A kind of ablation-resistant polyphenylene sulfide composite material and preparation method thereof

Abstract

The present application relates to the field of polyphenylene sulfide materials, and specifically discloses an ablation-resistant polyphenylene sulfide composite material and its preparation method. The ablation-resistant polyphenylene sulfide composite material includes the following raw material components in parts by mass: 30-90 parts of polyphenylene sulfide, 20-60 parts of composite ceramic filler, 5-20 parts of composite flux, and 0.1-5 parts of other additives; the composite ceramic filler includes glass fiber, mica powder, and silica in a mass ratio of 1: (0.6-1.5): (0.01-0.1); the composite flux includes low-temperature glass powder and borax in a mass ratio of (1-3): 1; the other additives include antioxidants, coupling agents, and lubricants. The ablation-resistant polyphenylene sulfide composite material of the present application has the advantage of excellent ablation resistance.

Description

Technical Field

[0001] The present application relates to the field of polyphenylene sulfide materials, and more specifically, to an ablation-resistant polyphenylene sulfide composite material and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS for short) is a semi-crystalline special engineering plastic with a structure of alternating benzene rings and sulfur. Therefore, it has the advantages of high strength, corrosion resistance, high temperature resistance, and flame retardancy. It is widely used in electronic appliances, automobiles and other fields, such as battery pack covers.

[0003] For battery pack cover products, the temperature can reach over 1000°C after a fire. The intrinsic flame retardant properties of PPS cannot meet the usage requirements in this situation. Therefore, there is an urgent need to develop an ablation-resistant PPS material. Summary of the Invention

[0004] In order to improve the ablation resistance of polyphenylene sulfide materials, the present application provides an ablation-resistant polyphenylene sulfide composite material and a preparation method thereof.

[0005] In a first aspect, the present application provides an ablation-resistant polyphenylene sulfide composite material, which adopts the following technical solution:

[0006] An ablation-resistant polyphenylene sulfide composite material comprises the following raw material components in parts by mass:

[0007] 30-90 parts of polyphenylene sulfide,

[0008] 20-60 parts of composite porcelain filler,

[0009] 5-20 parts of composite flux,

[0010] Other additives 0.1-5 parts;

[0011] The composite porcelain filler comprises glass fiber, mica powder and silicon dioxide in a mass ratio of 1:(0.5-1.5):(0.01-0.1);

[0012] The composite flux comprises low-temperature glass powder and borax in a mass ratio of (1-3):1;

[0013] The other additives include antioxidants, coupling agents, and lubricants.

[0014] By adopting the above technical solution, when the polyphenylene sulfide material is exposed to open flame or high temperature, when the temperature reaches 400-500°C, the polyphenylene sulfide resin gradually degrades and the composite flux begins to melt, connecting the composite ceramic filler particles. As the temperature reaches above 800°C, the polyphenylene sulfide residue, the composite flux, and the composite ceramic filler undergo a eutectic reaction. When the temperature exceeds 1000°C, the ablation-resistant polyphenylene sulfide composite material forms a hard ceramic layer, preventing the material from being further burned through, thereby achieving ablation resistance.

[0015] The inventors discovered that the combination of low-temperature glass powder and borax can provide a better fluxing effect; the combination of glass fiber, mica powder, and silica as a composite porcelain filler, the lamellar mica powder and the flux have a larger contact surface, the porcelain-forming effect is better, and it can promote the formation of the ceramic layer and improve the ablation resistance. The addition of silica can further increase the thermal conductivity of the polyphenylene sulfide material, improve the thermal insulation effect of the material, and promote further improvement of the ablation resistance. The three fillers work together to give the polyphenylene sulfide material excellent ablation resistance.

[0016] Preferably, the fluidity of the polyphenylene sulfide is 300-1000 g / 10 min.

[0017] Preferably, the glass fiber is selected from one or more of alkali-free glass fiber yarn and flat glass fiber; the diameter of the glass fiber is 10-20 μm.

[0018] Preferably, the silicon dioxide is silicon dioxide aerogel, and the particle size of the silicon dioxide is 300-1000 mesh.

[0019] Preferably, the particle size of the mica powder is 200-1000 mesh.

[0020] Preferably, the melting point of the low-melting-point glass powder is 400-800° C., and the particle size of the low-melting-point glass powder is 1000-2000 mesh.

[0021] Preferably, the borax is selected from one or more of borax decahydrate and anhydrous borax.

[0022] Preferably, the lubricant is selected from at least one of calcium stearate, ethylene bisstearamide, pentaerythritol stearate, polyethylene wax, and silicone powder.

[0023] Preferably, the coupling agent is a silane coupling agent, selected from at least one of KH540, KH550, KH560, KH570, KH602, and KH792.

[0024] Preferably, the antioxidant is obtained by compounding antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0025] In a second aspect, the present application provides a method for preparing an ablation-resistant polyphenylene sulfide composite material, which adopts the following technical solution:

[0026] A method for preparing an ablation-resistant polyphenylene sulfide composite material comprises the following steps:

[0027] According to the ratio, polyphenylene sulfide and coupling agent are premixed, and then composite flux, antioxidant and lubricant are added for high mixing. After sufficient mixing, the mixture is added into a twin-screw extruder by main feeding, and composite ceramic filler is added thereto by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0028] In summary, this application has the following beneficial effects:

[0029] 1. This application uses a combination of low-temperature glass powder and borax as a composite flux, which can produce a eutectic reaction with composite porcelain fillers at high temperatures, effectively improving the ablation resistance of polyphenylene sulfide composite materials;

[0030] 2. The present application adopts a compound of glass fiber, mica powder and silica, which has an excellent porcelain-forming effect, reduces the thermal conductivity of the polyphenylene sulfide composite material, and can effectively form a heat-insulating and ablation-resistant ceramic layer under high temperature or combustion conditions, preventing the polyphenylene sulfide composite material from being further burned through. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the final ablation state of the residue after the ablation-resistant polyphenylene sulfide composite material of Example 1 of the present application is burned in a muffle furnace at 650°C. DETAILED DESCRIPTION

[0032] To further help understand the technical solution of the present invention, the following provides several specific implementation examples to describe the technical solution of the present invention in more detail. All of these described embodiments are only some embodiments of the present invention, not all.

[0033] The following specific embodiments may be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments; and the reaction devices, monomer compounds, etc. involved in the following embodiments are all commercially available.

[0034] The following specific embodiments may be combined with each other, and the same or similar concepts or processes therein may not be described in detail in some embodiments.

[0035] The following examples are further explanations of the present invention, but the present invention is not limited thereto. Unless otherwise specified in the examples, the percentages are all by mass.

[0036] Example

[0037] Example 1

[0038] This embodiment discloses an ablation-resistant polyphenylene sulfide composite material, the preparation method of which is as follows:

[0039] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 10 parts by mass of low-temperature glass powder, 5 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0040] The above mixture is added into a twin-screw extruder by main feeding, and 20 parts by mass of glass fiber, 20 parts by mass of mica powder and 1 part by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0041] In this embodiment, the model of polyphenylene sulfide is Xinhecheng PPS1190C; the particle size of the low-temperature glass powder is 1000-1500 μm, the melting point of the low-temperature glass powder is 460-550° C., and the particle size is 1000-1500 mesh; the borax is anhydrous borax with a particle size of 1000-1500 mesh; the glass fiber is an alkali-free glass fiber yarn with a diameter of 10 μm and a length of 3-5 mm; the particle size of the mica powder is 200-500 mesh, and the silica is a silica aerogel with a particle size of 1000-1500 mesh.

[0042] Example 2

[0043] The only difference between this embodiment and embodiment 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0044] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 11 parts by mass of low-temperature glass powder, 4 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0045] The above mixture is added into a twin-screw extruder by main feeding, and 20 parts by mass of glass fiber, 20 parts by mass of mica powder and 1 part by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0046] Example 3

[0047] The only difference between this embodiment and embodiment 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0048] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 8 parts by mass of low-temperature glass powder, 7 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0049] The above mixture is added into a twin-screw extruder by main feeding, and 20 parts by mass of glass fiber, 20 parts by mass of mica powder and 1 part by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0050] Example 4

[0051] The only difference between this embodiment and embodiment 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0052] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 10 parts by mass of low-temperature glass powder, 5 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0053] The above mixture is added into a twin-screw extruder by main feeding, and 24 parts by mass of glass fiber, 16 parts by mass of mica powder and 1 part by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0054] Example 5

[0055] The only difference between this embodiment and embodiment 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0056] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 10 parts by mass of low-temperature glass powder, 5 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0057] The above mixture is added into a twin-screw extruder by main feeding, and 16 parts by mass of glass fiber, 24 parts by mass of mica powder and 1 part by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0058] Example 6

[0059] The only difference between this embodiment and embodiment 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0060] 43.7 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 10 parts by mass of low-temperature glass powder, 5 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture;

[0061] The above mixture is added into a twin-screw extruder by main feeding, and 20 parts by mass of glass fiber, 20 parts by mass of mica powder and 0.5 parts by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0062] Example 7

[0063] The only difference between this embodiment and embodiment 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0064] 42.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 10 parts by mass of low-temperature glass powder, 5 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture;

[0065] The above mixture is added into a twin-screw extruder by main feeding, and 20 parts by mass of glass fiber, 20 parts by mass of mica powder and 2 parts by mass of silica are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0066] Comparative Example

[0067] Comparative Example 1

[0068] The only difference between this comparative example and Example 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0069] 58.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture;

[0070] The above mixture was added into a twin-screw extruder by main feeding, and 41 parts by mass of glass fiber was added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material was obtained.

[0071] Comparative Example 2

[0072] The only difference between this comparative example and Example 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0073] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 15 parts by mass of low-temperature glass powder, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0074] The above mixture was added into a twin-screw extruder by main feeding, and 41 parts by mass of glass fiber was added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material was obtained.

[0075] Comparative Example 3

[0076] The only difference between this comparative example and Example 1 is that the preparation method of the ablation-resistant polyphenylene sulfide composite material is as follows:

[0077] 43.2 parts by mass of polyphenylene sulfide and 0.2 parts by mass of silane coupling agent KH560 were premixed, and then 10 parts by mass of low-temperature glass powder, 5 parts by mass of borax, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, and 0.2 parts of calcium stearate were added, and the raw materials were fully mixed to obtain a mixture.

[0078] The above mixture is added into a twin-screw extruder by main feeding, and 21 parts by mass of glass fiber and 20 parts by mass of mica powder are added into the extruder by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

[0079] Performance testing

[0080] The polyphenylene sulfide materials prepared in each embodiment and comparative example were dried at 120°C for 5 hours and then injection molded. The injection molding conditions were: zone 1 temperature 280-290°C, zone 2 temperature 290-310°C, zone 3 temperature 310-320°C, zone 4 temperature 320-325°C, pressure 65-85 MPa, and speed 30-70 mm / s.

[0081] The tensile strength test was carried out according to the ISO 527 standard at a tensile speed of 50 mm / min. The flexural strength test was carried out according to the ISO 178 standard at a test speed of 10 mm / min. The notched cantilever beam impact strength test was carried out according to the ISO 180 standard with a V-shaped notch. The simply supported beam unnotched impact strength test was carried out according to the ISO 179 standard.

[0082] Each polyphenylene sulfide material was injection molded into a combustion plate of 356×100×3 mm. The combustion plate was ablated using a butane spray gun at 1200-1300° C., and the burn-through time of the combustion plate was recorded.

[0083] Table 1

[0084]

[0085]

[0086] Combined with Examples 1-7 and Comparative Examples 1-2 and Table 1, Figure 1 It can be seen that, referring to the method disclosed in the present application, the combination of low-temperature glass sand and borax as a composite flux, and the combination of glass fiber, mica powder and silica as a composite porcelain filler can give the polyphenylene sulfide material excellent ablation resistance, and it can not be burned through and only slightly deformed after burning with an open flame at 1300°C for 15 minutes.

[0087] From Examples 1-7, Comparative Examples 2-3 and Table 1, it can be seen that mica powder can effectively improve the porcelain-forming effect of polyphenylene sulfide materials and promote the improvement of ablation resistance; the addition of silicon dioxide can further promote the improvement of ablation resistance of polyphenylene sulfide materials and help improve the mechanical properties of polyphenylene sulfide materials.

[0088] 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. An ablation-resistant polyphenylene sulfide composite material, characterized in that: The raw material components include the following parts by weight: 30-90 parts of polyphenylene sulfide, 20-60 parts of composite porcelain filler, 5-20 parts of composite flux, Other additives 0.1-5 parts; The composite porcelain filler is glass fiber, mica powder, and silicon dioxide in a mass ratio of 1: (0.6-1.5): (0.01-0.1), and the silicon dioxide is silicon dioxide aerogel; The composite flux is low-temperature glass powder and borax in a mass ratio of (1-3):1; The other additives include antioxidants, coupling agents, and lubricants.

2. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The glass fiber is selected from one or more of alkali-free glass fiber yarn and flat glass fiber; the diameter of the glass fiber is 10-20µm.

3. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The particle size of the silicon dioxide is 300-1000 meshes.

4. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The particle size of the mica powder is 200-1000 meshes.

5. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The melting point of the low-temperature glass powder is 460-550° C., and the particle size of the low-temperature glass powder is 1000-1500 mesh.

6. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The borax is selected from one or more of borax decahydrate and anhydrous borax.

7. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The lubricant is selected from at least one of calcium stearate, ethylene bisstearamide, pentaerythritol stearate, polyethylene wax, and silicone powder.

8. The ablation-resistant polyphenylene sulfide composite material according to claim 1, characterized in that: The coupling agent is a silane coupling agent, and is selected from at least one of KH540, KH550, KH560, KH570, KH602, and KH792.

9. A method for preparing the ablation-resistant polyphenylene sulfide composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: According to the ratio, polyphenylene sulfide and coupling agent are premixed, and then a composite flux, antioxidant and lubricant are added for high mixing. After sufficient mixing, the mixture is added into a twin-screw extruder by main feeding, and the composite ceramic filler is added thereto by side feeding. After melting, cooling, pulling and pelletizing, the ablation-resistant polyphenylene sulfide material is obtained.

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