A high-filled polymer composite material of waste printed circuit board non-metal powder with phase change characteristics and its preparation method

Abstract

The present invention discloses a high-filled non-metallic powder polymer composite material with phase change characteristics and a preparation method thereof. The method includes mixing NPCB, a polymer, its processing aids, and a phase change material by open milling, placing the blend in a mold, and then obtaining the composite material through hot pressing, curing. The composite material prepared by the present invention realizes high doping of NPCB, provides a method for large-scale recycling of NPCB, and the composite material has good bending performance and thermal stability, and some of them also have phase change characteristics.

Description

Technical Field

[0001] The present invention belongs to the technical field of recycling of non-metal powder from waste printed circuit boards, and particularly relates to a high-filled polymer composite material of non-metal powder from waste printed circuit boards (NPCB) with phase change characteristics and a preparation method thereof. Background Art

[0002] A printed circuit board, also known as a printed wiring board, is made by electronic printing technology. It is the core component of electronic products, the support for electronic components, and the carrier for electrical connection of electronic components. As an indispensable component of electronic terminal devices, the development level of the printed circuit board industry to a certain extent reflects the speed and technical level of the development of the national or regional electronic information industry. Therefore, as the replacement speed of electronic products increases, a large number of electronic wastes such as waste printed circuit boards, waste parts, and waste electronic components have not been scientifically and reasonably treated, but are piled up in large quantities, and then incinerated and landfilled, resulting in soil pollution, water pollution, air pollution, and even affecting human health.

[0003] Among electronic wastes, waste printed circuit boards account for the main part, including both metal and non-metal parts. The metal part accounts for about 30%, including copper, iron, nickel, lead, platinum, palladium, etc., and the non-metal part accounts for about 70%, mainly composed of glass fiber, epoxy resin, phenolic resin, etc. At present, the recycling technology for the metal part is relatively mature, but there is no very complete recycling treatment and resource utilization method for the relatively low-value non-metal part, which is extremely likely to cause secondary pollution. Therefore, it is very necessary to recycle and utilize the non-metal powder of waste printed circuits.

[0004] Energy is the basis for human survival and development. With the rapid progress of the world economy, the development of industrial technology is also changing with each passing day. Nowadays, fossil energy is still the main energy source, but fossil resources such as coal and natural gas are facing the crisis of exhaustion, and energy shortage has gradually become a shackle for the development of various countries. In order to achieve sustainable development, the exploration and application of non-fossil energy such as wind energy and solar energy, how to efficiently utilize limited resources, and research and develop new energy storage materials to improve energy utilization efficiency have become increasingly urgent research topics. Phase change energy storage materials store energy through latent heat storage, utilize the thermal effect during the phase change process of the material to store energy, and release the stored energy under appropriate conditions. They can store a large amount of energy density, and the temperature of the output energy is stable, which improves the energy utilization rate. They are a kind of green energy materials. Therefore, it is very important to broaden the application fields of phase change materials. Summary of the Invention

[0005] Based on the above problems, the purpose of the present invention is to provide a high-filled polymer composite material of non-metal powder from waste printed circuit boards (NPCB) with phase change characteristics and a preparation method thereof, so as to realize large-scale and mass recycling and reuse of NPCB, and promote the development of the new energy industry.

[0006] The highly filled NPCB polymer composite material with phase change properties provided in this article is a composite material with non-toxic raw materials, simple preparation process, good mechanical properties, thermal stability and high phase change thermal enthalpy value, and can realize large-scale recycling of NPCB, reduce production costs and realize resource recycling.

[0007] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0008] The method for preparing a highly filled NPCB polymer composite material with phase change characteristics provided by the present invention comprises the following steps:

[0009] (1) using a melt blending method, NPCB, a high molecular polymer and its processing aid and a phase change material are mixed uniformly, and added to an open mill for further mixing to obtain a blend; the high molecular polymer is polyvinyl chloride (PVC); the processing aid mainly includes a heat stabilizer, a processing modifier, a foaming agent, a foaming aid, calcium carbonate and a plasticizer;

[0010] (2) placing the blend of step (1) in a mold by a molding process, first hot pressing it in a hot press, and then curing it in a cold press to obtain the highly filled NPCB polymer composite material with phase change properties.

[0011] Furthermore, the NPCB described in step (1) is a non-metallic part recovered from waste printed circuit boards.

[0012] Preferably, the components of the NPCB include glass fiber and thermosetting resin; the mass ratio of the glass fiber to the thermosetting resin is 50-60:40-50.

[0013] Furthermore, the high molecular polymer in step (1) is polyvinyl chloride, brand SG5.

[0014] Furthermore, the processing aids of the high molecular polymer in step (1) are calcium zinc stabilizer, stearic acid, AC foaming agent, calcium carbonate, ACR530, epoxidized soybean oil and ACR401.

[0015] Furthermore, in the highly filled NPCB polymer composite material with phase change properties described in step (1), the phase change material is erythritol and an alloy.

[0016] Furthermore, in step (1), based on the mass fraction,

[0017]

[0018]

[0019] If calculated by mass percentage, in the blend described in step (1), the proportion of NPCB is 63.75 - 90%, the high molecular polymer and its additives are 11.25 - 30%, and the phase change material is 5 - 15%.

[0020] Further, the temperature of the mixing in step (1) is 160°C - 165°C, preferably 160°C, and the mixing time is 15 - 20 min.

[0021] Further, the temperature of the hot pressing in step (2) is 170°C - 175°C, preferably 170°C.

[0022] Further, the time of the hot pressing in step (2) is 4 - 5 min, preferably 4 min.

[0023] Further, the pressure of the hot pressing in step (2) is 9 - 12 MPa.

[0024] Further, the pressure of the curing in step (2) is 9 - 12 MPa.

[0025] Further, the time of the curing in step (2) is 4 - 5 min, preferably 4 min.

[0026] Further, the temperature of the curing in step (2) is room temperature.

[0027] The present invention provides a high - filled NPCB polymer composite material with phase - change characteristics prepared by the above - mentioned preparation method.

[0028] The high - filled NPCB polymer composite material with phase - change characteristics has a relatively high phase - change enthalpy value, good thermal stability and chemical stability, no liquid leakage after the phase - change process, and also has good bending properties.

[0029] Moreover, the high - filled NPCB polymer composite material with phase - change characteristics greatly realizes the recycling of NPCB, reduces the production cost, improves the resource utilization rate, and has good application prospects.

[0030] The preparation method provided by the present invention adopts the melt blending method and the molding method. The preparation process is simple, the raw materials are pollution - free, and the cost is low, which is suitable for industrial production.

[0031] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0032] (1) The preparation process of the present invention is simple, the raw materials are pollution - free, the cost is low, and it is suitable for industrial production.

[0033] (2) The NPCB used in the present invention is a low-value powder that is difficult to process in industry and extremely harmful to the environment, the body, and society. It is a non-metallic material recovered from waste printed circuit boards, and the present invention realizes the renewable utilization of waste resources.

[0034] (3) The polymer used in the present invention is polyvinyl chloride, which binds the fillers in the composite material well, making the prepared board have certain mechanical strength, and there will be no liquid leakage during the phase change process, and it has good thermal stability and chemical stability.

[0035] (4) The phase change materials used in the present invention are erythritol and alloy. The phase change enthalpy value can be changed by varying the amount of erythritol with a high latent heat value, while the alloy with a low phase change temperature mainly plays a role in enhancing the mechanical properties. The present invention also broadens the application ideas and scenarios of the two. Description of the Drawings

[0036] Figure 1 It is a graph of the flexural properties and heat distortion temperature of the NPCB / PVC composite materials prepared in Examples 1-3.

[0037] Figure 2 It is a graph of the flexural properties, heat distortion temperature, and DSC curve of the NPCB / PVC / erythritol composite materials prepared in Examples 4-6.

[0038] Figure 3 It is a graph of the flexural properties, heat distortion temperature, and DSC curve of the NPCB / PVC / erythritol / alloy composite materials prepared in Examples 7-9. Detailed Embodiments

[0039] The following further illustrates the specific implementation of the present invention in combination with examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that for the processes not specifically described in detail below, those skilled in the art can implement or understand them with reference to the prior art. The reagents or instruments not indicating the manufacturer are regarded as conventional products that can be obtained through commercial purchase.

[0040] The weight (mass) parts used in the following examples and comparative examples, as an example, the weight unit can be grams, kilograms, etc., or any other commonly used dosage in the art.

[0041] The NPCB used in the following examples is the non-metallic part recovered from waste printed circuit boards. The components of the NPCB include glass fiber and thermosetting resin; the mass ratio of the glass fiber to the thermosetting resin is 56:44.

[0042] The polymer described in the following examples is polyvinyl chloride, grade SG5, purchased from Hubei Yihua Chemical Industry Co., Ltd.

[0043] In the following examples, by mass parts, the amounts of the polymer and processing aids used are as follows:

[0044]

[0045] The phase change material described in the following examples was purchased from Shanghai Macklin Biochemical Co., Ltd.; the phase change material includes erythritol and an alloy, and the alloy is composed of 25% lead, 12.5% tin, 50% bismuth, and 12.5% cadmium by mass percentage.

[0046] Example 1

[0047] A high-filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and a preparation method thereof. It is prepared by the following method:

[0048] (1) Weigh 38 g of polyvinyl chloride and additives in accordance with the above ratio, mix them evenly and then add them to a two-roll mill for mixing, and set the temperature to 160 °C; after mixing evenly, add 152 g of NPCB for mixing. After mixing for 18 min, a blend is obtained, that is, the mass ratio of NPCB / polyvinyl chloride and additives is 80 / 20;

[0049] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 min, and the hot pressing pressure is 10 MPa;

[0050] (3) Directly place the hot-pressed die into a cold press for curing. The curing time is 4 min, and the curing pressure is 10 MPa to obtain an NPCB / PVC composite material.

[0051] (4) Take out the composite material and make it into a standard specimen on a universal sample preparation machine for bending property testing (in accordance with GB / T9341-2000 "Test Method for Bending Properties of Plastics"), and use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature Under Bending Load of Plastics").

[0052] After testing, the bending modulus of the composite material is 9.02 GPa, the bending strength is 50.34 MPa, and the heat distortion temperature is 84.1 °C. Attached Figure 1 is the bending property and heat distortion temperature diagram of the composite material.

[0053] Example 2

[0054] A high-filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and a preparation method thereof. It is prepared by the following method:

[0055] (1) Weigh a total of 31.5 g of polyvinyl chloride and additives according to the above ratio. After mixing them evenly, add them to a two-roll mill for mixing, and set the temperature to 160 °C; after mixing evenly, add 178.5 g of NPCB for mixing. After mixing for 18 minutes, a blend is obtained, that is, the mass ratio of NPCB / polyvinyl chloride and additives is 85 / 15;

[0056] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 minutes, and the hot pressing pressure is 10 MPa;

[0057] (3) Immediately place the mold after hot pressing into a cold press for curing. The curing time is 4 minutes, and the curing pressure is 10 MPa to obtain the NPCB / PVC composite material.

[0058] (4) Take out the composite material and make it into standard specimens on a universal sample preparation machine for bending property testing (in accordance with GB / T9341-2000 "Test Method for Bending Properties of Plastics"), and use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature Under Bending Load of Plastics").

[0059] After testing, the bending modulus of this composite material is 9.51 GPa, the bending strength is 55.02 MPa, and the heat distortion temperature is 94.37 °C. Attached Figure 1 is the bending property and heat distortion temperature diagram of this composite material.

[0060] Example 3

[0061] A high-filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and its preparation method. It is prepared by the following method:

[0062] (1) Weigh a total of 21.5 g of polyvinyl chloride and additives according to the above ratio. After mixing them evenly, add them to a two-roll mill for mixing, and set the temperature to 160 °C; after mixing evenly, add 193.5 g of NPCB for mixing. After mixing for 18 minutes, a blend is obtained, that is, the mass ratio of NPCB / polyvinyl chloride and additives is 90 / 10;

[0063] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 minutes, and the hot pressing pressure is 10 MPa;

[0064] (3) Immediately place the mold after hot pressing into a cold press for curing. The curing time is 4 minutes, and the curing pressure is 10 MPa to obtain the NPCB / PVC composite material.

[0065] (4) Take out the composite material and make standard specimens on a universal specimen making machine for flexural property testing (in accordance with GB / T 9341-2000 "Test Method for Flexural Properties of Plastics"), and use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature Under Bending Load of Plastics").

[0066] After testing, the flexural modulus of the composite material is 11.95 GPa, the flexural strength is 58.61 MPa, and the heat distortion temperature is 94.37 °C. Attached Figure 1 is the flexural property and heat distortion temperature diagram of the composite material.

[0067] Example 4

[0068] A high-filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and its preparation method. It is prepared by the following method:

[0069] (1) Weigh 27.08 g of polyvinyl chloride and additives according to the above ratio, mix them evenly and then add them to a two-roll mill for mixing, and set the temperature to 160 °C; after mixing evenly, alternately add 153.43 g of NPCB and 9.5 g of erythritol for mixing. After mixing for 14 minutes, a blend is obtained, that is, the mass ratio of (NPCB / polyvinyl chloride and additives) / erythritol is 95(85 / 15) / 5;

[0070] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 minutes, and the hot pressing pressure is 10 MPa;

[0071] (3) Directly put the hot-pressed die into a cold press for curing. The curing time is 4 minutes, and the curing pressure is 10 MPa to obtain an NPCB / PVC / erythritol composite material (the high-filled NPCB polymer composite material with phase change characteristics).

[0072] (4) Take out the composite material and make standard specimens on a universal specimen making machine for flexural property testing (in accordance with GB / T 9341-2000 "Test Method for Flexural Properties of Plastics"), use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature Under Bending Load of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase change characteristics (in accordance with GB / T19466.3-2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0073] The flexural modulus of the composite material was measured to be 12.01 GPa, the flexural strength was 47.06 MPa, the heat distortion temperature was 82.2 °C, the phase transition temperature was 116.8 °C, and the phase transition enthalpy was 5.44 J / g. Attachment Figure 2 is the curve graph of the flexural property, heat distortion temperature and the heating section of the DSC test of the composite material.

[0074] Example 5

[0075] A highly filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and its preparation method. It is prepared by the following method:

[0076] (1) Weigh a total of 25.65 g of polyvinyl chloride and additives according to the above ratio, mix them evenly and then add them to a two-roll mill for mixing, with the temperature set at 160 °C; after mixing evenly, alternately add 145.35 g of NPCB and 19 g of erythritol for mixing. After mixing for 14 min, a blend is obtained, that is, the mass ratio of (NPCB / polyvinyl chloride and additives) / erythritol is 90(85 / 15) / 10;

[0077] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 min, and the hot pressing pressure is 10 MPa;

[0078] (3) Immediately place the hot-pressed die into a cold press for curing. The curing time is 4 min, and the curing pressure is 10 MPa to obtain an NPCB / PVC / erythritol composite material (the highly filled NPCB polymer composite material with phase change characteristics).

[0079] (4) Take out the composite material and make standard specimens on a universal specimen making machine for flexural property testing (in accordance with GB / T9341-2000 "Test Method for Flexural Properties of Plastics"), use a microcomputer-controlled heat distortion Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Distortion Temperature under Bending Load of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase change characteristics (in accordance with GB / T19466.3-2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0080] The flexural modulus of the composite material was measured to be 11.57 GPa, the flexural strength was 31.39 MPa, the heat distortion temperature was 82.9 °C, the phase transition temperature was 118.5 °C, and the phase transition enthalpy was 21.77 J / g. Attachment Figure 2 is the curve graph of the flexural property, heat distortion temperature and the heating section of the DSC test of the composite material.

[0081] Example 6

[0082] A highly filled non - metallic powder of waste printed circuit boards (NPCB) polymer composite material with phase - change characteristics and its preparation method. It is prepared by the following method:

[0083] (1) Weigh 24.23 g of polyvinyl chloride and additives according to the above ratio, mix them evenly and then add them to a two - roll mill for mixing, with the temperature set at 160 °C; after mixing evenly, alternately add 137.28 g of NPCB and 28.5 g of erythritol for mixing. After mixing for 14 min, a blend is obtained, that is, the mass ratio of (NPCB / polyvinyl chloride and additives) / erythritol is 85(85 / 15) / 15;

[0084] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot - pressing temperature is 170 °C, the hot - pressing time is 4 min, and the hot - pressing pressure is 10 MPa;

[0085] (3) Directly put the hot - pressed die into a cold press for curing. The curing time is 4 min, and the curing pressure is 10 MPa to obtain the NPCB / PVC / erythritol composite material (the highly filled NPCB polymer composite material with phase - change characteristics).

[0086] (4) Take out the composite material and make it into standard specimens on a universal sample - making machine for bending property testing (in accordance with GB / T9341 - 2000 "Test Method for Bending Properties of Plastics"), use a microcomputer - controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634 - 2004 "Test Method for Heat Deflection Temperature Under Bending Load of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase - change characteristics (in accordance with GB / T19466.3 - 2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0087] After testing, the bending modulus of this composite material is 10.19 GPa, the bending strength is 30.21 MPa, the heat distortion temperature is 88.4 °C, the phase - change temperature is 119.2 °C, and the phase - change enthalpy is 40.49 J / g. Attached Figure 2 is the curve graph of the bending property, heat distortion temperature and the heating section of the DSC test of this composite material.

[0088] Example 7

[0089] A highly filled non - metallic powder of waste printed circuit boards (NPCB) polymer composite material with phase - change characteristics and its preparation method. It is prepared by the following method:

[0090] (1) Weigh 26.78 g of polyvinyl chloride and additives according to the above ratio, mix them evenly and then add them to a two-roll mill for mixing, with the temperature set at 160 °C; after mixing evenly, alternately add 151.73 g of NPCB, 25.2 g of erythritol and 6.3 g of alloy for mixing. After mixing for 14 minutes, a blend is obtained, that is, the mass ratio of (NPCB / polyvinyl chloride and additives) / (erythritol / alloy) is 85(85 / 15) / 15(80 / 20);

[0091] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 minutes, and the hot pressing pressure is 10 MPa;

[0092] (3) Immediately put the mold after hot pressing into a cold press for curing. The curing time is 4 minutes and the curing pressure is 10 MPa to obtain an NPCB / PVC / erythritol / alloy composite material (the high-filled NPCB polymer composite material with phase change characteristics).

[0093] (4) Take out the composite material and make it into standard specimens on a universal specimen making machine for bending property testing (in accordance with GB / T9341-2000 "Test Method for Bending Properties of Plastics"), use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature Under Bending Load of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase change characteristics (in accordance with GB / T19466.3-2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0094] After testing, the bending modulus of the composite material is 11.84 GPa, the bending strength is 34.34 MPa, the heat distortion temperature is 101.1 °C, the phase change temperature is 118.2 °C, and the phase change enthalpy is 24.21 J / g. Attached Figure 3 is the curve graph of the bending property, heat distortion temperature and DSC test heating section of the composite material.

[0095] Example 8

[0096] A high-filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and its preparation method. It is prepared by the following method:

[0097] (1) Weigh 26.78 g of polyvinyl chloride and additives according to the above ratio, mix them evenly and then add them to a two-roll mill for mixing, with the temperature set at 160 °C; after mixing evenly, alternately add 151.73 g of NPCB, 23.63 g of erythritol and 7.88 g of alloy for mixing. After mixing for 14 min, a blend is obtained, that is, the mass ratio of (NPCB / polyvinyl chloride and additives) / (erythritol / alloy) is 85(85 / 15) / 15(75 / 25);

[0098] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 min, and the hot pressing pressure is 10 MPa;

[0099] (3) Immediately place the hot-pressed die into a cold press for curing. The curing time is 4 min and the curing pressure is 10 MPa to obtain an NPCB / PVC / erythritol / alloy composite material (the high-filled NPCB polymer composite material with phase change characteristics).

[0100] (4) Take out the composite material and make it into standard specimens on a universal sample preparation machine for bending property testing (in accordance with GB / T9341-2000 "Test Method for Bending Properties of Plastics"), use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature under Bending Load of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase change characteristics (in accordance with GB / T19466.3-2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0101] After testing, the bending modulus of the composite material is 13.94 GPa, the bending strength is 37.67 MPa, the heat distortion temperature is 103.2 °C, the phase change temperature is 118.2 °C, and the phase change enthalpy is 19.73 J / g. Attached Figure 3 is the curve graph of the bending property, heat distortion temperature and DSC test heating section of the composite material.

[0102] Example 9

[0103] A high-filled waste printed circuit board non-metallic powder (NPCB) polymer composite material with phase change characteristics and its preparation method. It is prepared by the following method:

[0104] (1) Weigh 26.78 g of polyvinyl chloride and additives according to the above ratio, mix them evenly and then add them to a two-roll mill for mixing, with the temperature set at 160 °C; after mixing evenly, alternately add 151.73 g of NPCB, 22.05 g of erythritol and 9.45 g of alloy for mixing. After mixing for 14 min, a blend is obtained, that is, the mass ratio of (NPCB / polyvinyl chloride and additives) / (erythritol / alloy) is 85(85 / 15) / 15(70 / 30);

[0105] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 min, and the hot pressing pressure is 10 MPa;

[0106] (3) Directly place the hot-pressed die in a cold press for curing. The curing time is 4 min and the curing pressure is 10 MPa to obtain an NPCB / PVC / erythritol / alloy composite material (the high-filled NPCB polymer composite material with phase change characteristics).

[0107] (4) Take out the composite material and make it into standard specimens on a universal sample preparation machine for bending property testing (in accordance with GB / T9341-2000 "Test Method for Bending Properties of Plastics"), use a microcomputer-controlled heat distortion and Vicat softening point testing machine to test its thermal stability (in accordance with GB / T 1634-2004 "Test Method for Heat Deflection Temperature under Bending Load of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase change characteristics (in accordance with GB / T19466.3-2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0108] After testing, the bending modulus of the composite material is 13.96 GPa, the bending strength is 39.45 MPa, the heat distortion temperature is 103.4 °C, the phase change temperature is 118 °C, and the phase change enthalpy is 18.84 J / g. Attached Figure 3 is the graph of the bending property, heat distortion temperature and the heating section of the DSC test of the composite material.

[0109] Comparative Example 1

[0110] A polymer composite shape-stabilized phase change material is prepared by the following method:

[0111] (1) Weigh 40 g of polyvinyl chloride and its additives and 30 g of NPCB according to the above ratio, mix them evenly and then add them to a two-roll mill for mixing, with the temperature set at 150 °C; after mixing evenly, add 30 g of polyethylene glycol (molecular weight 2000) for mixing. After mixing for 8 min, a blend is obtained;

[0112] (2) Place the blend in a molding die with a thickness of 4 mm and place it in a hot press for molding. The hot pressing temperature is 170 °C, the hot pressing time is 4 min, and the hot pressing pressure is 10 MPa;

[0113] (3) Immediately place the mold after hot pressing into a cold press for curing. The curing time is 5 min, and the curing pressure is 10 MPa to obtain a polyethylene glycol / polyvinyl chloride / N-PCB composite shaped phase change material.

[0114] (4) Take out the composite material and make it into standard specimens on a universal specimen making machine for bending property testing (in accordance with GB / T9341-2000 "Test Method for Bending Properties of Plastics"), and use a differential scanning calorimeter (DSC) to test its phase change characteristics (in accordance with GB / T19466.3-2004 "Plastics - Differential Scanning Calorimetry (DSC) - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpies").

[0115] Through testing, the phase change temperature of the composite shaped phase change material is 58.7 °C, the phase change enthalpy is 38.08 J / g, the bending strength is 14.30 MPa, and the bending modulus is 2.42 GPa.

[0116] The performance tests of the composite materials prepared in the above several groups of examples and comparative examples are shown in the following table:

[0117] Table 1 Influence of Examples and Comparative Examples on the Properties of Composite Materials

[0118]

[0119]

[0120] Conclusion: It can be seen from the performance comparison in Table 1 that in Examples 1, 2, and 3, NPCB is doped up to 90 wt%, the filling amount is higher than that of NPCB in Comparative Example 1, and at this time, the bending performance of the composite material is also better. However, since no phase change material is added, the composite material does not have phase change characteristics. In Examples 4, 5, and 6, the NPCB filling amount is still higher than that of Comparative Example 1, and at the same time, it has higher bending performance and heat distortion temperature. Notably, in Example 6, the phase change enthalpy value is also higher than that of Comparative Example 1. The NPCB filling amounts in Examples 7, 8, and 9 are also higher than that of Comparative Example 1, and the bending performance and heat distortion temperature are higher than those in Examples 4, 5, and 6, but the phase change enthalpy value has decreased. This is because although the phase change enthalpy value of erythritol is relatively high, the content of the added phase change material is relatively low, so the enthalpy value is slightly lower than that of Comparative Example 1. As long as the ratio is slightly adjusted, it is possible to obtain an excellent composite material with high doping of NPCB, low cost, high bending performance, high thermal stability, and phase change characteristics.

[0121] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is impossible to list all the implementation manners here. Any obvious changes or variations derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A preparation method of a high-filled polymer composite material of waste printed circuit board non-metal powder with phase change characteristics, characterized in that, It includes the following steps: (1) Mix NPCB, a high molecular polymer, its processing aids, and a phase change material evenly by open milling to obtain a blend; the high molecular polymer is polyvinyl chloride (PVC); the processing aids mainly include a heat stabilizer, a processing modifier, a foaming agent, a foaming aid, calcium carbonate, and a plasticizer; (2) Place the blend obtained in step (1) into a mold, perform hot pressing to form, and then cure to obtain a highly filled NPCB high molecular composite material with phase change characteristics; In step (1), the phase change material is erythritol and an alloy, and the alloy is composed of 25% lead, 12.5% tin, 50% bismuth, and 12.5% cadmium by mass percentage; the high molecular polymer is polyvinyl chloride (PVC); the processing aids are a calcium-zinc stabilizer, stearic acid, an AC foaming agent, calcium carbonate, ACR530, epoxidized soybean oil, and ACR401; The components of NPCB include glass fiber and a thermosetting resin; the mass ratio of the glass fiber to the thermosetting resin is 50 - 60:40 - 50; In step (1), by mass fraction, PVC: 100 parts Calcium-zinc stabilizer: 4 parts Stearic acid: 0.6 part AC foaming agent: 5 parts Calcium carbonate: 5 parts ACR530: 8 parts Epoxidized soybean oil: 2 parts ACR401: 6 parts Phase change material: 33 parts - 165 parts NPCB: 233 parts - 900 parts.

2. The preparation method of the high-filled waste printed circuit board non-metallic powder polymer composite material with phase change characteristics according to claim 1, characterized in that The NPCB is the non-metallic powder part recovered from waste printed circuit boards.

3. The preparation method of the high-filled waste printed circuit board non-metal powder polymer composite material with phase change characteristics according to claim 1, characterized in that In step (1), the temperatures of the front and rear rollers during open milling are both 160°C - 165°C, and the open milling time is 15 - 20 min.

4. The preparation method of the high-filled waste printed circuit board non-metallic powder polymer composite material with phase change characteristics according to claim 1, characterized in that, In step (2), the temperature for hot pressing to form is 170°C - 175°C, the hot pressing time is 4 - 5 min, and the hot pressing pressure is 9 - 12 MPa.

5. The preparation method of the high-fill NPCB polymer composite material with phase change characteristics according to claim 1, characterized in that, In step (2), the curing pressure is 9 - 12 MPa, and the curing time is 4 - 5 min.

6. A highly filled NPCB high molecular composite material with phase change characteristics prepared by the preparation method according to any one of claims 1 - 5.

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