CN111073116A - Graphene modified composite material and preparation method and application thereof - Google Patents
Graphene modified composite material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a graphene modified composite material and a preparation method and application thereof. The method for preparing the graphene modified composite material comprises the following steps: (1) mixing graphene, a filler, a coating agent, a surface treatment agent, a dispersing agent and an antioxidant to obtain a mixed filler; (2) mixing the mixed filler with a first polymer matrix and carrying out first melt blending so as to obtain a composite material precursor; (3) and carrying out second melt blending on the composite material precursor so as to obtain the graphene modified composite material. The method can obviously improve the effect of mixing and dispersing the graphene in the polymer matrix, improve the filling proportion of the graphene in the composite material, and enable the graphene and other fillers to form a perfect network system in the composite material matrix, thereby obviously improving the heat conductivity, oxygen resistance and compression resistance of the graphene modified composite material.
Description
Technical Field
The invention belongs to the technical field of carbon nano composite materials, and particularly relates to a graphene modified composite material and a preparation method and application thereof.
Background
In the form of winter heating, ground radiation heating is a heating mode with economy and comfortableness, and the ground surface temperature is uniform, the temperature gradually decreases from bottom to top, the body feeling is comfortable, and the heating mode meets the thermal environment required by a human body. The ground radiation heating is generally accepted in domestic large and medium-sized cities, and is widely applied to various occasions such as families, hospitals, schools, office buildings and the like. The ground heating pipe is an important heat dissipation component adopted for ground radiation, and the heat conduction performance of the ground heating pipe directly influences the utilization efficiency of a heat source and the indoor heating effect. At present, a heat-resistant polyethylene (PE-RT) pipe is mainly used as a ground heating pipe, and the heat conductivity coefficient is only 0.2-0.3W/m.K, so that the heating efficiency is low. Moreover, when the system runs, the oxygen content in the system is higher due to the fact that after the pipe is heated, the distance between molecules is increased, oxygen molecules easily enter the pipeline system, hot water in the pipe is higher in oxygen content, the oxygen content in the system is finally increased, and bacteria and microorganisms are easy to breed in the pipeAnd the pipeline can be blocked after long-term use, so that the hot water circulation capacity is reduced, and the use performance of the pipe is greatly influenced. The use of oxygen-impermeable heated plastic pipes in floor heating engineering is therefore mandatory in the united states, europe and australia (e.g. DIN4726, the german application standard for plastic pipes). The importance of oxygen resistance of the pipe is gradually recognized in China, and experts in the industry consider that the popularization and application of the oxygen resistance type pipe are imperative and provide requirements for the oxygen resistance of the pipe in the relevant standards of plastic pipes: in the local regulations of floor radiant heating engineering promulgated in 2000 in Beijing, the requirements for oxygen resistance of the pipe are mentioned; in the PE-RT tube industry Standard (CJ/T175-3D); the requirements for the oxygen-resistant pipe are also provided in the technical regulation of ground radiant heating (JGJ 142-2004) of the industry standard issued and implemented in 2004. The oxygen-resistant pipe is the direction of future plastic pipes, and particularly applied to heating systems, and the advantages of the oxygen-resistant pipe are more obvious.
In addition, graphene is well known for its good heat conduction performance and two-dimensional lamellar structure, so it shows good application prospects in the fields of heat conduction, heat dissipation, oxygen barrier, etc., but graphene still has great difficulty in the application process: the interaction force between graphene layers is large, the agglomeration is serious, and effective stripping and uniform dispersion in a resin matrix are difficult to obtain. At present, a tube is placed in graphene glue solution for soaking, and then a layer of mixed solution is sprayed on the tube for drying to obtain an oxygen-barrier tube, the oxygen-barrier tube has good oxygen-barrier performance, but the preparation process is very complex, the used materials are various, and the graphene glue solution needs to be subjected to ultrasonic stripping and dispersion for 300 hours, so that the tube is not suitable for industrial mass production; the heat conductivity coefficient and the oxygen resistance effect of the floor heating pipe are improved by forming the inner layer, the outer layer, the adhesive layer and the oxygen resistance layer structure, but the method uses five layers of oxygen resistance, so that the cost is high, the process preparation is complex, and organic solvents such as acetone, chloroform, tetrahydrofuran, N-dimethylformamide or toluene are used, so that the production environment and the human health are also unfavorable.
Therefore, the development of novel heat-conducting oxygen-resistant composite materials has become an important direction for the development of high-performance floor heating pipes.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a graphene modified composite material and a preparation method and application thereof. The method for preparing the graphene modified composite material can obviously improve the effect of mixing and dispersing graphene in a polymer matrix, improve the filling proportion of the graphene in the composite material, and enable the graphene and other fillers to form a perfect network system in the composite material matrix, thereby obviously improving the heat conductivity, the oxygen resistance and the compression resistance of the graphene modified composite material.
The present inventors have proposed based on the following problems:
(1) the intermolecular force among the layers of the graphene is strong, the graphene is easy to stack and agglomerate together, and is not easy to fully strip and uniformly disperse in a polymer matrix, so that a uniform and stable network is difficult to form, and the potential advantage of high heat conductivity and high oxygen resistance of the graphene in the field of application of the floor heating pipe cannot be exerted; (2) the density of the graphene powder is low, the density difference between the graphene powder and a polymer matrix is large, high-concentration filling is difficult to realize in the blending granulation process, so that the processing difficulty of master batches is large, the consistency problem that part of the concentration is higher or lower is easy to exist, and the stable high-content filling of graphene is difficult to realize; (3) the heat conductivity coefficient of the common heat-resistant polyethylene floor heating pipe is 0.2-0.3W/m.K, the heat conductivity is poor, the heating efficiency is low, the heating cannot be started quickly, and energy is wasted; (4) the common floor heating pipe has poor oxygen resistance, and the oxygen permeability is generally 0.17g/m3D is about d, which can not meet the requirement of 0.1g/m for oxygen-resistant type floor heating pipe in the national standard GB/T28799.2-20123D, oxygen molecules enter the pipeline after long-term use, so that the thermal-oxidative aging of the pipeline is easily accelerated, bacteria and microorganisms are bred in the pipeline, the pipeline is blocked, and the use is influenced; moreover, the oxygen-resistant type ground heating pipe generally adopts three to five oxygen-resistant layers, and an EVOH oxygen-resistant layer and a bonding layer are added on the basis of the common pipe without adding an EVOH oxygen-resistant layer and a bonding layerOnly the processing technology is complex and the cost is higher; (5) the water pressure resistance of the floor heating pipe is poor, and the phenomenon of pipe explosion caused by the tiny defects of the pipe often occurs under the condition that the indoor water pressure is suddenly high and suddenly low and is unstable, so that certain potential safety hazards exist.
To this end, according to a first aspect of the present invention, the present invention proposes a method of preparing a graphene-modified composite material. According to an embodiment of the invention, the method comprises:
(1) mixing graphene, a filler, a coating agent, a surface treatment agent, a dispersing agent and an antioxidant to obtain a mixed filler;
(2) mixing the mixed filler with a first polymer matrix and carrying out first melt blending so as to obtain a composite material precursor;
(3) and carrying out second melt blending on the composite material precursor so as to obtain the graphene modified composite material.
The inventor finds that not only can graphene and other fillers be fully stripped and uniformly dispersed in a polymer matrix, but also high-density filling of the graphene in a composite material can be realized by premixing graphene, fillers, a coating agent, a surface treatment agent, a dispersing agent and an antioxidant and then carrying out multiple melt blending with the polymer matrix, so that the composite material with a uniform, stable and perfect heat-conducting oxygen-blocking reinforced network structure formed by the fillers such as the graphene in the polymer matrix can be obtained; however, as the number of melt blending increases, the mechanical properties, aging resistance and oxidation resistance of the composite material decrease. Therefore, the method for preparing the graphene modified composite material has at least the following advantages: 1. by optimizing the multi-scale design of the filler structure and adopting a three-step production process of premixing graphene and other fillers and then carrying out twice melt blending, the mixing and dispersing effects of the graphene in a polymer matrix can be obviously improved, and the filling proportion of the graphene in the composite material can be improved, so that the uniformity and the stability of the graphene modified composite material can be greatly improved, the advantages of the graphene in the aspects of heat conduction, oxygen resistance and reinforcement can be fully exerted, and the graphene composite material can be ensured to have better mechanical property, oxidation resistance and aging resistance; 2. the method has simple process and low cost, and can realize large-scale and industrialized production of the graphene modified composite material; 3. the graphene modified composite material prepared by the method has good heat conductivity, oxygen resistance and compression resistance, and can be widely applied to ground heating pipes and other pipes in the fields of heat conductivity, oxygen resistance and hydraulic pressure resistance.
In addition, the method for preparing the graphene modified composite material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the mass ratio of the first polymer matrix, the graphene, the filler, the coating agent, the surface treatment agent, the dispersant and the antioxidant is (18-80): (10-40): (5-10): (5-20): (0.1-1): (0.5-10): (0.1 to 3).
In some embodiments of the present invention, the mass ratio of the first polymer matrix, the graphene, the filler, the coating agent, the surface treatment agent, the dispersant, and the antioxidant is (18 to 80): (10-40): (5-10): (5-20): (0.1-1): (0.5-10): (0.1 to 3).
In some embodiments of the present invention, in the step (1), the temperature of the mixing treatment is 20 to 90 ℃, the rotation speed is 200 to 1500 rpm, and the time is 5 to 30 min.
In some embodiments of the present invention, the graphene has a radial dimension of 0.5 to 40 μm and a thickness of 1 to 20 nm.
In some embodiments of the present invention, the graphene is prepared by a mechanical exfoliation method, a biomass catalytic carbonization method, a high temperature activation method, a redox method, or a chemical vapor deposition method.
In some embodiments of the present invention, the filler is at least one selected from the group consisting of array-type carbon nanotubes, wound-type carbon nanotubes, micro powder graphite, expanded graphite, flake graphite, high purity graphite, and carbon black.
In some embodiments of the present invention, the capping agent is at least one selected from the group consisting of ethylene-vinyl acetate copolymer, thermoplastic elastomer, polyolefin elastomer, styrenic thermoplastic elastomer, styrene-ethylene-butylene-styrene block copolymer, polyester elastomer, linear low density polyethylene, ethylene propylene diene monomer rubber, nitrile rubber, and acrylate rubber.
In some embodiments of the present invention, the surface treatment agent is at least one selected from the group consisting of a silane coupling agent, an organic metal ester coupling agent, octadecylamine, and an isocyanate.
In some embodiments of the present invention, the dispersant is at least one selected from the group consisting of polyethylene wax, calcium stearate, EVA wax, ethylene bis stearamide, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, and ethylene butyl acrylate copolymer.
In some embodiments of the present invention, the antioxidant is at least one selected from the group consisting of a phosphorus-based antioxidant, a phenolic antioxidant, a sulfur-based antioxidant, and a natural antioxidant.
In some embodiments of the invention, in step (2), the temperature of the first melt blending is 160 to 250 ℃.
In some embodiments of the invention, in step (2), the first polymer matrix is heat resistant polyethylene and/or polybutylene. In some embodiments of the invention, the temperature of the second melt blending in step (3) is 160 to 250 ℃.
In some embodiments of the present invention, in the step (3), the composite material precursor is subjected to second melt blending and extrusion granulation, so as to obtain the graphene modified composite material.
According to a second aspect of the present invention, the present invention provides a graphene-modified composite material. According to the embodiment of the invention, the graphene modified composite material is prepared by adopting the method for preparing the graphene modified composite material. The graphene modified composite material is formed with a uniform, stable and perfect heat-conducting and oxygen-resisting reinforced network structure, is high in filling density, has good mechanical property, oxidation resistance and aging resistance, has good heat-conducting property, oxygen-resisting effect and compression-resisting effect, and can be widely applied to ground heating pipes and other pipes in the fields of heat conduction, oxygen resistance and hydraulic pressure resistance.
According to a third aspect of the present invention, a method of manufacturing a floor heating pipe is provided. According to an embodiment of the invention, the method mixes the graphene modified composite material with a second polymer matrix and carries out molding treatment so as to obtain the floor heating pipe, wherein the graphene modified composite material is the graphene modified composite material or the graphene modified composite material prepared by the method for preparing the graphene modified composite material. The method is simple in process, low in cost and easy for large-scale batch production, and can enable graphene to be uniformly dispersed in the pipe and serve as a compact nanometer barrier wall to construct a good structural heat conduction, oxygen resistance and reinforcing network, so that the prepared floor heating pipe has the advantages of high heat conduction, high oxygen resistance, high strength and high safety, the heat conductivity coefficient of the prepared floor heating pipe can be up to more than 1.2W/m.K, and the oxygen permeability can be as low as 0.05 g/m.K3D, the pressure of the blasting pressure ring can reach more than 14MPa, and the pipe explosion phenomenon caused by the sudden high and low water pressure is not easy to occur, so that the national standard and the industrial standard of the ground heating pipe can be met even if the prepared ground heating pipe is of a single-layer structure.
In some embodiments of the present invention, the mass ratio of the graphene-modified composite material to the second polymer matrix is (0.5-2): 1.
in some embodiments of the invention, the second polymer matrix is at least one of heat resistant polyethylene and/or polybutylene.
In some embodiments of the invention, the second polymer matrix is the same as the first polymer matrix.
According to a fourth aspect of the present invention, a floor heating pipe is provided. According to an embodiment of the invention, the floor heating pipe is obtained by adopting the method for preparing the floor heating pipe. The floor heating pipe has the advantages of high heat conductivity, high oxygen resistance, high strength and high safety, wherein the heat conductivity coefficient of the floor heating pipe can be as high as 1.2W/m.KThe oxygen permeability can be as low as 0.05g/m3D, the pressure of the blasting pressure ring can reach more than 14MPa, the pipe explosion phenomenon is not easy to occur due to the fact that the water pressure is suddenly high or low, and even if the floor heating pipe is of a single-layer structure, the national standard and the industrial standard of the floor heating pipe can be met.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow chart of a method of preparing a graphene-modified composite material according to one embodiment of the present invention.
Fig. 2 is a flow chart of a method of preparing a graphene-modified composite material according to yet another embodiment of the present invention.
Fig. 3 is a scanning electron microscope image of a ground heating pipe prepared by using the graphene-modified composite material obtained in example 1.
Fig. 4 is a scanning electron microscope image of a ground heating pipe prepared using the graphene-modified composite material obtained in comparative example 1.
Fig. 5 is a scanning electron microscope image of a ground heating pipe prepared using the graphene-modified composite material obtained in comparative example 2.
Fig. 6 is a scanning electron microscope image of a ground heating pipe prepared using the graphene-modified composite material obtained in comparative example 3.
Fig. 7 is a scanning electron microscope image of a ground heating pipe prepared using the graphene-modified composite material obtained in comparative example 4.
Fig. 8 is a scanning electron microscope image of a floor heating pipe prepared using the graphene-modified composite material obtained in comparative example 5.
Fig. 9 is a scanning electron microscope image of a ground heating pipe prepared using the graphene-modified composite material obtained in comparative example 6.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to the invention, the multi-scale design of the filler structure is optimized, the effect of mixing and dispersing graphene in the polymer matrix is improved by adopting a three-step method production process, the filling proportion of graphene in the composite material is improved by organically combining a new material with a new technology and a new method, the composite material (plastic mass or master batch) with a perfect network structure formed by the fillers such as graphene in the polymer matrix is obtained, the heat conduction and oxygen resistance of the composite material can be obviously improved by well building the network, and the application potential of the graphene in the pipes in the fields of heat conduction, oxygen resistance and hydraulic pressure resistance is fully exerted, so that the technical challenge facing the industrialization of the graphene composite material can be solved, and a good foundation is laid for the large-scale application of the graphene material in the ground heating pipes or other pipes.
According to a first aspect of the present invention, a method of preparing a graphene-modified composite material is presented. According to an embodiment of the invention, as shown in fig. 1 or 2, the method comprises: (1) mixing graphene, a filler, a coating agent, a surface treatment agent, a dispersing agent and an antioxidant to obtain a mixed filler; (2) mixing the mixed filler with a first polymer matrix and carrying out first melt blending so as to obtain a composite material precursor; (3) and carrying out second melt blending on the composite material precursor so as to obtain the graphene modified composite material. The method has at least the following advantages: 1. by optimizing the multi-scale design of the filler structure and adopting a three-step production process of premixing graphene and other fillers and then carrying out two-time melt blending, the mixing and dispersing effects of the graphene in a polymer matrix can be obviously improved, the filling proportion of the graphene in the composite material can be improved, so that the uniformity and the stability of the graphene modified composite material can be greatly improved, the advantages of the graphene in the aspects of heat conduction, oxygen resistance and reinforcement can be fully exerted, the graphene modified composite material can be ensured to have better mechanical property, oxidation resistance and aging resistance, the heat conduction property, the oxygen resistance and the compression resistance of the pipe can be obviously improved when the graphene modified composite material is used in the pipe such as a ground heating pipe, and the service life and the safety of the pipe can be improved; 2. the method has simple process and low cost, and can realize large-scale and industrialized production of the graphene modified composite material; 3. the graphene modified composite material prepared by the method has good heat conductivity, oxygen resistance and compression resistance, and can be widely applied to ground heating pipes and other pipes in the fields of heat conductivity, oxygen resistance and hydraulic pressure resistance.
The method for preparing the graphene modified composite material according to the above embodiment of the present invention is described in detail with reference to fig. 1 to 2.
S100, mixing the graphene, the filler, the coating agent, the surface treating agent, the dispersing agent and the antioxidant to obtain a mixed filler
According to the embodiment of the invention, the graphene, the filler, the coating agent, the surface treatment agent, the dispersing agent and the antioxidant are mixed in advance, so that the components are fully mixed, and the coating agent is effectively coated on the surfaces of the graphene, the filler and the like, so that the problems that the graphene is easy to stack and agglomerate and the graphene is difficult to fill in a polymer matrix at high concentration can be overcome to a certain extent, further, the graphene can be fully stripped and uniformly dispersed in the polymer matrix in a subsequent melt blending process, the filling proportion of the graphene in the polymer matrix is remarkably improved, the graphene, the filler and the like can form a uniform, stable and complete heat-conducting and oxygen-blocking reinforced network structure in the polymer matrix, and the advantages of the graphene in the aspects of heat conduction, oxygen blocking and reinforcement can be fully exerted. Further, the temperature of the mixing treatment can be 20-90 ℃, the rotating speed can be 200-1500 rpm, and the time can be 5-30 min.
According to a specific embodiment of the invention, the radial dimension of the graphene can be 0.5-40 μm, and the thickness can be 1-20 nm, so that the graphene can be uniformly dispersed in a polymer matrix, and can be used as a compact nanometer barrier wall to construct a good structural heat conduction, oxygen resistance and reinforcing network, so that the prepared graphene modified composite material has the advantages of high heat conduction, high oxygen resistance and high strength.
According to another embodiment of the present invention, the source of the graphene in the present invention is not particularly limited, and those skilled in the art can select the source according to actual needs, for example, the graphene can be prepared by a mechanical exfoliation method, a biomass catalytic carbonization method, a high temperature activation method, a redox method, or a chemical vapor deposition method; preferably, the graphene can be prepared by adopting a mechanical stripping method, so that the heat conductivity and the oxygen barrier effect of the finally prepared graphene modified composite material can be further improved.
According to still another embodiment of the present invention, the kinds of the filler, the coating agent, the surface treatment agent, the dispersant and the antioxidant in the present invention are not particularly limited and may be selected by those skilled in the art according to actual needs. For example, the filler may be at least one selected from the group consisting of array-type carbon nanotubes, wound-type carbon nanotubes, micro powder graphite, expanded graphite, flake graphite, high purity graphite, and carbon black; the coating agent can be one or more of ethylene-vinyl acetate copolymer (EVA), thermoplastic elastomer (TPE), polyolefin elastomer (POE), styrene thermoplastic elastomer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), polyester elastomer (TPEE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), Ethylene Propylene Diene Monomer (EPDM), Nitrile Butadiene Rubber (NBR) and acrylate rubber (ACM); the surface treatment agent can be selected from one or more of silane coupling agent, organic metal ester coupling agent (titanate coupling agent, aluminate coupling agent or zirconate coupling agent), octadecylamine and isocyanate; the dispersant can be one or more of polyethylene wax, calcium stearate, EVA wax, Ethylene Bis Stearamide (EBS), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) and ethylene-butyl acrylate copolymer (EBA); the antioxidant can be one or more of phosphorus antioxidant, phenol antioxidant, sulfur antioxidant and natural antioxidant. Therefore, the comprehensive performance of the graphene modified composite material can be improved.
According to another embodiment of the present invention, the equipment for performing the mixing process is not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, the mixing process may be performed using a high-speed mixer, a plastic blender, a vertical mixer, a horizontal mixer, or a conical mixer, so as to allow the graphene to be sufficiently mixed with the other components.
S200, mixing the mixed filler with a first polymer matrix, and performing first melt blending to obtain a composite material precursor
According to the embodiment of the invention, the graphene, the coating agent and the filler are premixed and then subjected to first melt blending with the first polymer matrix, so that the graphene and the like can be better dispersed in the polymer matrix, and the problems that the graphene is easy to stack and agglomerate and the graphene is difficult to fill in the polymer matrix at high concentration can be further solved, thereby being further beneficial to forming a uniform, stable and complete heat-conducting oxygen-blocking reinforced network structure in the polymer matrix by the graphene, the filler and the like, and further improving the heat-conducting property, the oxygen-blocking property and the reinforcing property of the finally prepared graphene modified composite material.
According to a specific embodiment of the present invention, the kind of the first polymer matrix in the present invention is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the first polymer matrix can be heat-resistant polyethylene (PE-RT) and/or Polybutylene (PB); for another example, when the graphene modified composite material is used for preparing a floor heating pipe, the first polymer matrix may preferably be heat-resistant polyethylene, so that the finally prepared floor heating pipe has high thermal conductivity, high oxygen resistance, high strength and good mechanical properties.
According to an embodiment of the present invention, the temperature of the first melt blending may be 160 to 250 ℃, for example, 165 ℃, 175 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃, 225 ℃, 235 ℃, 245 ℃ or the like, so that not only can the polymer matrix be uniformly mixed with the mixed filler in a molten state, thereby further improving the dispersion effect of the filler such as graphene in the polymer matrix, but also the polymer matrix can be effectively prevented from being decomposed at an excessively high temperature.
According to another embodiment of the present invention, the mixture ratio of the first polymer matrix, the graphene, the filler, the coating agent, the surface treatment agent, the dispersant and the antioxidant may be as follows: the mass ratio of the first polymer matrix to the graphene to the filler to the coating agent to the surface treatment agent to the dispersant to the antioxidant can be (18-80): (10-40): (5-10): (5-20): (0.1-1): (0.5-10): (0.1 to 3). The inventors found that when the mass concentration of graphene in the composite material is too small, especially less than 10%, the graphene is difficult to form a complete network structure in the polymer matrix, so that the effect of enhancing the heat conduction and oxygen barrier is greatly reduced; when the mass concentration of the graphene in the composite material is too high, particularly more than 40%, the graphene is easy to form more joints with a polymer when dispersed in a polymer matrix, and the joints are easy to break due to tensile deformation of the polymer and no deformation of the graphene when the polymer is stretched at the combined positions, so that the toughness of the composite material is greatly reduced, the material becomes hard and brittle, and the performance of the pipe prepared from the composite material is greatly reduced in the processes of processing, mounting and using; when the components are controlled to be in the proportion, the finally prepared graphene modified composite material has excellent heat conduction, oxygen resistance and reinforcing effects on the basis of ensuring the mechanical property, and particularly, when the graphene modified composite material is used as a master batch or used as an additive to be mixed with a polymer matrix to prepare a pipe, such as a ground heating pipe, the heat conduction coefficient of the pipe can be up to more than 1.2W/m.K, and the oxygen permeability is as low as 0.05g/m3D is less than, the pressure of the blasting pressure ring reaches more than 14MPa, and the heat conductivity, oxygen resistance, oxidation resistance, hydraulic resistance and safety of the pipe are greatly improved. IntoIn one step, based on 100 parts by weight of the graphene modified composite material, the mass ratio of the first polymer matrix, the graphene, the filler, the coating agent, the surface treatment agent, the dispersing agent and the antioxidant can be (18-80): (10-40): (5-10): (5-20): (0.1-1): (0.5-10): (0.1-3), on the basis of ensuring the mechanical property, the finally prepared graphene modified composite material has more excellent heat conduction, oxygen resistance and reinforcing effects, and when the graphene modified composite material is used for preparing pipes such as ground heating pipes, the heat conduction performance, the oxygen resistance and oxidation resistance, the hydraulic resistance and the safety of the pipes can be further improved.
According to another embodiment of the present invention, the form of the composite material precursor is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the composite material precursor may be in a plastic pellet or a masterbatch form, and for example, the mixed filler may be mixed with the first polymer matrix and subjected to first melt blending and extrusion granulation, so as to obtain the composite material precursor masterbatch.
According to still another embodiment of the present invention, the apparatus for performing the first melt blending is not particularly limited and may be selected by those skilled in the art according to actual needs, for example, the first melt blending apparatus may be one or more selected from a twin-screw extruder, a single-screw extruder, a multi-screw extruder, a planetary screw extruder, a reciprocating extruder, a tumble mixer, a drop mixer, a batch mixer, and a continuous mixer.
S300, carrying out second melting blending on the composite material precursor to obtain the graphene modified composite material
According to the embodiment of the invention, the inventor finds that the graphene and other fillers can be fully stripped and uniformly dispersed in the polymer matrix and the high-density filling of the graphene in the composite material can be realized by premixing the graphene, the fillers, the coating agent, the surface treatment agent, the dispersing agent and the antioxidant and then mixing, dispersing and melting and shearing the premixed graphene, the fillers, the antioxidant and the polymer matrix for multiple times, so that the composite material with a uniform, stable and perfect heat-conducting and oxygen-blocking reinforced network structure formed by the graphene, the fillers and the like in the polymer matrix can be obtained; however, as the number of melt blending increases, the mechanical properties, aging resistance and oxidation resistance of the composite material decrease. According to the invention, the mixed filler and the polymer matrix are mixed and then subjected to twice melt blending, so that the uniformity and stability of the graphene modified composite material can be greatly improved, the advantages of graphene in the aspects of heat conduction, oxygen resistance and reinforcement are fully exerted, the graphene modified composite material can be ensured to have better mechanical property, oxidation resistance and aging resistance, and further, when the graphene modified composite material is used as a master batch or a part of the master batch for preparing pipes such as floor heating pipes and the like, the heat conduction property, the oxygen resistance and the compression resistance of the pipes can be obviously improved, and the service life and the safety of the pipes are improved.
According to a specific embodiment of the present invention, the temperature of the second melt blending may be 160 to 250 ℃, for example, 165 ℃, 175 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃, 225 ℃, 235 ℃ or 245 ℃, so that not only can the graphene be more sufficiently peeled and dispersed in the polymer, and a uniform, stable and complete heat-conducting and oxygen-blocking reinforced network structure is formed in the polymer matrix, but also the polymer matrix and the like can be effectively prevented from being decomposed at an excessively high temperature, thereby ensuring that the finally prepared graphene modified composite material has high heat conductivity, high oxygen resistance, high strength and better mechanical properties.
According to another embodiment of the present invention, the form of the finally prepared graphene modified composite material is not particularly limited, and those skilled in the art can select the finally prepared graphene modified composite material according to actual needs, for example, the graphene modified composite material may be in a plastic mass or a masterbatch form, and for example, the composite material precursor may be subjected to second melt blending and extrusion granulation to obtain the graphene modified composite material masterbatch.
According to still another embodiment of the present invention, the apparatus for performing the second melt blending is not particularly limited and may be selected by those skilled in the art according to actual needs, for example, the second melt blending apparatus may be one or more selected from a twin-screw extruder, a single-screw extruder, a multi-screw extruder, a planetary screw extruder, a reciprocating extruder, a tumble mixer, a drop mixer, a batch mixer, and a continuous mixer.
According to a second aspect of the present invention, the present invention provides a graphene-modified composite material. According to the embodiment of the invention, the graphene modified composite material is prepared by adopting the method for preparing the graphene modified composite material. The graphene modified composite material is formed with a uniform, stable and perfect heat-conducting and oxygen-resisting reinforced network structure, is high in filling density, has good mechanical property, oxidation resistance and aging resistance, has good heat-conducting property, oxygen-resisting effect and compression-resisting effect, and can be widely applied to ground heating pipes and other pipes in the fields of heat conduction, oxygen resistance and hydraulic pressure resistance as a master batch or an additive. It should be noted that the features and effects described above for the method for preparing the graphene modified composite material are also applicable to the graphene modified composite material, and are not described in detail here.
According to a third aspect of the present invention, a method of manufacturing a floor heating pipe is provided. According to an embodiment of the invention, the method mixes the graphene modified composite material with the second polymer matrix and carries out molding treatment so as to obtain the floor heating pipe, wherein the graphene modified composite material is the graphene modified composite material or the graphene modified composite material prepared by the method for preparing the graphene modified composite material. The method for preparing the ground heating pipe is simple in process, low in cost and easy to realize large-scale batch production, and can enable graphene to be uniformly dispersed in the pipe and serve as a compact nanometer barrier wall to construct a good structural heat conduction, oxygen resistance and reinforcing network, so that the prepared ground heating pipe has the advantages of high heat conduction, high oxygen resistance, high strength and high safety, wherein the heat conduction coefficient of the prepared ground heating pipe can be up to more than 1.2W/m.K, and the oxygen permeability can be as low as 0.05 g/m.K3D, the pressure of the blasting pressure ring can reach more than 14MPa, and the pipe blasting phenomenon is not easy to occur due to the fact that the water pressure is suddenly high or low, so that the prepared floor heating pipe can be full of even if the prepared floor heating pipe is of a single-layer structureNational standard and industrial standard of foot ground heating pipe.
According to an embodiment of the invention, the mass ratio of the graphene modified composite material to the second polymer matrix may be (0.5-2): 1, the inventors found that if the mass ratio of the graphene-modified composite material to the second polymer matrix is less than 0.5: 1, the heat conduction, oxygen resistance, reinforcement and other properties of the processed and formed pipe are difficult to reach higher levels due to the excessively low graphene content, and if the mass ratio is more than 2: 1, the content of graphene is too high, the processing performance of the pipe is greatly reduced, the pipe extrusion forming effect is poor, and the appearance, the outer diameter, the wall thickness and other dimensions of the pipe are not qualified, wherein the mass ratio is controlled to be (0.5-2): 1, the pipe can be ensured to have the effect of processing and forming, and the pipe can have good heat conduction, oxygen resistance and reinforcement performance, so that the fillers such as graphene can be further dispersed in a polymer matrix, and the requirements of different heat conduction, oxygen resistance and reinforcement performance are further met.
According to another embodiment of the present invention, the kind of the second polymer matrix is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the second polymer matrix can be heat-resistant polyethylene (PE-RT) and/or Polybutylene (PB); further, the second polymer matrix can be preferably made of heat-resistant polyethylene, so that the finally prepared floor heating pipe has the advantages of high heat conductivity, high oxygen resistance, high strength and better mechanical property. Preferably, the second polymer matrix is the same as the first polymer matrix, so that the compatibility of the graphene modified composite material and the second polymer matrix can be further improved, and the finally prepared floor heating pipe has more excellent comprehensive performance.
It should be noted that the features and effects described above for the graphene modified composite material and the method for preparing the graphene modified composite material are also applicable to the method for preparing the floor heating pipe, and are not described in detail here.
According to a fourth aspect of the present invention, a floor heating pipe is provided. According to the embodiment of the invention, the floor heating pipe adopts the above-mentioned systemThe floor heating pipe is obtained by a method for preparing the floor heating pipe. The floor heating pipe has the advantages of high heat conductivity, high oxygen resistance, high strength and high safety, wherein the heat conductivity coefficient of the floor heating pipe can be up to more than 1.2W/m.K, and the oxygen permeability can be as low as 0.05g/m3D, the pressure of the blasting pressure ring can reach more than 14MPa, the pipe explosion phenomenon is not easy to occur due to the fact that the water pressure is suddenly high or low, and even if the floor heating pipe is of a single-layer structure, the national standard and the industrial standard of the floor heating pipe can be met.
According to a specific embodiment of the invention, the floor heating pipe can be of a single-layer structure, compared with the existing multilayer oxygen-blocking floor heating pipe, the single-layer floor heating pipe not only has simple preparation process and low cost, but also has the advantages of high heat conduction, high oxygen resistance, high strength and high safety, and can completely replace the three-layer or five-layer oxygen-blocking structure floor heating pipe.
It should be noted that the features and effects described above for the method for manufacturing the floor heating pipe are also applicable to the floor heating pipe, and are not described in detail herein.
In summary, the technical solution of the present invention has at least the following advantages: (1) the technology of premixing and twice melt blending can realize full stripping and uniform dispersion of graphene in a polymer matrix by a three-step method, so that the graphene modified composite material (master batch) with excellent performance is prepared, and the ground heating pipe with good heat conduction, oxygen resistance and reinforcing performance is further processed. (2) By exerting the advantages of the graphene in the aspects of heat conduction, oxygen resistance and reinforcement, the graphene is further matched with the filler to form a complete network system, and the performance advantage of the composite material is improved more synergistically. (3) Through the use of the coating agent, the graphene and the filler can be fully coated and mixed, the high-concentration filling of the master batch is realized, and the guarantee is provided for the high performance of the final floor heating pipe. (4) Can the heat conduction of full play graphite alkene in polymer base member, hinder oxygen and reinforcing effect, obtain having the ground heating coil of high heat conduction, high oxygen resistance, high resistance to compression concurrently, this ground heating coil security is higher, is difficult for taking place the pipe explosion phenomenon. (5) The processing process has simple route and low cost, and is easy to realize large-scale batch production
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Preparing a graphene modified composite material:
(1) adding 20 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 10 parts by weight of SEBS, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS and 0.5 part by weight of phosphorus antioxidant into a high-speed mixer, mixing at 60 ℃ for 20min, and rotating at 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 59.2 parts by weight of PE-RT resin particles into a turnover internal mixer for first melt blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (2) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
Example 2
Preparing a graphene modified composite material:
(1) adding 40 parts by weight of graphene prepared by a mechanical stripping method, 10 parts by weight of micro-powder graphite, 20 parts by weight of SEBS, 1 part by weight of silane coupling agent KH550, 10 parts by weight of EBS and 0.3 part by weight of phosphorus antioxidant into a high-speed mixer, mixing at 60 ℃ for 20min and at 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 18.7 parts by weight of PE-RT resin particles into a turnover internal mixer for first melt blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (2) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
Example 3
Preparing a graphene modified composite material:
(1) adding 10 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 5 parts by weight of SEBS, 0.1 part by weight of silane coupling agent KH550, 0.5 part by weight of EBS and 0.1 part by weight of phosphorus antioxidant into a high-speed mixer, mixing at 60 ℃ for 20min, and rotating at 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 79.3 parts by weight of PE-RT resin particles into a turnover internal mixer for first melt blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (2) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
Example 4
Preparing a graphene modified composite material:
(1) adding 20 parts by weight of graphene prepared by a high-temperature activation method, 5 parts by weight of wound carbon nano tube, 10 parts by weight of POE, 0.3 part by weight of titanate coupling agent, 5 parts by weight of EVA and 0.5 part by weight of phenol antioxidant into a horizontal mixer, mixing at 30 ℃ for 30min and at 200rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 59.2 parts by weight of PE-RT resin particles into a double-screw extruder for first melt blending, and extruding and granulating at the extrusion temperature of 210 ℃ to obtain initial graphene modified plastic master batches, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic master batch obtained in the step (2) through a double-screw extruder again, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite master batch.
Example 5
Preparing a graphene modified composite material:
(1) adding 20 parts by weight of graphene prepared by a redox method, 5 parts by weight of expanded graphite, 10 parts by weight of TPE, 0.3 part by weight of isocyanate coupling agent, 5 parts by weight of calcium stearate and 0.5 part by weight of sulfur antioxidant into a plastic stirrer, and mixing at 40 ℃ for 30min at the rotating speed of 300rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 59.2 parts by weight of PE-RT resin particles into a reciprocating extruder for first melt blending, and extruding and granulating at the extrusion temperature of 210 ℃ to obtain initial graphene modified plastic master batches, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic master batch obtained in the step (2) through a reciprocating extruder again, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite master batch.
Comparative example 1
And (3) comparison content: without second melt blending
(1) Adding 20 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 10 parts by weight of SEBS, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS and 0.5 part by weight of phosphorus antioxidant into a high-speed mixer, mixing at 60 ℃ for 20min, and rotating at 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 59.2 parts by weight of PE-RT resin particles into a double-screw extruder for first melt blending and granulation, wherein the extrusion temperature is 210 ℃, so as to obtain graphene modified composite material master batches;
comparative example 2
And (3) comparison content: without premixing
(1) Adding 20 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 10 parts by weight of SEBS, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS, 0.5 part by weight of phosphorus antioxidant and 59.2 parts by weight of PE-RT resin particles into a turnover internal mixer for first melting and blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk;
(2) and (2) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (1) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
Comparative example 3
And (3) comparison content: no premixing and second melt blending
Melting, blending, extruding and granulating 20 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 10 parts by weight of SEBS, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS, 0.5 part by weight of phosphorus antioxidant and 59.2 parts by weight of PE-RT resin particles through a double-screw extruder at 210 ℃ to obtain the graphene modified composite master batch.
Comparative example 4
And (3) comparison content: replacing graphene with filler
(1) Adding 25 parts by weight of micro-powder graphite, 10 parts by weight of SEBS, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS and 0.5 part by weight of phosphorus antioxidant into a high-speed mixer, and mixing at 60 ℃ for 20min and 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 59.2 parts by weight of PE-RT resin particles into a turnover internal mixer for first melt blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (2) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
Comparative example 5
And (3) comparison content: without addition of coating agent
(1) Adding 20 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS and 0.5 part by weight of phosphorus antioxidant into a high-speed mixer, mixing at 60 ℃ for 20min and at 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 69.2 parts by weight of PE-RT resin particles into a turnover internal mixer for first melt blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (2) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
Comparative example 6
And (3) comparison content: three times of melt blending
(1) Adding 20 parts by weight of graphene prepared by a mechanical stripping method, 5 parts by weight of micro-powder graphite, 10 parts by weight of SEBS, 0.3 part by weight of silane coupling agent KH550, 5 parts by weight of EBS and 0.5 part by weight of phosphorus antioxidant into a high-speed mixer, mixing at 60 ℃ for 20min, and rotating at 500rpm to obtain a pre-dispersed coated mixed filler;
(2) adding the mixed filler obtained in the step (1) and 59.2 parts by weight of PE-RT resin particles into a turnover internal mixer for first melt blending, and mixing for 20min at 200 ℃ to obtain an initial graphene modified plastic bulk, namely a composite material precursor;
(3) and (3) carrying out second melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (2) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the composite master batch.
(4) And (4) carrying out third melting blending and granulation on the initial graphene modified plastic bulk obtained in the step (3) through a double-screw extruder, wherein the extrusion temperature is 210 ℃, and thus obtaining the graphene modified composite material master batch.
TABLE 1 Mass ratios of the components in the graphene-modified composite materials
The graphene-modified composite materials obtained in examples 1 to 5 and comparative examples 1 to 6 were evaluated for their thermal conductivity, oxygen barrier and reinforcing effects.
The evaluation method comprises the following steps: the graphene modified composite master batches prepared in the examples 1-5 and the comparative examples 1-6 are dried at 80 ℃ for 1-2 hours respectively, then are uniformly mixed with a polymer matrix (PE-RT resin) according to the mass ratio of 1:1 to form a mixed material, and then a floor heating pipe (20mm multiplied by 2.0mm) is extruded. The graphene modified heat-conducting oxygen-resistant reinforced floor heating pipe prepared in the examples and the comparative examples is tested as follows:
(1) coefficient of thermal conductivity: cutting the pipe into pieces, hot-pressing or injection-molding to obtain 10cm × 10cm × 6mm samples, and measuring according to a GB/T10297-2015 hot line method;
(2) oxygen permeability: the oxygen permeability of the thermoplastic plastic pipe is measured according to the ISO 17455 test method;
(3) burst pressure: the method is characterized in that the method is measured according to a GB/T15560 and 1995 method for testing hydraulic instantaneous explosion and pressure resistance of the plastic pipe for fluid transmission;
wherein, the test results of the floor heating pipes prepared in examples 1 to 5 and comparative examples 1 to 6 are shown in table 2, and the scanning electron micrographs of example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 and comparative example 6 observed by a Scanning Electron Microscope (SEM) are shown in fig. 3 to 9.
Example 6
Drying the graphene modified composite material master batch prepared in the embodiment 1 at 80 ℃ for 1-2 hours, and then mixing the graphene modified composite material master batch with a polymer matrix (PE-RT resin) according to a mass ratio of 2: 1, uniformly mixing to form a mixed material, and extruding a floor heating pipe (20mm multiplied by 2.0 mm). The graphene modified heat-conducting oxygen-resistant reinforced floor heating pipe is tested by the same evaluation method as the evaluation method, and the test results are shown in table 2.
Example 7
Drying the graphene modified composite material master batch prepared in the embodiment 1 at 80 ℃ for 1-2 hours, and then mixing the graphene modified composite material master batch with a polymer matrix (PE-RT resin) according to a mass ratio of 0.5: 1, uniformly mixing to form a mixed material, and extruding a floor heating pipe (20mm multiplied by 2.0 mm). The graphene modified heat-conducting oxygen-resistant reinforced floor heating pipe is tested by the same evaluation method as the evaluation method, and the test results are shown in table 2.
Table 2 graphene modified heat-conducting oxygen-resisting ground heating coil each performance test result
Results and conclusions:
(1) by combining the examples 1-5 and tables 1 and 2, it can be known that the higher the graphene content in the graphene modified composite material is, the lower the oxygen permeability of the composite material is, and the higher the thermal conductivity and the burst pressure are; in addition, compared with graphene prepared by a high-temperature activation method and a redox method, when the graphene prepared by a mechanical stripping method is used for preparing the graphene modified composite material, the thermal conductivity coefficient and the bursting pressure of the graphene modified composite material can be further improved, and the oxygen permeability is reduced.
(2) As can be seen from fig. 3, in the floor heating pipe obtained in example 1, the graphene lamellar structure is well dispersed in the polymer matrix, so that a relatively ideal three-dimensional network structure is realized, and the heat conduction, oxygen resistance and enhancement performance of the composite material are improved; as can be seen from fig. 4, the graphene lamellar structure in the floor heating pipe obtained in comparative example 1 is not clearly revealed and is not well dispersed; as can be seen from fig. 5, the graphene lamellar structures in the floor heating pipe obtained in comparative example 2 have different sizes and are not uniformly distributed; as can be seen from fig. 6, in the floor heating pipe obtained in comparative example 3, since the graphene is not completely dispersed, the graphene lamellar structure is not well represented, and may be wrapped by the polymer and other fillers; as can be seen from fig. 7, the floor heating pipe obtained in comparative example 4 did not have a graphene sheet structure, but a bulk structure of graphite; as can be seen from fig. 8, the graphene in the floor heating pipe obtained in comparative example 5 failed to achieve good dispersion; as can be seen from fig. 9, the graphene in the floor heating pipe obtained in comparative example 6 has a certain degree of dispersion effect, and the joint of the graphene and the polymer has a certain degree of extrusion deformation due to multiple melt blending.
As can be seen from fig. 3 to 9, when the ground heating pipe is prepared by using the graphene modified composite master batch prepared by not pre-mixing the fillers and additives such as graphene and the like, not performing the second melt blending, not adding the coating agent, or performing the third melt blending under the same conditions, the graphene cannot be uniformly and stably dispersed in the polymer, or the structural change of the polymer is caused, so that in the processing technology of the composite material, the problems of uniform and stable dispersion of the graphene fillers in the polymer and excessive shearing and mixing of the melt blending are both satisfied, and therefore, the processing technology of pre-mixing and secondary melt blending is suggested to be used for preparing the composite material; as can be seen from table 2, compared with example 1, when the ground heating pipe is prepared by using the graphene modified composite master batch prepared without premixing the fillers and additives such as graphene, performing the second melt blending, adding no coating agent, or performing the third melt blending, the thermal conductivity and the burst pressure of the ground heating pipe are also significantly reduced, the oxygen permeation rate is increased, and the thermal conductivity, the oxygen barrier property and the hydraulic pressure resistance of the ground heating pipe are greatly reduced. Therefore, when the graphene modified composite material obtained by the method for preparing the graphene modified composite material according to the embodiment of the invention is used for preparing the ground heating pipe, the heat conduction performance, the oxygen resistance performance and the hydraulic pressure resistance performance of the ground heating pipe can be remarkably improved.
(3) When the ground heating pipe is prepared, the heat conduction performance, the oxygen resistance performance and the reinforcing performance of the ground heating pipe are improved to a certain extent along with the increase of the using amount of the graphene modified composite material compared with those of the common ground heating pipe, but the heat conduction performance, the oxygen resistance performance and the reinforcing performance of the ground heating pipe are limited within a reasonable range.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a graphene-modified composite material, comprising:
(1) mixing graphene, a filler, a coating agent, a surface treatment agent, a dispersing agent and an antioxidant to obtain a mixed filler;
(2) mixing the mixed filler with a first polymer matrix and carrying out first melt blending so as to obtain a composite material precursor;
(3) and carrying out second melt blending on the composite material precursor so as to obtain the graphene modified composite material.
2. The method according to claim 1, wherein the mass ratio of the first polymer matrix, the graphene, the filler, the coating agent, the surface treatment agent, the dispersant and the antioxidant is (18-80): (10-40): (5-10): (5-20): (0.1-1): (0.5-10): (0.1 to 3).
3. The method according to claim 1, wherein the mass ratio of the first polymer matrix, the graphene, the filler, the coating agent, the surface treatment agent, the dispersant and the antioxidant is (18-80) based on 100 parts by weight of the graphene-modified composite material: (10-40): (5-10): (5-20): (0.1-1): (0.5-10): (0.1 to 3).
4. The method according to any one of claims 1 to 3, wherein in the step (1), the temperature of the mixing treatment is 20 to 90 ℃, the rotating speed is 200 to 1500 rpm, and the time is 5 to 30 min;
optionally, the graphene has a radial size of 0.5-40 μm and a thickness of 1-20 nm;
optionally, the graphene is prepared by a mechanical stripping method, a biomass catalytic carbonization method, a high-temperature activation method, an oxidation-reduction method or a chemical vapor deposition method;
optionally, the filler is at least one selected from the group consisting of array-type carbon nanotubes, wound-type carbon nanotubes, micro powder graphite, expanded graphite, flake graphite, high-purity graphite, and carbon black;
optionally, the coating agent is at least one selected from ethylene-vinyl acetate copolymer, thermoplastic elastomer, polyolefin elastomer, styrene thermoplastic elastomer, styrene-ethylene-butylene-styrene block copolymer, polyester elastomer, linear low density polyethylene, ethylene propylene diene monomer rubber, nitrile rubber and acrylate rubber;
optionally, the surface treatment agent is at least one selected from silane coupling agents, organometallic ester coupling agents, octadecylamine and isocyanates;
optionally, the dispersant is at least one selected from the group consisting of polyethylene wax, calcium stearate, EVA wax, ethylene bis stearamide, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer;
optionally, the antioxidant is at least one selected from the group consisting of a phosphorus antioxidant, a phenolic antioxidant, a sulfur antioxidant, and a natural antioxidant.
5. The method according to claim 4, wherein in the step (2), the temperature of the first melt blending is 160-250 ℃;
optionally, the first polymer matrix is heat resistant polyethylene and/or polybutylene.
6. The method according to claim 1 or 5, wherein in the step (3), the temperature of the second melt blending is 160 to 250 ℃;
optionally, in the step (3), performing second melt blending and extrusion granulation on the composite material precursor so as to obtain the graphene modified composite material.
7. A graphene-modified composite material, characterized by being prepared by the method of any one of claims 1 to 6.
8. A method for preparing a floor heating pipe is characterized in that a graphene modified composite material and a second polymer matrix are mixed and subjected to forming treatment to obtain the floor heating pipe,
the graphene modified composite material is the graphene modified composite material of claim 7 or the graphene modified composite material prepared by the method of any one of claims 1 to 6.
9. The method according to claim 8, wherein the mass ratio of the graphene-modified composite material to the second polymer matrix is (0.5-2): 1;
optionally, the second polymer matrix is heat resistant polyethylene and/or polybutylene;
preferably, the second polymer matrix is the same as the first polymer matrix.
10. A floor heating pipe characterized by being obtained by the production method of claim 9.
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| CN111925594A (en) * | 2020-08-17 | 2020-11-13 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene reinforced polypropylene composite material, preparation method thereof and heat conduction product |
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| CN113061406A (en) * | 2021-05-07 | 2021-07-02 | 哈尔滨凯美斯科技有限公司 | Nano-oriented heat-conducting adhesive film for electronic component packaging and preparation method thereof |
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| CN115044128A (en) * | 2022-05-24 | 2022-09-13 | 国网冀北电力有限公司电力科学研究院 | Heat exchange polyethylene composite material, preparation thereof and heat exchange plastic pipe prepared from same |
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| CN111117041A (en) * | 2020-01-15 | 2020-05-08 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Graphene modified oxygen-resistant polyethylene master batch and preparation method and application thereof |
| CN111925594A (en) * | 2020-08-17 | 2020-11-13 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene reinforced polypropylene composite material, preparation method thereof and heat conduction product |
| CN111995811A (en) * | 2020-08-17 | 2020-11-27 | 新奥石墨烯技术有限公司 | Graphene modified ultra-high molecular weight polyethylene and preparation method thereof |
| CN111995811B (en) * | 2020-08-17 | 2024-02-06 | 新奥集团股份有限公司 | Graphene modified ultra-high molecular weight polyethylene and preparation method thereof |
| CN112143072A (en) * | 2020-09-02 | 2020-12-29 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene/polyethylene heat conduction material, preparation method thereof, pipe using heat conduction material and ground source heat pump |
| CN112143093A (en) * | 2020-09-27 | 2020-12-29 | 新奥石墨烯技术有限公司 | Graphene reinforced polypropylene composite material and preparation method and application thereof |
| CN113292773A (en) * | 2021-04-22 | 2021-08-24 | 安徽杰蓝特新材料有限公司 | Graphene modified efficient heat-conducting heat source floor heating pipe fitting and preparation method thereof |
| CN113248825A (en) * | 2021-04-27 | 2021-08-13 | 安徽杰蓝特新材料有限公司 | Graphene modified efficient heat-conducting heat source floor heating pipe and preparation method thereof |
| CN113248825B (en) * | 2021-04-27 | 2022-04-12 | 安徽杰蓝特新材料有限公司 | Preparation method of graphene modified efficient heat-conducting heat source floor heating pipe |
| CN113061406A (en) * | 2021-05-07 | 2021-07-02 | 哈尔滨凯美斯科技有限公司 | Nano-oriented heat-conducting adhesive film for electronic component packaging and preparation method thereof |
| CN115044128A (en) * | 2022-05-24 | 2022-09-13 | 国网冀北电力有限公司电力科学研究院 | Heat exchange polyethylene composite material, preparation thereof and heat exchange plastic pipe prepared from same |
| CN115232443A (en) * | 2022-08-17 | 2022-10-25 | 安徽宇航派蒙健康科技股份有限公司 | Method for preparing heat-conducting composite material from graphene and polymer |
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