CN112812400A - Composite polyethylene material and preparation method and application thereof - Google Patents
Composite polyethylene material and preparation method and application thereof Download PDFInfo
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- CN112812400A CN112812400A CN202011623027.8A CN202011623027A CN112812400A CN 112812400 A CN112812400 A CN 112812400A CN 202011623027 A CN202011623027 A CN 202011623027A CN 112812400 A CN112812400 A CN 112812400A
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 186
- -1 polyethylene Polymers 0.000 title claims abstract description 186
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 186
- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002245 particle Substances 0.000 claims abstract description 57
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 49
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000002480 mineral oil Substances 0.000 claims abstract description 20
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 229920001903 high density polyethylene Polymers 0.000 claims description 38
- 239000004700 high-density polyethylene Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 15
- 238000011049 filling Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 238000004513 sizing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000004378 air conditioning Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000007909 melt granulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K7/00—Use of ingredients characterised by shape
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a composite polyethylene material and a preparation method and application thereof. The composite polyethylene material takes polyethylene powder, polyethylene particles, flaky graphite, graphene oxide, a dispersing agent, mineral oil, a coupling agent and an antioxidant as raw materials, and functional groups on the surface of the graphene oxide can be well compatible with other raw materials of the polyethylene heat-conducting master batch, so that the dispersibility of the heat-conducting filler in a polyethylene matrix is improved, the graphene oxide is embedded into a heat-conducting network formed by the polyethylene matrix and the flaky graphite, good heat-conducting property can be obtained under a low filling amount, the production cost is low, and the composite polyethylene material is particularly suitable for a ground source heat pump system. The polyethylene heat-conducting master batch is prepared by two-step mixing, so that the polyethylene powder, the flaky graphite, the graphene oxide and other fillers and other raw materials can be uniformly mixed, the material dispersibility is good, the raw material caking is prevented, the inner surface and the outer surface of the prepared composite polyethylene pipe are smooth, and the long-term hydraulic resistance is good.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a composite polyethylene material and a preparation method and application thereof.
Background
The ground source heat pump system is an energy exchange system for providing heating, air conditioning and hot water for a building space by utilizing a large amount of low-temperature heat source energy stored in shallow underground (about tens of meters to one hundred meters deep) soil, rock, underground water or other media, utilizes the relatively stable shallow underground temperature and huge energy storage, and is the most comfortable, efficient and environment-friendly technology so far. The operation efficiency of the ground source heat pump system is about 30-40% higher than that of the traditional air conditioning system; the operating cost of the whole year is reduced by 30 to 60 percent compared with a heat network central heating system or a fuel gas heating system. The ground source heat pump system can be applied to the fields of central air conditioning systems, floor heating, hot water supply and the like in projects such as office buildings, villas, school schools, hotels, hospitals, factory buildings, houses, shopping malls, expressway service areas and the like, wherein the ground source heat pump system is most commonly applied to the central air conditioning systems.
The polyethylene pipe is an important component of a ground source heat pump system, mainly bears a heat exchange task, has the characteristics of reliable connection, aging resistance, good wear resistance and good chemical corrosion resistance, and particularly needs to have high heat conduction performance. However, the common polyethylene pipe material has low heat conductivity coefficient and poor heat conductivity efficiency, and can not meet the use requirements of a ground source heat pump system; the heat conductivity of the polyethylene pipe of the ground source heat pump is improved, the heat conduction and the utilization rate can be improved, the system performance of the ground source heat pump is improved, and the cooling and heating requirements of a building are met.
Most ground source heat pump pipes in the market are polyethylene-carbon black system extrusion pipes, the heat conduction capacity is poor, and high-utilization-rate heat energy cannot be obtained. The polyethylene extrusion pipe filled with graphite has better heat-conducting property, however, the graphite filling amount required to be filled is large, the creep resistance of the polyethylene pipe can be greatly reduced by filling the high-component heat-conducting inorganic substance, and the hidden danger of pipe explosion exists in the use process. Although the polyethylene-graphene system extruded pipe has good heat-conducting property, the cost of graphene as a heat-conducting filler is too high, so that the polyethylene-graphene system extruded pipe cannot be widely applied to a ground source heat pump system.
Disclosure of Invention
Therefore, there is a need for a composite polyethylene material with good thermal conductivity and low cost, and a preparation method and applications thereof.
The invention provides a composite polyethylene material, which comprises the following preparation raw materials in parts by weight:
25-40 parts of polyethylene heat-conducting master batch; and
60-75 parts of polyethylene particles;
the polyethylene heat-conducting master batch comprises the following raw materials in parts by weight:
in some of these embodiments, the exfoliated graphite has a layer thickness of 5 to 10 layers and a radial dimension of 4 to 10 μm.
In some of these embodiments, the graphene oxide has a layer thickness of 4 to 10 layers and a radial dimension of 3 to 10 μm.
In some of these embodiments, the polyethylene powder is a high density polyethylene powder; the polyethylene particles are high density polyethylene particles.
In some of these embodiments, the dispersant is selected from at least one of maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, and glycidyl methacrylate grafted polyethylene.
In some of these embodiments, the coupling agent is selected from at least one of titanate-based coupling agents, silane coupling agents, and aluminate coupling agents.
In some of these embodiments, the antioxidant is selected from at least one of hindered phenolic antioxidants, thioester antioxidants, and phosphite antioxidants.
In some embodiments, the polyethylene heat-conducting master batch is 32 to 38 parts by weight, and the polyethylene particles are 62 to 68 parts by weight; and/or
In the polyethylene heat-conducting master batch, by weight, 30-40 parts of polyethylene powder, 20-35 parts of polyethylene particles, 70-75 parts of flaky graphite, 8-10 parts of graphene oxide, 0.8-1.0 part of dispersing agent, 0.75-1.0 part of mineral oil, 0.1-0.3 part of coupling agent and 0.2-0.5 part of antioxidant are added.
The invention also provides a preparation method of the composite polyethylene material, which comprises the following steps:
providing a raw material for preparing the composite polyethylene material;
premixing the polyethylene powder, the dispersant and the mineral oil to obtain a premix;
mixing the pre-mixture with the flake graphite, the graphene oxide, the coupling agent and the antioxidant to obtain a mixture;
melting and granulating the mixture and the polyethylene particles to obtain polyethylene heat-conducting master batches;
and blending the polyethylene heat-conducting master batch and the polyethylene particles, and extruding and molding.
In some of the embodiments, in the step of premixing the polyethylene powder, the dispersant and the mineral oil, the mixing time is 3min to 8min, and the mixing temperature is 50 ℃ to 70 ℃.
In some of the embodiments, in the step of mixing the pre-mixture with the flake graphite, the graphene oxide, the coupling agent, and the antioxidant, the mixing time is 10min to 20min, and the mixing temperature is 70 ℃ to 90 ℃.
In some embodiments, in the steps of melting and granulating the mixture and the polyethylene particles, and blending the polyethylene heat-conducting master batch and the polyethylene particles, and performing extrusion molding, the rotation speed of the granulation and the extrusion molding is 150 rpm-400 rpm, and the melting temperature is 160 ℃ to 220 ℃.
The invention also provides the application of the composite polyethylene material or the composite polyethylene material obtained by the preparation method of the composite polyethylene material in preparing pipes.
The invention also provides a composite polyethylene pipe which is made of the composite polyethylene material or the composite polyethylene material obtained by the preparation method of the composite polyethylene material.
The preparation raw materials of the composite polyethylene material comprise polyethylene particles and polyethylene heat-conducting master batches with specific content, the polyethylene heat-conducting master batches take the flaky graphite and the graphene oxide as heat-conducting fillers, and functional groups on the surface of the graphene oxide can be well compatible with other raw materials of the polyethylene heat-conducting master batches, so that the dispersity of the heat-conducting fillers in a polyethylene matrix is improved, the graphene oxide is embedded into a heat-conducting network formed by the polyethylene matrix and the flaky graphite, and good heat-conducting performance can be obtained under the lower filling amount of the heat-conducting fillers, and the pressure-resistant performance of the composite polyethylene material cannot be reduced due to the overhigh filling amount of the heat-conducting fillers. And the production cost of the oxidized graphene and the flaky graphite is relatively low, and the method is particularly suitable for a ground source heat pump system.
The preparation method of the composite polyethylene material comprises the steps of premixing polyethylene powder with a dispersing agent and mineral oil, mixing the premixed polyethylene powder with raw materials such as flake graphite and graphene oxide, carrying out melt granulation on the mixture and polyethylene particles to obtain polyethylene heat-conducting master batches, and then melting and extruding the polyethylene heat-conducting master batches and the polyethylene particles to obtain the composite polyethylene pipe. The polyethylene heat-conducting master batch is prepared by two-step mixing, and the polyethylene powder, the flaky graphite, the graphene oxide and other fillers are uniformly mixed, so that the dispersibility of the material is further improved. The composite polyethylene pipe prepared from the composite polyethylene material has smooth inner and outer surfaces and good long-term hydraulic resistance, and is free of pipe explosion hidden danger when being applied to a ground source heat pump system for a long time.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a composite polyethylene material, which comprises the following preparation raw materials in parts by weight:
25-40 parts of polyethylene heat-conducting master batch; and
60-75 parts of polyethylene particles;
the polyethylene heat-conducting master batch comprises the following raw materials in parts by weight:
the raw materials of the composite polyethylene material comprise polyethylene particles and polyethylene heat-conducting master batch with specific content, and the heat-conducting filler of the polyethylene heat-conducting master batch is flaky graphite and graphene oxide. The flaky graphite has good performances of high temperature resistance, electric conduction, heat conduction, lubrication and the like. The graphene oxide has a large number of functional groups on the surface, such as carboxyl, hydroxyl, epoxy and the like, so that intermolecular interaction with other raw materials is easy to generate, and dispersion is easy. The scaly graphite forms a heat conduction network in the resin matrix, the high-heat-conductivity graphene oxide is embedded into the heat conduction network to further improve the heat conductivity of the pipe, the heat conductivity coefficient of the pipe can be greatly improved under the condition of small filling amount of the heat conduction filler, the production cost is low, and the method is particularly suitable for a ground source heat pump system.
In some embodiments, the graphene oxide is prepared by a Brodie method, a Staudenmaier method or a Hummers method, and the preparation process is simple and low in cost.
In some of these embodiments, the graphene oxide has a layer thickness of 4 to 10 layers and a radial dimension of 3 to 10 μm.
In some of these embodiments, the exfoliated graphite has a layer thickness of 5 to 10 layers and a radial dimension of 4 to 10 μm.
In some of these embodiments, the polyethylene powder is a High Density Polyethylene (HDPE) powder; the polyethylene particles are High Density Polyethylene (HDPE) particles. Specifically, the High Density Polyethylene (HDPE) powder and the High Density Polyethylene (HDPE) particles are PE100 grade or PE80 grade.
In particular, High Density Polyethylene (HDPE) has good heat resistance and cold resistance, good chemical stability, and also has high rigidity and toughness. The PE100 grade and the PE80 grade are grades according to the Minimum Required Strength (MRS) of polyethylene. MRS of PE80 reaches 8MPa, and MRS of PE100 reaches 10 MPa.
In some of these embodiments, the dispersant is selected from at least one of maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, and glycidyl methacrylate grafted polyethylene. The dispersing agent has good compatibility with a polyethylene matrix, and the grafting functional group can generate intermolecular force with graphene oxide, so that the flaky graphite and the graphene oxide can be uniformly dispersed in the polyethylene matrix, and the condition that heat-conducting fillers are accumulated to generate a bridge and influence the heat-conducting property of the pipe is avoided.
In some of these embodiments, the coupling agent is selected from at least one of titanate-based coupling agents, silane coupling agents, and aluminate coupling agents.
In some of these embodiments, the antioxidant is selected from at least one of hindered phenolic antioxidants, thioester antioxidants, and phosphite antioxidants.
In some embodiments, the weight parts of the polyethylene heat-conducting master batch are 32-38 parts, and the weight parts of the polyethylene particles are 62-68 parts; and/or
In the polyethylene heat-conducting master batch, by weight, 30 to 40 parts of polyethylene powder, 20 to 35 parts of polyethylene particles, 70 to 75 parts of flaky graphite, 8 to 10 parts of graphene oxide, 0.8 to 1.0 part of dispersing agent, 0.75 to 1.0 part of mineral oil, 0.1 to 0.3 part of coupling agent and 0.2 to 0.5 part of antioxidant are added.
The invention also provides a preparation method of the composite polyethylene material, which comprises the following steps of S1-S5.
Step S1: taking the raw materials of the composite polyethylene material for later use.
Step S2: premixing polyethylene powder, a dispersing agent and mineral oil to obtain a premix.
Step S3: and mixing the premix with the flaky graphite, the graphene oxide, the coupling agent and the antioxidant to obtain a mixture.
Step S4: and melting and granulating the mixture and polyethylene particles to obtain the polyethylene heat-conducting master batch.
Step S5: and (3) blending the polyethylene heat-conducting master batch and the polyethylene particles, and extruding and molding.
The preparation method of the composite polyethylene material comprises the steps of preparing the polyethylene heat-conducting master batch by two-step mixing, mixing the polyethylene powder with the dispersing agent and the mineral oil at first, and wrapping the dispersing agent and the mineral oil around the polyethylene powder, so that the subsequent uniform mixing of the polyethylene powder, fillers such as flake graphite, graphene oxide and the like and other raw materials is facilitated, the material dispersibility is good, and the raw materials are prevented from caking. Meanwhile, the scaly graphite and the graphene oxide are used as heat-conducting fillers, so that good heat-conducting property can be obtained under a low filling amount, the production cost is low, and the prepared composite polyethylene material is smooth in surface and good in hydraulic resistance, and is particularly suitable for being applied to a ground source heat pump system.
In some embodiments, in step S2, the mixing time is 3min to 8min, and the mixing temperature is 50 ℃ to 70 ℃.
In some embodiments, in step S3, the mixing time is 10min to 20min, and the mixing temperature is 70 ℃ to 90 DEG C
In some embodiments, in steps S4 and S5, the rotation speed of the granulation and extrusion molding is 150rpm to 400rpm, and the melting temperature is 160 ℃ to 220 ℃.
In some of these embodiments, step S1 is performed in a high speed mixer.
In some of these embodiments, the polyethylene thermally conductive masterbatch is prepared using a twin screw extruder. Specifically, polyethylene particles are fed into a main feeder and subjected to melt extrusion, the mixture is added into a double-screw extruder through a side feeder, and the polyethylene heat-conducting master batch is obtained through melting, shearing, blending, granulating and molding.
In some of these embodiments, step S4 is performed in a pipe extruder to produce a composite polyethylene pipe. Specifically, the polyethylene heat-conducting master batch and polyethylene particles are blended, melted and blended through a pipe extruder, a melt is extruded, and the composite polyethylene pipe is obtained after sizing.
The invention also provides the application of the composite polyethylene material or the composite polyethylene material obtained by the preparation method of the composite polyethylene material in preparing pipes.
The invention also provides a composite polyethylene pipe which is made of the composite polyethylene material or the composite polyethylene material obtained by the preparation method of the composite polyethylene material.
The composite polyethylene pipe has the heat conductivity coefficient of more than 0.6W/(m.K), is low in production cost and is particularly suitable for ground source heat pump systems.
In some embodiments, the composite polyethylene pipe is a ground source heat pump pipe.
The following are specific examples.
Example 1:
the ground source heat pump pipe is prepared as follows:
polyethylene heat conduction master batch, by weight fraction includes: 20 parts of high-density polyethylene powder, 20 parts of high-density polyethylene particles, 60 parts of flaky graphite, 8 parts of graphene oxide, 0.5 part of maleic anhydride grafted polyethylene, 0.5 part of mineral oil, 0.2 part of titanate coupling agent and 0.3 part of hindered phenol antioxidant; the molecular weight of the high-density polyethylene particles is more than or equal to 3 multiplied by 105Density greater than 0.935g/cm3(ii) a The thickness of the flaky graphite layer is 6 layers, and the particle size is 8 mu m; the graphene oxide layer is 4 layers thick and has a particle size of 6 μm.
Adding polyethylene powder, maleic anhydride grafted polyethylene and mineral oil into a high-speed mixer in proportion, and stirring for 5min at the temperature of 60 +/-5 ℃; then adding the flaky graphite, the graphene oxide, the titanate coupling agent and the hindered phenol antioxidant in proportion, and continuously stirring at a high speed for 12min at a temperature of 75 +/-5 ℃ to obtain the mixed material. The extrusion granulator adopts a double-screw extruder, the rotating speed of the screw is 270 +/-30 rpm, the granular high-density polyethylene is fed through the main feeder, the mixed materials are fed through the auxiliary feeder, and the melting temperature from a feed opening to a machine head is between 160 and 190 ℃. And extruding the materials into molten strips through a filter screen and a port die under the shearing and blending action of a charging barrel and a screw, and cooling, drawing, cutting and screening by a vibrating screen to obtain the polyethylene heat-conducting master batch.
The ground source heat pump pipe comprises the following components in parts by weight: 71 parts of high-density polyethylene particles and 29 parts of polyethylene heat-conducting master batch. Adding the high-density polyethylene particles and the polyethylene heat-conducting master batch into a high-speed mixer, stirring for 15min to obtain a uniform mixture, conveying the mixture to a single-screw extruder through a feeding pipe, and distributing the melting temperature from the feeding section of the extruder to a mold between 160 ℃ and 200 ℃. And (3) carrying out vacuum cooling and sizing on the melted mixed blank of the extrusion die through a sizing sleeve, and then carrying out coil pipe after passing through a diameter measuring instrument, a laser identifier and a tractor.
Example 2:
the ground source heat pump pipe is prepared as follows:
polyethylene heat conduction master batch, by weight fraction includes: 30 parts of high-density polyethylene powder, 20 parts of high-density polyethylene particles, 70 parts of flaky graphite, 9 parts of graphene oxide,1.0 part of maleic anhydride grafted polyethylene, 1.0 part of mineral oil, 0.3 part of titanate coupling agent and 0.5 part of hindered phenol antioxidant; the molecular weight of the high-density polyethylene particles is more than or equal to 3 multiplied by 105Density greater than 0.935g/cm3(ii) a The thickness of the flaky graphite layer is 8 layers, and the particle size is 9 mu m; the graphene oxide layer is 5 layers thick and has a particle size of 8 μm.
Adding polyethylene powder, maleic anhydride grafted polyethylene and mineral oil into a high-speed mixer in proportion, and stirring for 7min at the temperature of 60 +/-5 ℃; then adding the flaky graphite, the graphene oxide, the titanate coupling agent and the hindered phenol antioxidant in proportion, and continuously stirring at a high speed for 15min at the temperature of 78 +/-5 ℃ to obtain the mixed material. The extrusion granulator adopts a double-screw extruder, the granular high-density polyethylene is fed through a main feeder, the mixed materials are fed through an auxiliary feeder, and the melting temperature from a feed opening to a machine head is between 160 and 200 ℃. And extruding the materials into molten strips through a filter screen and a mouth die under the shearing and blending action of a charging barrel and a screw, and cooling, drawing and cutting and screening by a vibrating screen to obtain the polyethylene heat-conducting master batch.
The ground source heat pump pipe comprises the following components in parts by weight: 68 parts of high-density polyethylene particles and 32 parts of polyethylene heat-conducting master batch. Adding the high-density polyethylene particles and the polyethylene heat-conducting master batch into a high-speed mixer, stirring for 17min to obtain a uniform mixture, conveying the mixture to a single-screw extruder through a feeding pipe, and distributing the melting temperature from the feeding section of the extruder to a mold between 160 ℃ and 200 ℃. And (3) carrying out vacuum cooling and sizing on the melted mixed blank of the extrusion die through a sizing sleeve, and then carrying out coil pipe after passing through a diameter measuring instrument, a laser identifier and a tractor.
Example 3:
the ground source heat pump pipe is prepared as follows:
polyethylene heat conduction master batch, by weight fraction includes: 40 parts of high-density polyethylene powder, 35 parts of high-density polyethylene particles, 75 parts of flaky graphite, 10 parts of graphene oxide, 0.8 part of maleic anhydride grafted polyethylene, 0.75 part of mineral oil, 0.3 part of titanate coupling agent and 0.3 part of hindered phenol antioxidant; the molecular weight of the high density polyethylene particles is more than or equal to 3 multiplied by 105Density greater than 0.935g/cm3(ii) a Flake graphite layer5 layers thick, particle size 7 μm; the graphene oxide layer is 6 layers thick and has a particle size of 8 μm.
Adding polyethylene powder, maleic anhydride grafted polyethylene and mineral oil into a high-speed mixer in proportion, and stirring for 8min at the temperature of 65 +/-5 ℃; then adding the flaky graphite, the graphene oxide, the titanate coupling agent and the hindered phenol antioxidant in proportion, and continuously stirring at a high speed for 20min at a temperature of 80 +/-5 ℃ to obtain the mixed material. The extrusion granulator adopts a double-screw extruder, the granular high-density polyethylene is fed through a main feeder, the mixed materials are fed through an auxiliary feeder, and the melting temperature from a feed opening to a machine head is between 160 and 210 ℃. And extruding the materials into molten strips through a filter screen and a mouth die under the shearing and blending action of a charging barrel and a screw, and cooling, drawing and cutting and screening by a vibrating screen to obtain the polyethylene heat-conducting master batch.
The ground source heat pump pipe comprises the following components in parts by weight: 62 parts of high-density polyethylene particles and 38 parts of polyethylene heat-conducting master batch. Adding the high-density polyethylene particles and the polyethylene heat-conducting master batch into a high-speed mixer, stirring for 15min to obtain a uniform mixture, conveying the mixture to a single-screw extruder through a feeding pipe, and distributing the melting temperature from the feeding section of the extruder to a mold between 160 ℃ and 200 ℃. And (3) carrying out vacuum cooling and sizing on the melted mixed blank of the extrusion die through a sizing sleeve, and then carrying out coil pipe after passing through a diameter measuring instrument, a laser identifier and a tractor.
Example 4:
the ground source heat pump pipe is prepared as follows:
the raw materials of the polyethylene heat-conducting master batch are the same as those in example 1.
Adding the granular high-density polyethylene, the powdery polyethylene, the flaky graphite, the graphene oxide, the maleic anhydride grafted polyethylene, the titanate coupling agent and the hindered phenol antioxidant mineral oil into a high-speed mixer in proportion, and stirring at a high speed for 10min to obtain a mixed ingredient. The extrusion granulator adopts a double-screw extruder, the mixed materials are fed through a main feeder, and the melting temperature from a feed opening to a machine head is between 160 and 190 ℃. And extruding the materials through a filter screen and a mouth die to obtain molten material strips under the shearing and blending action of a material cylinder and a screw, and cooling, drawing, cutting and screening by a vibrating screen to obtain the high-thermal-conductivity polyethylene-based master batch.
The raw materials and preparation method of the ground source heat pump pipe are the same as those of example 1.
Comparative example 1:
the ground source heat pump pipe is prepared as follows:
the raw materials and preparation method of the polyethylene heat-conducting master batch are the same as those of example 2.
The ground source heat pump pipe comprises the following components in parts by weight: 70 parts of high-density polyethylene particles and 15 parts of polyethylene heat-conducting master batch. Adding the high-density polyethylene particles and the polyethylene heat-conducting master batch into a high-speed mixer, stirring for 17min to obtain a uniform mixture, conveying the mixture to a single-screw extruder through a feeding pipe, and distributing the melting temperature from the feeding section of the extruder to a mold between 160 ℃ and 200 ℃. And (3) carrying out vacuum cooling and sizing on the melted mixed blank of the extrusion die through a sizing sleeve, and then carrying out coil pipe after passing through a diameter measuring instrument, a laser identifier and a tractor.
Comparative example 2:
the ground source heat pump pipe is prepared as follows:
polyethylene heat conduction master batch, by weight fraction includes: 10 parts of high-density polyethylene powder, 10 parts of high-density polyethylene particles, 80 parts of flaky graphite, 10 parts of graphene oxide, 0.5 part of maleic anhydride grafted polyethylene, 0.5 part of mineral oil, 0.2 part of titanate coupling agent and 0.3 part of hindered phenol antioxidant; the molecular weight of the high-density polyethylene particles is more than or equal to 3 multiplied by 105Density greater than 0.935g/cm3(ii) a The thickness of the flaky graphite layer is 6 layers, and the particle size is 8 mu m; the graphene oxide layer is 4 layers thick and has a particle size of 6 μm.
The preparation method of the polyethylene heat-conducting master batch is the same as that of the example 1.
The raw materials and preparation method of the ground source heat pump pipe are the same as those of example 1.
The performance test results of the ground source heat pump pipes prepared in examples 1 to 4 and comparative examples 1 to 2 are shown in table 1.
TABLE 1
As can be seen from the data in table 1, in the embodiments 1 to 3, the polyethylene heat-conducting master batch is prepared by mixing the flaky graphite and the graphene oxide as the heat-conducting filler of the pipe material in two steps, the finally prepared ground source heat pump pipe has a smooth inner and outer wall surface, does not crack or leak under long-term hydraulic pressure, has an oxidation induction time of 35-43 min, a fracture elongation of 386-446%, and has good creep resistance; the thermal conductivity is more than 0.6W/(m.K), and the thermal conductivity is good.
Compared with the example 1, the ground source heat pump pipe in the example 4 has no two-step mixing in the preparation of the polyethylene heat-conducting master batch, all the raw materials are mixed and granulated in one step according to a proportion, the finally prepared ground source heat pump pipe has a heat conduction coefficient equivalent to that of the pipe material which cannot be broken under long-term hydraulic pressure, but the inner and outer walls of the pipe material are slightly rough, the pipe material has leakage condition under long-term hydraulic pressure, the fracture elongation is lower than that of the ground source heat pump pipe in the example 1, and the creep resistance is poor, which is mainly caused by poor dispersibility of the raw materials in the pipe material preparation.
Compared with the example 2, in the ground source heat pump pipe in the comparative example 1, the content of the polyethylene heat-conducting master batch is low, and the heat conductivity coefficient of the pipe material is obviously lower than that of the ground source heat pump pipe in the example 2, so that the industrial standard requirement of the ground source heat pump pipe cannot be met.
Compared with the example 1, the ground source heat pump pipe of the comparative example 2 has the advantages that the heat conductivity coefficient of the pipe is obviously increased to 0.736W/(m.K) due to the higher adding amount of the heat-conducting filler, namely the flaky graphite, but the inner wall surface and the outer wall surface of the pipe are slightly rough, the pipe is broken under long-term hydraulic pressure, the fracture elongation is obviously lower than that of the example 1, and the creep resistance of the pipe is reduced mainly due to the high adding amount of the flaky graphite and the poor dispersibility.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. The composite polyethylene material is characterized by comprising the following preparation raw materials in parts by weight:
25-40 parts of polyethylene heat-conducting master batch; and
60-75 parts of polyethylene particles;
the polyethylene heat-conducting master batch comprises the following raw materials in parts by weight:
2. the polyethylene composite material according to claim 1, wherein the flake graphite has a layer thickness of 5 to 10 layers and a radial dimension of 4 to 10 μm.
3. The composite polyethylene material according to claim 1, wherein the graphene oxide has a layer thickness of 4 to 10 layers and a radial dimension of 3 to 10 μm.
4. The composite polyethylene material according to claim 1, wherein the polyethylene powder is a high density polyethylene powder; the polyethylene particles are high density polyethylene particles.
5. The composite polyethylene material according to claim 1, wherein the dispersant is at least one selected from the group consisting of maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, and glycidyl methacrylate grafted polyethylene.
6. The composite polyethylene material according to claim 1, wherein the coupling agent is at least one selected from the group consisting of titanate-based coupling agents, silane-based coupling agents, and aluminate-based coupling agents.
7. The composite polyethylene material according to claim 1, wherein the antioxidant is at least one selected from hindered phenol antioxidants, thioester antioxidants and phosphite antioxidants.
8. The composite polyethylene material according to any one of claims 1 to 7, wherein the polyethylene heat-conducting masterbatch is 32 to 38 parts by weight, and the polyethylene particles are 62 to 68 parts by weight; and/or
In the polyethylene heat-conducting master batch, by weight, 30-40 parts of polyethylene powder, 20-35 parts of polyethylene particles, 70-75 parts of flaky graphite, 8-10 parts of graphene oxide, 0.8-1.0 part of dispersing agent, 0.75-1.0 part of mineral oil, 0.1-0.3 part of coupling agent and 0.2-0.5 part of antioxidant are added.
9. The preparation method of the composite polyethylene material is characterized by comprising the following steps:
providing a preparation raw material of the composite polyethylene material according to any one of claims 1 to 8;
premixing the polyethylene powder, the dispersant and the mineral oil to obtain a premix;
mixing the pre-mixture with the flake graphite, the graphene oxide, the coupling agent and the antioxidant to obtain a mixture;
melting and granulating the mixture and the polyethylene particles to obtain polyethylene heat-conducting master batches;
and blending the polyethylene heat-conducting master batch and the polyethylene particles, and extruding and molding.
10. The method for preparing a composite polyethylene material according to claim 9, wherein the step of premixing the polyethylene powder, the dispersant and the mineral oil is performed at a mixing temperature of 50 ℃ to 70 ℃ for 3min to 8 min.
11. The method for preparing a composite polyethylene material according to claim 9, wherein in the step of mixing the pre-mixture with the flake graphite, the graphene oxide, the coupling agent and the antioxidant, the mixing time is 10 to 20min, and the mixing temperature is 70 to 90 ℃.
12. The method for preparing the composite polyethylene material according to claim 9, wherein the mixture is melted and granulated with polyethylene particles, and the polyethylene heat-conducting master batch and the polyethylene particles are blended, and in the step of extrusion molding, the rotation speed of the granulation and the extrusion molding is 150rpm to 400rpm, and the melting temperature is 160 ℃ to 220 ℃.
13. Use of a composite polyethylene material according to any one of claims 1 to 8 or obtained according to the process for the preparation of a composite polyethylene material according to any one of claims 9 to 12 for the preparation of pipes.
14. A composite polyethylene pipe material, characterized in that the material is the composite polyethylene material according to any one of claims 1 to 8 or the composite polyethylene material obtained by the method for preparing the composite polyethylene material according to any one of claims 9 to 12.
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| CN108285576A (en) * | 2018-01-05 | 2018-07-17 | 北京大学 | Crystalline flake graphite-graphene heat-conductive composite material and preparation method thereof and system, radiator |
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