CN110240805A - Graphene-modified polyphenylene sulfide material, preparation method thereof, and heat-conducting plastic tube - Google Patents

Abstract

The invention discloses a graphene polyphenylene sulfide modified material, a preparation method thereof, and a heat-conducting plastic pipe. The polyphenylene sulfide modified material includes 80-100 parts by weight of polyphenylene sulfide substrate, and at least one selected from the following: 5-30 parts by weight of toughening modifier; 2-50 parts by weight of stabilizer performance enhancer; 1-50 parts by weight of thermal conductivity additive; and 0.5-4 parts by weight of additives. The polyphenylene sulfide modified material has good mechanical properties, heat-resistant strength and thermal conductivity, and is resistant to acid and alkali corrosion, and can be applied in relatively harsh environments.

Description

Graphene-modified polyphenylene sulfide material, preparation method thereof, and heat-conducting plastic tube

technical field

The present invention relates to the field of polymer composite materials, specifically, polyphenylene sulfide modified materials and their preparation methods, heat-conducting plastic pipes, and more specifically, graphene-modified polyphenylene sulfide materials and their preparation methods, heat-conducting plastics Tube.

Background technique

With the improvement of corrosion resistance, mechanical properties, electrical insulation properties and processing properties of thermal conductive materials in recent years, traditional thermal conductive materials (such as metals) can no longer meet the application requirements in some chemical fields. Polymer materials have the characteristics of light weight, chemical corrosion resistance, excellent forming and processing performance, excellent electrical insulation performance, excellent mechanical and fatigue properties, etc., but polymer materials themselves are mostly poor conductors of heat, and need to be modified to improve the thermal conductivity of the material performance. Polyphenylene sulfide (PPS) is one of the most stable resins in thermoplastic polymers. It is considered to be a good chemical corrosion-resistant material second only to polytetrafluoroethylene, and it has high strength, high Fatigue performance and creep resistance performance, can be used to prepare heat-conducting plastic pipes. However, the thermal conductivity of polyphenylene sulfide material itself is not outstanding, and the corrosion resistance and mechanical properties of polyphenylene sulfide modified materials are difficult to maintain at a good level.

Therefore, the current polyphenylene sulfide modified material and its preparation method, and the thermally conductive plastic pipe based on the polyphenylene sulfide modified material still need to be improved.

Contents of the invention

The present invention is based on the inventor's discovery and recognition of the following facts and problems:

Although polyphenylene sulfide can be mixed with other polymer materials or inorganic materials (such as carbon nanomaterials) to form modified materials to achieve the purpose of improving thermal conductivity or improving processing performance, but the current polyphenylene sulfide modification It is difficult to take into account the improvement of acid and alkali corrosion resistance, thermal conductivity and mechanical properties at the same time. Therefore, the application of the current polyphenylene sulfide modified materials is still relatively limited, and cannot be applied to chemical scenes with harsh environments. If the composition of the modified polyphenylene sulfide material can be improved to obtain a material that is resistant to acid and alkali, and can maintain the excellent mechanical properties of polyphenylene sulfide and the thermal conductivity of the modified polyphenylene sulfide material, it will be greatly improved. Expand the application of polyphenylene sulfide modified materials.

The present invention aims to alleviate or solve at least one of the above-mentioned problems, at least to some extent.

In one aspect of the present invention, the present invention provides an acid and alkali resistant polyphenylene sulfide modified material. The polyphenylene sulfide modified material includes 80-100 parts by weight of polyphenylene sulfide substrate, and at least one selected from the following: 5-30 parts by weight of toughening modifier; 2-50 parts by weight of stabilizer performance enhancer; 1-50 parts by weight of thermal conductivity additive; and 0.5-4 parts by weight of additives. The polyphenylene sulfide modified material has good mechanical properties and thermal conductivity, and is resistant to acid and alkali corrosion, and can be used in chemical fields with relatively harsh environments.

According to an embodiment of the present invention, the toughening modifier includes at least one of nylon and modified nylon. Among them, the modified nylon includes carbon fiber modified nylon, glass fiber modified nylon and carbon fiber glass fiber co-modified nylon. The above-mentioned toughening modifier can not only improve the mechanical properties of the modified material, but also improve the corrosion resistance of the modified material to acid and alkali.

According to an embodiment of the present invention, the stability enhancer includes at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer. Thus, the performance of the modified material can be further improved.

According to an embodiment of the present invention, the thermal conductivity aid includes at least one of graphene, graphite, carbon nanotube, carbon fiber, silicon carbide, and boron nitride. Thus, the thermal conductivity of the modified material can be further improved.

According to an embodiment of the present invention, the additive includes at least one of wax, process oil, and silane coupling agent. Thus, the performance of the modified material can be further improved.

According to an embodiment of the present invention, the polyphenylene sulfide modified material includes: 95-100 parts by weight of the polyphenylene sulfide substrate and 4-30 parts by weight of the toughening modifier, the toughened The modifier is nylon. The polyphenylene sulfide modified material has good corrosion resistance to acid, alkali and organic matter while maintaining good mechanical properties.

According to an embodiment of the present invention, the polyphenylene sulfide modified material further includes at least one selected from the following: 2-15 parts by weight of the stability enhancer, and the stability enhancer is polytetrafluoroethylene; 10-25 parts by weight of the thermal conduction aid; and 1-3 parts by weight of the additive, wherein the thermal conduction aid includes at least one of silicon carbide powder, carbon fiber, graphene, and carbon nanotube. The polyphenylene sulfide modified material has good corrosion resistance to acid, alkali and organic matter while maintaining good mechanical properties and thermal conductivity.

According to an embodiment of the present invention, the polyphenylene sulfide modified material includes: 95-100 parts by weight of the polyphenylene sulfide substrate and 4-6 parts by weight of the stability enhancer, the stability enhancement The agent is polytetrafluoroethylene. The polyphenylene sulfide modified material has good corrosion resistance to acid, alkali and organic matter while maintaining good mechanical properties.

In another aspect of the present invention, the present invention proposes a method for preparing a polyphenylene sulfide modified material. The method comprises: high-speed mixing of raw materials according to the ratio, extrusion and granulation of the high-speed mixed raw materials to form polyphenylene sulfide modified materials, and the raw materials include 80-100 parts by weight of polyphenylene sulfide A sulfide base material, and at least one selected from the following: 5-30 parts by weight of a toughening modifier; 2-50 parts by weight of a stability enhancer; 1-50 parts by weight of a thermal conductivity aid; and 0.5- 4 parts by weight of additives. Thus, the polyphenylene sulfide modified material can be obtained relatively easily, and the obtained modified material can have better performance.

In yet another aspect of the present invention, the present invention provides a thermally conductive plastic pipe. The thermally conductive plastic pipe includes the aforementioned polyphenylene sulfide modified material. Therefore, the heat-conducting plastic pipe has all the features and advantages of the polyphenylene sulfide modified material described above, which will not be repeated here. In general, the heat-conducting plastic pipe can be used in harsh chemical environments.

Detailed ways

The following describes the embodiments of the present invention in detail, and the following descriptions of the present invention through the embodiments are exemplary, and are only used to explain the present invention, and cannot be construed as limiting the present invention.

In one aspect of the present invention, the present invention provides an acid and alkali resistant polyphenylene sulfide modified material. The polyphenylene sulfide modified material includes a polyphenylene sulfide base material and at least one selected from toughening modifiers, stability enhancers, heat conduction aids, and additives. When the polyphenylene sulfide substrate is mixed with at least one of the above additives, the modified material can have better mechanical properties and better acid and alkali resistance. Therefore, it can be used in harsher environments. The polyphenylene sulfide modified material may contain 80-100 parts by weight of polyphenylene sulfide substrate, and may contain at least one of the following components in parts by weight: 5-30 parts by weight of toughening Modifier, 2-50 parts by weight of stability enhancer, 1-50 parts by weight of heat conduction aid, and 0.5-4 parts by weight of additives.

According to some embodiments of the present invention, the polyphenylene sulfide modified material may contain 80-100 parts by weight of the polyphenylene sulfide substrate, and one or both of the toughening modifier and the stability enhancer, It also contains at least one of thermal conductivity additives and additives.

According to an embodiment of the present invention, the toughening modifier may include at least one of PA and modified PA. It may also include at least one of toughening agents such as EPDM, SBS, and SEBS. For example, glass fiber reinforced PA, glass fiber and carbon fiber co-modified PA can be included. For example, it may be 15% glass fiber reinforced nylon (PA). Specifically, at least one selected from PA, PA6 and PA66 may be included. The above-mentioned toughening modifier can not only improve the mechanical properties of the modified material, but at the same time, the inventor surprisingly found that the above-mentioned nylon, especially glass fiber reinforced PA, can also improve the corrosion resistance of the modified material to acid and alkali.

According to an embodiment of the present invention, the stability enhancer includes polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF) and tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer ( at least one of PFA). Thus, the performance of the modified material can be further improved. The inventors found that the stability enhancer mentioned above is not only beneficial to improve the processability of the polyphenylene sulfide modified material, but also can improve the acid and alkali corrosion resistance of the modified material to a certain extent. And, when the modified material contains 80 to 100 parts by weight of the polyphenylene sulfide substrate and 2 to 50 parts by weight of the stability enhancer, for example, 5 to 15 parts by weight of the stability enhancer can be Improve the corrosion resistance of the polyphenylene sulfide modified material to inorganic acids, alkalis (such as sodium hydroxide) and some organic substances (such as toluene). According to the embodiments of the present invention, the stability enhancer such as PTFE can also improve the acid and alkali resistance of the modified material. However, excessive addition will lead to poor processing performance of the modified material.

According to an embodiment of the present invention, in order to further improve the thermal conductivity of the polyphenylene sulfide modified material, the polyphenylene sulfide composite material may further include a thermal conductivity aid. The addition amount of the thermal conduction aid may be 1-50 parts by weight, and the thermal conduction aid may include carbon-based materials, for example, may include at least one of graphene, graphite, carbon nanotubes, carbon fibers, silicon carbide, and boron nitride. Thus, the thermal conductivity of the modified material can be further improved, and the acid-base weather resistance of the modified material can be improved to a certain extent. Moreover, carbon nanomaterials with a certain two-dimensional or three-dimensional morphology, such as carbon fibers, carbon nanotubes, and graphene, can not only improve the thermal conductivity of the polyphenylene sulfide modified material, but also alleviate the modification caused by the addition of additives. Decrease in the mechanical properties of permanent materials. For example, the thermal conduction aid may include silicon carbide. In addition to improving the thermal conductivity of the modified material, silicon carbide can also improve the acid-base weather resistance of the modified material to a certain extent. When silicon carbide is included in the thermal conductivity additive, it is necessary to control the amount of silicon carbide added: due to the large specific gravity of silicon carbide itself, it is not easy to obtain a better filling rate if the addition amount is too small, and it is difficult to improve the thermal conductivity of the material. When , the adhesiveness of the material is affected and the processing performance becomes poor.

According to the embodiments of the present invention, in order to further improve the processability of the modified material, further improve the performance of the modified material, and ensure that the PPS matrix and other additives can be fully mixed and dispersed, the polyphenylene sulfide modified material can also include additives . The specific type of the additive is not particularly limited, and may include, for example, at least one of wax, process oil, and a coupling agent, such as a silane coupling agent. According to the embodiment of the present invention, since the chemical composition and content of the toughening modifier, stability enhancer and heat conduction aid selected in the present invention are controlled and screened, the amount of additives added can be less. As a result, while ensuring that each component in the modified material can be well dispersed, it is possible to avoid excessive addition of additives that would affect the performance of the modified material.

According to some specific embodiments of the present invention, the polyphenylene sulfide modified material may include 95-100 parts by weight of polyphenylene sulfide base material and 4-30 parts by weight of toughening modifier. Wherein, the toughening modifier can be PA, such as 15% glass fiber modified PA. The phenylene sulfide modified material has good corrosion resistance to acid, alkali and organic matter while maintaining good mechanical properties.

According to an embodiment of the present invention, while the polyphenylene sulfide modified material includes a polyphenylene sulfide substrate and a toughening modifier (for example, 15% glass fiber modified PA), it may further include the following materials At least one of: 2 to 15 parts by weight of the stability enhancer, the stability enhancer is polytetrafluoroethylene; 10 to 25 parts by weight of the thermal conduction aid; and 1 to 3 parts by weight of the The above additive, wherein, the thermal conduction additive includes at least one of silicon carbide powder, carbon fiber, graphene, and carbon nanotubes. The polyphenylene sulfide modified material has good corrosion resistance to acid, alkali and organic matter while maintaining good mechanical properties and thermal conductivity.

According to other embodiments of the present invention, the polyphenylene sulfide modified material may also include 95-100 parts by weight of polyphenylene sulfide substrate and 4-6 parts by weight of a stability enhancer, and the stability enhancer may be PTFE. The polyphenylene sulfide modified material has good corrosion resistance to acid, alkali and organic matter while maintaining good mechanical properties.

In another aspect of the present invention, the present invention proposes a method for preparing a polyphenylene sulfide modified material. The polyphenylene sulfide modified material prepared by this method may be the polyphenylene sulfide modified material described above. According to an embodiment of the present invention, the method includes: mixing the raw materials at a high speed according to the ratio, and extruding the high-speed mixed raw materials to form polyphenylene sulfide modified materials. Wherein, the proportioning of the raw materials can be proportioned according to the chemical composition of the polyphenylene sulfide modified material described above. For example, the raw material may include 80-100 parts by weight of polyphenylene sulfide substrate, and at least one selected from the following: 5-30 parts by weight of toughening modifier, 2-50 parts by weight of stability enhancer, 1-50 parts by weight of thermal conductivity additive, and 0.5-4 parts by weight of additives. Thus, the polyphenylene sulfide modified material can be obtained relatively easily, and the obtained modified material can have better performance.

According to an embodiment of the present invention, the chemical composition of the toughening modifier, the stability enhancer, the thermal conductivity additive, and the additive may have the same chemical composition as that of the corresponding components in the polyphenylene sulfide modified material described above, No more details here.

According to other embodiments of the present invention, the method of synthesizing the polyphenylene sulfide modified material may not be limited to extrusion molding, or not limited to single-screw extrusion granulation. For example, the polyphenylene sulfide modified material with the above components can be formed by twin-screw, banbury, 10,000-horsepower, planetary screw and other molding methods or equipment.

In yet another aspect of the present invention, the present invention provides a thermally conductive plastic pipe. The thermally conductive plastic pipe includes the aforementioned polyphenylene sulfide modified material. Therefore, the heat-conducting plastic pipe has all the features and advantages of the polyphenylene sulfide modified material described above, which will not be repeated here. In general, the heat-conducting plastic pipe can be used in harsh chemical environments.

The solutions of the present invention are described below through specific examples. It should be noted that the following examples are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. If no specific technique or condition is indicated in the examples, it shall be carried out according to the technique or condition described in the literature in this field or according to the product specification.

Example 1

Add 100g of PPS and 5g of PA into the high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 2

Add 100g of PPS and 30g of PA into the high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 3

Add 100g of PPS and 10g of PA into the high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 4

Add 100g of PPS and 5g of PTFE into the high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 5

Add 100g of PPS, 5g of graphene, and 2g of additives into a high-speed mixer, and perform high-speed mixing for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 6

Add 100g of PPS, 30g of PA, and 30g of silicon carbide powder into the high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 7

Add 100g of PPS, 30g of PA, 2g of carbon fiber, 18g of silicon carbide powder, and 2g of additives into a high-speed mixer, and mix at a high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Example 8

Add 100g of PPS, 15g of PA, 10g of PTFE, 10g of graphene, 1g of carbon nanotubes, 2g of carbon fiber, 10g of silicon carbide powder, and 2g of additives into a high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Comparative example 1

Add 100g of PPS and 60g of PA into the high-speed mixer, and mix at high speed for 15 minutes. The uniformly mixed material is put into a single-screw extruder for extrusion, and the rear end of the extruder is processed by a granulator to obtain a modified PPS masterbatch. The masterbatch is put into the extruder to obtain the modified PPS pipe through extrusion, pressurization and cooling process.

Performance Testing

The properties of the master batches obtained in Examples 1 to 7 were tested. Among them, the tensile strength is tested according to GB/T 1040-2006. Thermal conductivity is tested by ASTM E1461. Wherein the strength retention rate is: according to the retention rate of the tensile strength after the pipe obtained in the above example is immersed in the reagent shown in the following Table 1 for 48 hours when the reagent is heated to 93 degrees Celsius.

Table 1. Performance summary of each embodiment

Table 2. Performance summary of comparative examples

1 Tensile strength (MPa) 67 Thermal conductivity (W/m·K) 0.2 37% hydrochloric acid 96 30% nitric acid 65 30% sulfuric acid 90 30% NaOH 83 Toluene 77

It can be seen from Table 1 that the pipes of all examples can maintain good strength in high-temperature acid, alkali and organic environment, that is, the pipes obtained in all examples have good corrosion resistance. At the same time, the tensile strength and thermal conductivity of the pipes in Examples 1 to 7 are also good, and can maintain the relatively excellent mechanical properties and thermal conductivity of the PPS material. Especially in Example 7, which has more types of thermal conductivity additives, the thermal conductivity is more than 20 times higher than that of traditional PPS materials.

It can be seen from Table 2 that when the amount of PA added is too high (see Comparative Example 1), although the fluidity and tensile properties of PPS resin can be improved to a certain extent, PA does not contribute to the thermal conductivity of the mixed resin, and because PA The resin itself has poor acid and alkali resistance, and it is prone to swelling reaction in organic solvents, which not only easily leads to the decline of the acid resistance of the modified material, but also tends to cause a large degree of strength loss of the mixed resin after the acid and alkali weather resistance test. decline. In the description of this specification, description with reference to the terms "one embodiment", "another embodiment", etc. means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention . In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.

Claims (10)

1. a kind of polyphenylene sulfide modified material of acid-alkali-corrosive-resisting, which is characterized in that the polyphenylene sulfide including 80~100 parts by weight Substrate, and selected from least one of following:

The plasticized modifier of 5~30 parts by weight；

The stability enhancer of 2~50 parts by weight；

The Thermal conductive additives of 1~50 parts by weight；And

The additive of 0.5~4 parts by weight.

2. polyphenylene sulfide modified material according to claim 1, which is characterized in that the plasticized modifier include nylon with And at least one of modification of nylon.

3. polyphenylene sulfide modified material according to claim 1, which is characterized in that the stability enhancer includes poly- four At least one of vinyl fluoride, Kynoar, polyvinyl fluoride and tetrafluoroethene-perfluorinated alkoxy vinyl ether copolymer.

4. polyphenylene sulfide modified material according to claim 1, which is characterized in that the Thermal conductive additives include graphene, At least one of graphite, carbon nanotube, carbon fiber, silicon carbide, boron nitride.

5. polyphenylene sulfide modified material according to claim 1, which is characterized in that the additive include wax, operation oil, At least one of silane coupling agent.

6. polyphenylene sulfide modified material according to claim 1 characterized by comprising

The polyphenylene sulfide substrate of 95~100 parts by weight and the plasticized modifier of 4~30 parts by weight, the toughening change Property agent be nylon.

7. polyphenylene sulfide modified material according to claim 6, which is characterized in that further comprise selected from it is following at least One of:

The stability enhancer of 2~15 parts by weight, the stability enhancer are polytetrafluoroethylene (PTFE)；

The Thermal conductive additives of 10~25 parts by weight；And

The additive of 1~3 parts by weight,

Wherein, the Thermal conductive additives include at least one of carborundum powder, carbon fiber, graphene and carbon nanotube.

8. polyphenylene sulfide modified material according to claim 1 characterized by comprising

The polyphenylene sulfide substrate of 95~100 parts by weight and the stability enhancer of 4~6 parts by weight, the stabilization Property reinforcing agent be polytetrafluoroethylene (PTFE).

9. a kind of method for preparing polyphenylene sulfide modified material characterized by comprising

Raw material is subjected to mixed at high speed according to the proportion, and the raw material Jing Guo the mixed at high speed is subjected to extruding pelletization, to be formed Polyphenylene sulfide modified material,

The raw material includes the polyphenylene sulfide substrate of 80~100 parts by weight, and selected from least one of following:

The plasticized modifier of 5~30 parts by weight；

The stability enhancer of 2~50 parts by weight；

The Thermal conductive additives of 1~50 parts by weight；And

The additive of 0.5~4 parts by weight.

10. a kind of heat-conduction plastic pipe, which is characterized in that described includes that the described in any item polyphenylene sulfides of claim 1-8 are modified Material.