A strong heat dissipation PPS / graphene composite material and its preparation method

Abstract

The present invention belongs to the field of thermally conductive and heat-dissipating materials, and specifically relates to a highly heat-dissipating PPS / graphene composite material and its preparation method. The raw materials for preparing the highly heat-dissipating PPS / graphene composite material, by weight, include 80-100 parts of PPS, 5-10 parts of branched polyethyleneimine, 10-20 parts of heat-dissipating graphene oxide mud, 3-5 parts of porous boron nitride, 2-5 parts of maleic anhydride grafted polymer, 0.4-0.8 parts of a coupling agent, 0.5-1 parts of a dispersant, and 1-2 parts of an antioxidant; the dispersant includes polyvinyl pyrrolidone, polyvinyl alcohol, and a polymer dispersion. This application improves the dispersibility of the heat-dissipating graphene oxide mud in PPS and also increases the toughness of PPS, thereby improving the thermal conductivity and flexural strength of the composite material.

Description

Technical Field

[0001] The present invention belongs to the field of thermal conductive and heat dissipation materials, and in particular relates to a strong heat dissipation PPS / graphene composite material and a preparation method thereof. Background Art

[0002] The information age has accelerated social development, and people's lives and work are inseparable from the support of data and networks. The information and data communications industry, as one of the representative industries of the information age, covers a wide range of applications, primarily including wireless and wired information processing, transmission, and delivery. From optical modules to base station equipment, the development of the information and data communications industry is inseparable from the issue of heat dissipation. Metal aluminum alloys have long been used as heat dissipation materials, but with the advancement of polymer science and technology and the rapid upgrading of the industry, new performance requirements have been put forward for polymer materials, hoping that polymer materials will also become good heat conductors.

[0003] Polyphenylene sulfide (PPS) is the leading specialty engineering plastic, boasting excellent heat resistance, chemical resistance, radiation resistance, flame retardancy, balanced physical and mechanical properties, and good processing properties. It is widely used in the textile, automotive, household appliances, electronics, mechanical instrumentation, petrochemical, defense, military, aerospace, and other fields. However, as a polymer, PPS lacks free electrons in its molecules, and heat transfer primarily relies on lattice vibrations. The random entanglement and polydispersity of the molecular chains mean that the polymer matrix material lacks the uniform, dense, and ordered crystal structure required for heat transfer, resulting in poor thermal conductivity for PPS.

[0004] Graphene is a two-dimensional crystal composed of carbon atoms, one atom thick, stripped from graphite. The carbon atoms bond together via sp2 hybridization to form a honeycomb lattice network. Graphene exhibits excellent thermal and electrical conductivity, and adding graphene to PPS can improve its thermal conductivity. However, due to its nanoparticle nature and high surface energy, graphene is difficult to disperse in PPS, making it difficult to construct a heat-dissipating network and thus hindering the full utilization of its excellent thermal conductivity. Summary of the Invention

[0005] In order to improve the dispersibility of graphene in PPS, the present application provides a strong heat dissipation PPS / graphene composite material and a preparation method thereof.

[0006] In the first aspect, the present application provides a strong heat dissipation PPS / graphene composite material, which is achieved by the following technical solution: a strong heat dissipation PPS / graphene composite material, whose preparation raw materials include 80-100 parts of PPS, 5-10 parts of branched polyethyleneimine, 10-20 parts of heat dissipation graphene oxide mud, 3-5 parts of porous boron nitride, 2-5 parts of maleic anhydride grafted polymer, 0.4-0.8 parts of coupling agent, 0.5-1 parts of dispersant and 1-2 parts of antioxidant; the dispersant includes polyvinyl pyrrolidone, polyvinyl alcohol and a high molecular polymer dispersion.

[0007] By adopting the above technical solution, polyvinyl pyrrolidone, polyvinyl alcohol and high molecular polymer dispersion are compounded as dispersants, which improves the dispersibility of heat-dissipating graphene oxide mud in PPS, constructs a heat-conducting and heat-dissipating network, and gives full play to the excellent thermal conductivity of graphene, thereby improving the thermal conductivity coefficient of the composite material. At the same time, the dispersant works together with the coupling agent and maleic anhydride grafted polymer to improve the compatibility between inorganic materials such as heat-dissipating graphene oxide mud and porous boron nitride and high molecular materials such as PPS and branched polyethyleneimine, which not only further improves the dispersibility of heat-dissipating graphene oxide mud in PPS, but also improves the toughness of PPS, thereby improving the bending strength of the composite material. In addition, the porous boron nitride and branched polyethyleneimine work together to improve the toughness of PPS, thereby improving the flexural strength of the composite material. This may be because the branched polyethyleneimine contains polymers of primary amino groups, secondary amino groups, and tertiary amino groups, which enhance the polarity of PPS. The branched polyethyleneimine can also functionalize the porous boron nitride to a certain extent. The branched structure of the branched polyethyleneimine and the porous structure of the porous boron nitride affect the internal stress distribution and other organizational structures of the PPS to a certain extent, thereby improving the toughness of the PPS.

[0008] Preferably, the mass ratio of the polyvinyl pyrrolidone, polyvinyl alcohol and high molecular polymer dispersion is (0.3-0.5):(0.4-0.6):1.

[0009] By adopting the above technical solution, graphene is evenly dispersed in PPS and the thermal conductivity of the composite material is high.

[0010] Preferably, the high molecular polymer dispersion is prepared by mixing ECO-2900 dispersion of Aikechuang and SDS-720 dispersion of Shengsheng in a mass ratio of 1:(1-1.5).

[0011] By adopting the above technical solution, Aikechuang's ECO-2900 dispersion is a high-molecular-weight block copolymer solution containing pigment-affinity groups, and Shengsheng's SDS-720 dispersion is a high-molecular-weight polymer solution containing N-anchoring groups. The two work together to further improve the dispersibility of heat-dissipating graphene oxide mud in PPS, and also improve the compatibility of porous boron nitride and branched polyethyleneimine with PPS, thereby improving the toughness of PPS, thereby improving the thermal conductivity and flexural strength of the composite material.

[0012] Preferably, the heat dissipating graphene oxide mud has a sheet diameter of 10-30 μm and a solid content of 35-45 wt%.

[0013] By adopting the above technical solution, the heat dissipating graphene oxide mud with a sheet diameter of 10-30 μm and a solid content of 35-45 wt% has good dispersion in PPS, and the thermal conductivity of the composite material is high.

[0014] Preferably, the coupling agent is composed of mercaptosilane, aminosilane and titanate coupling agent in a mass ratio of 1:(0.5-0.7):(1-1.2).

[0015] By adopting the above technical solution, the coupling agent composed of mercaptosilane, aminosilane, and titanate coupling agent not only improves the dispersibility of heat-dissipating graphene oxide mud in PPS, but also increases the toughness of PPS, thereby significantly improving the thermal conductivity and flexural strength of the composite material. This is likely due to the interaction between aminosilane and mercaptosilane with the heat-dissipating graphene oxide mud and branched polyethyleneimine, which improves the compatibility between the heat-dissipating graphene oxide mud and PPS. The mercapto group of mercaptosilane promotes the interaction between the coupling agent and PPS, and the titanate coupling agent improves the compatibility between porous boron nitride, heat-dissipating graphene oxide mud, PPS, and branched polyethyleneimine.

[0016] Preferably, the mercaptosilane is bis[γ-(triethoxysilyl)propyl]tetrasulfide.

[0017] The above technical solution improves the toughness of PPS and further enhances the flexural strength of the composite material. This is likely due to the six ethoxy groups and tetrasulfide bonds in bis[γ-(triethoxysilyl)propyl]tetrasulfide, which further enhance its coupling effect on PPS and improve the internal stress distribution of PPS, thereby increasing the toughness of PPS.

[0018] Preferably, the aminosilane is N-β (aminoethyl) -3-aminopropyltrimethoxysilane and / or N-β (aminoethyl) -3-aminopropylmethyldimethoxysilane; more preferably, the aminosilane is N-β (aminoethyl) -3-aminopropyltrimethoxysilane.

[0019] By adopting the above technical solution, the above aminosilane is bisaminosilane, which further improves the dispersibility of the heat-dissipating graphene oxide mud in PPS, thereby improving the thermal conductivity of the composite material.

[0020] Preferably, the porous boron nitride is amino-functionalized porous boron nitride.

[0021] By adopting the above technical solution, the amino-functionalized porous boron nitride, branched polyethyleneimine and aminosilane all have amino groups, and the components interact with each other, further improving the dispersibility of the heat-dissipating graphene oxide mud in PPS and the toughness of PPS, thereby improving the thermal conductivity and bending strength of the composite material.

[0022] Preferably, the weight average molecular weight of the branched polyethyleneimine is 25,000-27,000.

[0023] In a second aspect, the present application provides a method for preparing a strong heat dissipation PPS / graphene composite material, which is achieved by the following technical solution:

[0024] A method for preparing a strong heat dissipation PPS / graphene composite material comprises the following steps:

[0025] PPS, branched polyethyleneimine, porous boron nitride, a coupling agent, a maleic anhydride grafted polymer and an antioxidant are stirred and mixed to obtain a mixture A;

[0026] The heat dissipating graphene oxide mud and the dispersant are stirred and mixed to obtain a mixture B;

[0027] Stirring and mixing the mixed material A and the mixed material B to obtain a mixed material C;

[0028] The mixed material C is melt-extruded and formed, and the extruded material is cooled and pelletized to obtain a strong heat dissipation PPS / graphene composite material.

[0029] The preparation method of the highly heat-dissipating PPS / graphene composite material of the present application is simple. The heat-dissipating graphene oxide mud and the dispersant are pre-mixed and then mixed with other components, which can significantly improve the dispersibility of the heat-dissipating graphene oxide mud, thereby improving the thermal conductivity of the composite material.

[0030] In summary, this application has the following beneficial effects:

[0031] 1. This application uses a compound of polyvinyl pyrrolidone, polyvinyl alcohol and high molecular polymer dispersion as a dispersant. The three work together to improve the dispersibility of heat-dissipating graphene oxide mud in PPS, construct a heat-conducting and heat-dissipating network, give full play to the excellent thermal conductivity of graphene, and thus improve the thermal conductivity coefficient of the composite material.

[0032] 2. The present application uses porous boron nitride and branched polyethyleneimine to work together to improve the toughness of PPS, thereby improving the bending strength of the composite material.

[0033] 3. This application uses a coupling agent compounded with mercaptosilane, aminosilane and titanate coupling agent, which not only improves the dispersibility of heat-dissipating graphene oxide mud in PPS, but also improves the toughness of PPS, thereby significantly improving the thermal conductivity and bending strength of the composite material.

[0034] 4. This application preferably uses bis[γ-(triethoxysilyl)propyl]tetrasulfide, which improves the toughness of PPS and further improves the flexural strength of the composite material.

[0035] 5. This application preferably uses N-β (aminoethyl) -3-aminopropyltrimethoxysilane and / or N-β (aminoethyl) -3-aminopropylmethyldimethoxysilane to further improve the dispersibility of heat-dissipating graphene oxide mud in PPS, thereby improving the thermal conductivity of the composite material.

[0036] 6. This application preferably uses amino-functionalized modified porous boron nitride to further improve the dispersibility of heat-dissipating graphene oxide mud in PPS and the toughness of PPS, thereby improving the thermal conductivity and bending strength of the composite material. DETAILED DESCRIPTION

[0037] The present application is further described in detail below with reference to the embodiments.

[0038] Preparation Example

[0039] Preparation Examples 1-5 provide a dispersant, and Preparation Example 1 is used as an example for description below.

[0040] The dispersant provided in Preparation Example 1 is prepared in the following steps:

[0041] Mix 3g of PVP K90, 6g of PVA 2488 and 10g of ECO-2900 dispersion to obtain a dispersant.

[0042] Preparation Example 2 is different from Preparation Example 1 in that the masses of PVP K90 and PVA 2488 are 5 g and 4 g, respectively.

[0043] Preparation Example 3 is different from Preparation Example 2 in that the mass of ECO-2900 dispersion of Aike Chuang is replaced with SDS-720 dispersion of Shengsheng.

[0044] Preparation Example 4 is different from Preparation Example 2 in that the dispersant is prepared by mixing 5 g of PVP K90, 4 g of PVA 2488, 5 g of Aikechuang ECO-2900 dispersion and 5 g of Shengsheng SDS-720 dispersion.

[0045] Preparation Example 5 is different from Preparation Example 4 in that the masses of ECO-2900 dispersion and Shengsheng SDS-720 are 4 g and 6 g, respectively.

[0046] Preparation Examples 6-12 provide a coupling agent, which will be described below using Preparation Example 6 as an example.

[0047] The coupling agent provided in Preparation Example 6 is prepared as follows:

[0048] 10 g of 3-mercaptopropyltrimethoxysilane, 7 g of 3-aminopropyltrimethoxysilane and 10 g of diisopropyl di(triethanolamine)titanate were mixed uniformly to obtain a coupling agent.

[0049] Preparation Example 7 is different from Preparation Example 6 in that the masses of 3-aminopropyltrimethoxysilane and diisopropyl bis(triethanolamine)titanate are 5 g and 12 g, respectively.

[0050] Preparation Example 8 differs from Preparation Example 6 in that 3-aminopropyltrimethoxysilane is replaced by N-β(aminoethyl)-3-aminopropyltrimethoxysilane.

[0051] Preparation Example 9 differs from Preparation Example 8 in that an equal amount of 3-mercaptopropyltrimethoxysilane is replaced by bis[γ-(triethoxysilyl)propyl]tetrasulfide.

[0052] Preparation Example 10 differs from Preparation Example 7 in that an equal amount of 3-aminopropyltrimethoxysilane is replaced by 3-mercaptopropyltrimethoxysilane.

[0053] Preparation Example 11 differs from Preparation Example 7 in that an equal amount of 3-mercaptopropyltrimethoxysilane is replaced by 3-aminopropyltrimethoxysilane.

[0054] Preparation Example 12 differs from Preparation Example 7 in that the mass of diisopropyl di(triethanolamine)titanate is replaced by 3-aminopropyltrimethoxysilane.

[0055] Preparation Comparative Example

[0056] Comparative Preparation Examples 1-3 provide a dispersant.

[0057] Comparative Example 1 was prepared, which differed from Preparation Example 1 only in that PVP K90 was replaced with PVA 2488.

[0058] Comparative Example 2 was prepared, which differed from Preparation Example 1 only in that PVA 2488 was replaced with PVP K90.

[0059] Comparative Example 3 was prepared, which differed from Preparation Example 1 only in that the mass of ECO-2900 dispersion was replaced by PVA 2488.

[0060] Example

[0061] Examples 1-19 provide a strong heat dissipation PPS / graphene composite material, which is described below using Example 1 as an example.

[0062] The strong heat dissipation PPS / graphene composite material provided in Example 1 is prepared in the following steps:

[0063] S1, 80g PPS, 5g branched polyethyleneimine, 3g alkynyl functionalized porous boron nitride, 0.4g 3-aminopropyltrimethoxysilane, 2g POE-g-MAH and 1g 4,4'-dihydroxydiphenylcyclohexane were stirred and mixed to obtain a mixture A;

[0064] S2. Stir and mix 10 g of heat-dissipating graphene oxide mud and 2 g of dispersant to obtain a mixture B;

[0065] S3, mixing the mixture A prepared in step S1 and the mixture B prepared in step S2 to obtain a mixture C;

[0066] S4, melt-extrude the mixture C obtained in step S3, cool the extruded material and pelletize it to obtain a strong heat dissipation PPS / graphene composite material;

[0067] Among them, PPS model BR42B was purchased from Dongguan Quanyou Plastic Raw Materials Co., Ltd.;

[0068] The weight average molecular weight of the branched polyethyleneimine is 25,000;

[0069] The model of alkyne-functionalized porous boron nitride is porous BN-ALK, which was purchased from Ruixi Biotechnology Co., Ltd.

[0070] POE-g-MAH model 1215HT, purchased from Dongguan Shenghao Plastic Materials Co., Ltd.;

[0071] Heat dissipation graphene oxide mud, item number 102815, with a sheet diameter of 10-30 μm and a solid content of 35-45 wt%, was purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.

[0072] The dispersant was obtained from Preparation 1.

[0073] The only difference between Examples 2-7 and Example 1 is that the quality of the raw materials used in the preparation is different, as shown in Table 1.

[0074] Table 1 Mass of raw materials for preparation of Examples 1-7 / g

[0075]

[0076] The only difference between Examples 8-11 and Example 7 is that the sources of the dispersants are different, as shown in Table 2.

[0077] Table 2 Sources of dispersants for Examples 7-11

[0078]

[0079] Example 12 is different from Example 10 only in that 3-aminopropyltrimethoxysilane is replaced by the coupling agent prepared in Preparation Example 12.

[0080] The only difference between Examples 13-18 and Example 12 is that the sources of the coupling agents are different, as shown in Table 3.

[0081] Table 3 Sources of coupling agents for Examples 12-18

[0082] Example 19 is different from Example 16 only in that the alkynyl-functionalized porous boron nitride is replaced by amino-functionalized porous boron nitride (model: porous BN-NH2, purchased from Ruixi Biotechnology Co., Ltd.).

[0083] Comparative Example

[0084] Comparative Example 1 is different from Example 1 only in that the dispersant is derived from the preparation of Comparative Example 1.

[0085] Comparative Example 2 is different from Example 1 only in that the dispersant is derived from the preparation of Comparative Example 2.

[0086] Comparative Example 3 is different from Example 1 only in that the dispersant is derived from the preparation of Comparative Example 3.

[0087] Comparative Example 4 is different from Example 1 only in that the dispersant is PVA 2488.

[0088] Comparative Example 5 is different from Example 1 only in that the branched polyethyleneimine is replaced by porous boron nitride.

[0089] Comparative Example 6 is different from Example 1 only in that the porous boron nitride is replaced by branched polyethyleneimine.

[0090] Performance testing

[0091] The following performance tests were performed on the strong heat dissipation PPS / graphene composite materials prepared in Examples 1-19 and Comparative Examples 1-6 of the present application.

[0092] 1. Thermal conductivity: The thermal conductivity of the strong heat dissipation PPS / graphene composite material was tested using the ASTM D5470 standard. The test results are shown in Table 4.

[0093] 2. Bending strength: According to the standard of GB / T 9341-2008, the bending strength of the strong heat dissipation PPS / graphene composite material was tested. The results are shown in Table 4.

[0094] Table 4 Test results

[0095]

[0096]

[0097] The following describes this application in detail with respect to the test data in Table 4.

[0098] From the test data of Example 1 and Comparative Examples 1-4, it can be seen that the present application adopts polyvinyl pyrrolidone, polyvinyl alcohol and high molecular polymer dispersion as dispersants, and the three work together to improve the thermal conductivity of the composite material.

[0099] From the test data of Example 1 and Comparative Examples 5-6, it can be seen that the porous boron nitride and the branched polyethyleneimine work together to improve the toughness of PPS, thereby improving the flexural strength of the composite material.

[0100] From the test data of Examples 8-9 and Examples 10-11, it can be seen that Example 10-11 uses ECO-2900 dispersion and Shengsheng SDS-720 dispersion as polymer dispersions, which work together with polyvinyl pyrrolidone and polyvinyl alcohol to further improve the thermal conductivity and flexural strength of the composite material.

[0101] From the test data of Examples 10, 12, 17-18 and Examples 13-14, it can be seen that Example 13-14 uses a coupling agent compounded with mercaptosilane, aminosilane and titanate coupling agent, which not only improves the dispersibility of the heat-dissipating graphene oxide mud in PPS, but also improves the toughness of PPS, thereby significantly improving the thermal conductivity and bending strength of the composite material.

[0102] From the test data of Example 13 and Example 15, it can be seen that Example 15 uses N-β (aminoethyl)-3-aminopropyltrimethoxysilane, and Example 13 uses 3-aminopropyltrimethoxysilane. N-β (aminoethyl)-3-aminopropyltrimethoxysilane significantly improves the thermal conductivity of the composite material.

[0103] From the test data of Example 15 and Example 16, it can be seen that Example 16 uses bis[γ-(triethoxysilyl)propyl]tetrasulfide and Example 15 uses 3-mercaptopropyltrimethoxysilane. The flexural strength of the composite material corresponding to bis[γ-(triethoxysilyl)propyl]tetrasulfide is significantly higher than the flexural strength of the composite material corresponding to 3-mercaptopropyltrimethoxysilane. This is because bis[γ-(triethoxysilyl)propyl]tetrasulfide contains six ethoxy groups and tetrasulfide bonds, which further enhances its coupling effect on PPS, improves the internal stress distribution of PPS, and enhances the toughness of PPS.

[0104] From the test data of Example 16 and Example 19, it can be seen that Example 19 uses amino-functionalized modified porous boron nitride to further improve the dispersibility of the heat-dissipating graphene oxide mud in PPS and the toughness of PPS, thereby improving the thermal conductivity and bending strength of the composite material.

[0105] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A strong heat dissipation PPS / graphene composite material, characterized in that: The raw materials for its preparation include, by weight, 80-100 parts of PPS, 5-10 parts of branched polyethyleneimine, 10-20 parts of heat-dissipating graphene oxide mud, 3-5 parts of porous boron nitride, 2-5 parts of maleic anhydride grafted polymer, 0.4-0.8 parts of coupling agent, 2-3 parts of dispersant and 1-2 parts of antioxidant; the dispersant includes polyvinyl pyrrolidone, polyvinyl alcohol and a high molecular polymer dispersion; The high molecular polymer dispersion is a mixture of ECO-2900 dispersion and / or SDS-720 dispersion; ECO-2900 dispersion is a high molecular weight block copolymer solution containing pigment affinity groups, and SDS-720 dispersion is a high molecular polymer solution containing N anchoring groups.

2. A strong heat dissipation PPS / graphene composite material according to claim 1, characterized in that: The mass ratio of the polyvinyl pyrrolidone, polyvinyl alcohol and high molecular polymer dispersion is (0.3-0.5): (0.4-0.6):

1.

3. A strong heat dissipation PPS / graphene composite material according to claim 1 or 2, characterized in that: The high molecular polymer dispersion is prepared by mixing ECO-2900 dispersion of Ai Ke Chuang and SDS-720 dispersion of Sheng Sheng at a mass ratio of 1: (1-1.5).

4. The strong heat dissipation PPS / graphene composite material according to claim 1, characterized in that: The heat dissipating graphene oxide mud has a sheet diameter of 10-30 μm and a solid content of 35-45 wt%.

5. The strong heat dissipation PPS / graphene composite material according to claim 1, characterized in that: The coupling agent comprises mercaptosilane, aminosilane and titanate coupling agent in a mass ratio of 1: (0.5-0.7): (1-1.2).

6. The strong heat dissipation PPS / graphene composite material according to claim 5, characterized in that: The mercaptosilane is bis[γ-(triethoxysilyl)propyl]tetrasulfide.

7. The strong heat dissipation PPS / graphene composite material according to claim 5, characterized in that: The aminosilane is N-β (aminoethyl)-3-aminopropyltrimethoxysilane and / or N-β (aminoethyl)-3-aminopropylmethyldimethoxysilane.

8. A strong heat dissipation PPS / graphene composite material according to claim 1 or 5, characterized in that: The porous boron nitride is amino-functionalized porous boron nitride.

9. The strong heat dissipation PPS / graphene composite material according to claim 1, characterized in that: The weight average molecular weight of the branched polyethyleneimine is 25,000-27,000.

10. A method for preparing the strong heat dissipation PPS / graphene composite material according to any one of claims 1 to 9, characterized in that: The steps include: PPS, branched polyethyleneimine, porous boron nitride, a coupling agent, a maleic anhydride grafted polymer and an antioxidant are stirred and mixed to obtain a mixture A; The heat dissipating graphene oxide mud and the dispersant are stirred and mixed to obtain a mixture B; Stirring and mixing the mixed material A and the mixed material B to obtain a mixed material C; The mixed material C is melt-extruded and formed, and the extruded material is cooled and pelletized to obtain a strong heat dissipation PPS / graphene composite material.

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