative example differs from example 5 above in that: the maleic anhydride grafted polystyrene resin was not used in this comparative example, and the rest of the comparative example is the same as example 5 and will not be described again.
Mechanical property tests were performed on the graphene polyvinyl chloride composite materials prepared in examples 1 to 5 and comparative examples 1 to 3, and the results are shown in table 1:
TABLE 1
| Item | Flexural Strength (MPa) | Tensile Strength (MPa) | Impact Strength (MPa) |
| Example 1 | 96.0 | 73.0 | 13.7 |
| Example 2 | 96.2 | 72.8 | 13.5 |
| Example 3 | 96.5 | 73.2 | 14.2 |
| Example 4 | 96.9 | 73.1 | 13.6 |
| Example 5 | 96.1 | 72.9 | 14.2 |
| Comparative example 1 | 54.6 | 47.2 | 7.6 |
| Comparative example 2 | 69.2 | 53.7 | 8.9 |
| Comparative example 3 | 75.4 | 63.1 | 9.7 |
From the above, the graphene polyvinyl chloride composite material of the present invention has excellent mechanical properties such as bending strength, tensile strength and impact strength. According to the modified graphene, the modifying agent is added when the graphene is modified, and the maleic anhydride grafted polystyrene resin adopted in the invention can improve various mechanical properties of the graphene polyvinyl chloride composite material, so that the graphene polyvinyl chloride composite material has the advantages of good mechanical properties, long service life and environmental friendliness.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. A graphene polyvinyl chloride composite material is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the graphene polyvinyl chloride composite material according to claim 1, wherein: each part of the modified graphene comprises the following raw materials in parts by weight:
the sodium hydroxide is a solution with the mass percentage concentration of 60-70%.
3. The graphene polyvinyl chloride composite material according to claim 2, wherein: the modified graphene is prepared by the following steps:
s1, adding the micron graphene into a hydroxide solution according to parts by weight, performing ultrasonic dispersion, heating to 100-120 ℃ water bath for 30-60min, and washing to be neutral to obtain micron graphene slurry for later use;
s2, adding the micron graphene slurry obtained in the step S1 into tetrahydrofuran, adding a modifier, performing ultrasonic dispersion, and drying at 80-100 ℃ to obtain modified graphene.
4. The graphene polyvinyl chloride composite material according to claim 2, wherein: each part of the modifier is a mixture of hydroxymethyl cellulose and triethylene tetramine according to the weight ratio of 0.8-1.2: 0.6-1.0.
5. The graphene polyvinyl chloride composite material according to claim 1, wherein: each portion of the plasticizer was tricresyl phosphate T306.
6. The graphene polyvinyl chloride composite material according to claim 1, wherein: each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0.
7. The graphene polyvinyl chloride composite material according to claim 1, wherein: each part of the initiator is at least one of di (2-ethylhexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate and azobisisobutyronitrile.
8. The graphene polyvinyl chloride composite material according to claim 1, wherein: each part of the filler is at least one of silicon lime, gas-phase silicon dioxide, aluminum powder and zinc powder.
9. A method of preparing a graphene polyvinyl chloride composite material according to any one of claims 1 to 8, wherein: is prepared by the following steps:
1) uniformly mixing polyvinyl chloride, maleic anhydride grafted polystyrene resin, a filler, a plasticizer, modified graphene and N-methyl pyrrolidone in parts by weight, adding the mixture into a stirrer, heating to 40-60 ℃, and stirring for 20-40min to obtain a mixture A for later use;
2) according to the parts by weight, uniformly mixing and stirring the acetylene black, the initiator and the antioxidant, heating to 120-140 ℃, and continuously stirring for 1-2h under the condition of 300-600r/min to obtain a mixture B for later use;
1. adding the mixture B obtained in the step 2) and zinc oxide into the mixture A obtained in the step 1), stirring for 40-50 minutes at the temperature of 80-90 ℃, discharging, filtering, feeding into an extruder, performing melt extrusion, and cooling to obtain the graphene polyvinyl chloride composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010972267.2A CN112063076B (en) | 2020-09-16 | 2020-09-16 | Graphene polyvinyl chloride composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010972267.2A CN112063076B (en) | 2020-09-16 | 2020-09-16 | Graphene polyvinyl chloride composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112063076A true CN112063076A (en) | 2020-12-11 |
| CN112063076B CN112063076B (en) | 2023-03-28 |
Family
ID=73696904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010972267.2A Active CN112063076B (en) | 2020-09-16 | 2020-09-16 | Graphene polyvinyl chloride composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112063076B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940411A (en) * | 2021-01-29 | 2021-06-11 | 大连理工大学 | Graphene/polyvinyl chloride composite packaging material and preparation method thereof |
| CN113024991A (en) * | 2021-04-07 | 2021-06-25 | 广东宇豪新材料科技有限公司 | Graphene functionalized modified light composite material for vehicles |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110095244A1 (en) * | 2008-06-30 | 2011-04-28 | Dow Global Technologies, Inc. | Polymer composite with intumescent graphene |
| CN103087404A (en) * | 2011-10-31 | 2013-05-08 | 上海杰事杰新材料(集团)股份有限公司 | Graphene filled polymer matrix composite material and its preparation method |
| CN103449420A (en) * | 2013-08-22 | 2013-12-18 | 中国科学院金属研究所 | High-quality graphene dispersion method and film preparation method |
| CN104098816A (en) * | 2013-04-09 | 2014-10-15 | 合肥杰事杰新材料股份有限公司 | Polyolefin/graphene nanocomposite and preparation method thereof |
| US20150368439A1 (en) * | 2014-06-24 | 2015-12-24 | Enerage Inc. | Graphene Polymer Composite Material |
| CN105295255A (en) * | 2015-12-01 | 2016-02-03 | 济南大学 | Graphene oxide and glass-fiber reinforced polyvinyl chloride composite material and preparation method thereof |
| WO2019180292A1 (en) * | 2018-03-23 | 2019-09-26 | Avanzare Innovacion Tecnologica S.L. | Use of high-aspect-ratio graphene materials as additives for thermoplastic materials |
| CN110655742A (en) * | 2019-10-15 | 2020-01-07 | 高静静 | Modified PVC cable material and preparation method thereof |
| US20200087150A1 (en) * | 2018-09-10 | 2020-03-19 | Board Of Regents, The University Of Texas System | Facile Direct Functionalization of Pristine Graphene Nanoparticles |
-
2020
- 2020-09-16 CN CN202010972267.2A patent/CN112063076B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110095244A1 (en) * | 2008-06-30 | 2011-04-28 | Dow Global Technologies, Inc. | Polymer composite with intumescent graphene |
| CN103087404A (en) * | 2011-10-31 | 2013-05-08 | 上海杰事杰新材料(集团)股份有限公司 | Graphene filled polymer matrix composite material and its preparation method |
| CN104098816A (en) * | 2013-04-09 | 2014-10-15 | 合肥杰事杰新材料股份有限公司 | Polyolefin/graphene nanocomposite and preparation method thereof |
| CN103449420A (en) * | 2013-08-22 | 2013-12-18 | 中国科学院金属研究所 | High-quality graphene dispersion method and film preparation method |
| US20150368439A1 (en) * | 2014-06-24 | 2015-12-24 | Enerage Inc. | Graphene Polymer Composite Material |
| CN105295255A (en) * | 2015-12-01 | 2016-02-03 | 济南大学 | Graphene oxide and glass-fiber reinforced polyvinyl chloride composite material and preparation method thereof |
| WO2019180292A1 (en) * | 2018-03-23 | 2019-09-26 | Avanzare Innovacion Tecnologica S.L. | Use of high-aspect-ratio graphene materials as additives for thermoplastic materials |
| US20200087150A1 (en) * | 2018-09-10 | 2020-03-19 | Board Of Regents, The University Of Texas System | Facile Direct Functionalization of Pristine Graphene Nanoparticles |
| CN110655742A (en) * | 2019-10-15 | 2020-01-07 | 高静静 | Modified PVC cable material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TING LI ET AL: "Polydopamine-functionalized graphene oxide compounded with polyvinyl alcohol/chitosan hydrogels on the recyclable adsorption of cu(II), Pb(II) and cd(II) from aqueous solution", 《JOURNAL OF POLYMER RESEARCH》 * |
| 赵永禄 等: "石墨烯/PVC原位聚合树脂的开发", 《聚氯乙烯》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940411A (en) * | 2021-01-29 | 2021-06-11 | 大连理工大学 | Graphene/polyvinyl chloride composite packaging material and preparation method thereof |
| CN112940411B (en) * | 2021-01-29 | 2022-08-05 | 大连理工大学 | Graphene/polyvinyl chloride composite packaging material and preparation method thereof |
| CN113024991A (en) * | 2021-04-07 | 2021-06-25 | 广东宇豪新材料科技有限公司 | Graphene functionalized modified light composite material for vehicles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112063076B (en) | 2023-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112063076B (en) | Graphene polyvinyl chloride composite material and preparation method thereof | |
| CN107383475B (en) | Lignin/nitrile rubber composite material and preparation method thereof | |
| CN101058621A (en) | Method of preparing ACS polymer based on continuous noumenon method | |
| CN108285598B (en) | Polyvinyl chloride processing aid master batch with toughening function and preparation method thereof | |
| CN114031874A (en) | Manufacturing method of CPVC cable protection pipe | |
| CN109294115A (en) | Nitrogen-doped graphene/PVC composite of water-proof coiled material and preparation method thereof | |
| CN111662561B (en) | Preparation method of flame-retardant and repeatedly-processable wood-plastic composite material | |
| CN114874551A (en) | Color master batch based on waste polypropylene and preparation method thereof | |
| CN112724588B (en) | Preparation method and application of ABS (acrylonitrile-butadiene-styrene) efficient flame-retardant toughening master batch | |
| CN105754040B (en) | High fluidity Heat-proof PVC resin and preparation method thereof | |
| CN101838358A (en) | Preparation method of nanometer silica-chloroethylene in-situ-polymerization hybrid material | |
| CN111454407B (en) | Preparation method of modified petroleum resin with remarkable light stability | |
| CN112940411B (en) | Graphene/polyvinyl chloride composite packaging material and preparation method thereof | |
| CN106751781A (en) | A kind of Graphene/nylon 6 composite board of high temperature resistant anti-dropping and preparation method thereof | |
| CN112159640A (en) | Environment-friendly sealing adhesive and preparation method thereof | |
| CN110713686A (en) | High-flame-retardance high-rigidity ABS material | |
| CN1687221B (en) | Method for preparing nano composite material of polyvinyl chloride/layer silicate | |
| KR20090071931A (en) | Thermoplastic resin composition including nano inorganic material and method of preparing the same | |
| CN115787970B (en) | Anti-static movable floor and preparation method thereof | |
| CN112029198B (en) | Graphene/polypropylene composite material and preparation method thereof | |
| CN113896887B (en) | Preparation method of nitrile group-containing epoxy resin toughening agent | |
| CN116082769B (en) | Environment-friendly polyvinyl chloride composite material and preparation method thereof | |
| CN110467790B (en) | Long glass fiber reinforced polypropylene composite material for foaming and preparation method thereof | |
| CN113667262A (en) | High-strength weather-resistant ABS composite material and preparation method thereof | |
| CN108546373A (en) | A kind of high-performance modified polyvinyl chloride and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230630 Address after: 516000 south of Guangzhou Shantou highway, niutianling village group, Xinjie village committee, Luoyang Town, BOLUO County, Huizhou City, Guangdong Province Patentee after: Guangdong Dongming New Material Technology Co.,Ltd. Address before: 516100 Luoyang Town Xinjie Village Committee Niutianling Village Committee South of Guangshan Highway, Boluo County, Huizhou City, Guangdong Province Patentee before: BOLUO DONGMING NEW MATERIALS Research Institute |
|
| TR01 | Transfer of patent right |