CN110240805B - Graphene modified polyphenylene sulfide material, preparation method thereof and heat-conducting plastic pipe - Google Patents
Graphene modified polyphenylene sulfide material, preparation method thereof and heat-conducting plastic pipe Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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 comprises 80-100 parts by weight of a polyphenylene sulfide base material and at least one selected from the following components: 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 heat-conducting auxiliary agent; and 0.5-4 parts by weight of an additive. The polyphenylene sulfide modified material has good mechanical property, heat-resistant strength and heat conductivity, can resist acid and alkali corrosion, and can be applied to severe environments.
Description
Technical Field
The invention relates to the field of polymer composite materials, in particular to a polyphenylene sulfide modified material and a preparation method thereof, and a heat-conducting plastic pipe, and more particularly relates to a graphene modified polyphenylene sulfide material and a preparation method thereof, and a heat-conducting plastic pipe.
Background
With the recent industrial development of the improvement of the requirements on corrosion resistance, mechanical property, electrical insulation property, processability and the like of heat conducting materials, the traditional heat conducting materials (such as metal and the like) can not meet the application requirements in certain chemical fields. The high polymer material has the characteristics of light weight, chemical corrosion resistance, excellent molding and processing performance, excellent electrical insulation performance, excellent mechanical and fatigue performance and the like, but the high polymer material is a poor thermal conductor and needs to be modified to improve the heat conduction performance of the material. Polyphenylene Sulfide (PPS) is one of the most stable resins in thermoplastic polymers, is considered to be a good chemical corrosion resistant material next to polytetrafluoroethylene, has high strength and rigidity, and excellent fatigue resistance and creep resistance, and can be used for preparing heat-conducting plastic pipes. However, the heat conductivity of the polyphenylene sulfide material is not outstanding, and the corrosion resistance and mechanical properties of the conventional polyphenylene sulfide modified material are difficult to maintain at a good level.
Therefore, the polyphenylene sulfide modified material, the preparation method thereof and the heat-conducting plastic pipe based on the polyphenylene sulfide modified material still need to be improved.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems:
although the polyphenylene sulfide can be mixed with other high molecular materials or inorganic materials (such as carbon nanomaterials) to form a modified material, so as to achieve the purpose of improving the heat conductivity or the processability, the conventional polyphenylene sulfide modified material is difficult to simultaneously improve the acid-base corrosion resistance, the heat conductivity and the mechanical property. Therefore, the application of the polyphenylene sulfide modified material at present is still limited, and the polyphenylene sulfide modified material cannot be applied to a chemical scene with harsh environment. If the composition of the polyphenylene sulfide modified material is improved, the material which can simultaneously resist acid and alkali and maintain the excellent mechanical property and the thermal conductivity of the polyphenylene sulfide modified material is obtained, and the application of the polyphenylene sulfide modified material is greatly expanded.
The present invention aims to alleviate or solve at least to some extent at least one of the above mentioned problems.
In one aspect of the invention, the invention provides an acid and alkali resistant polyphenylene sulfide modified material. The polyphenylene sulfide modified material comprises 80-100 parts by weight of a polyphenylene sulfide base material and at least one selected from the following components: 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 heat-conducting auxiliary agent; and 0.5-4 parts by weight of an additive. The polyphenylene sulfide modified material has good mechanical property and thermal conductivity, can resist acid and alkali corrosion, and can be applied to the field of chemical industry with severe environment.
According to an embodiment of the present invention, the toughening modifier comprises at least one of nylon and modified nylon. The modified nylon comprises carbon fiber modified nylon, glass fiber modified nylon and carbon fiber and glass fiber co-modified nylon. The toughening modifier can improve the mechanical property of the modified material and can also improve the acid and alkali corrosion resistance of the modified material.
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 heat conduction auxiliary agent includes 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.
According to an embodiment of the invention, the additive comprises at least one of a wax, a process oil, a 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 base material and 4-30 parts by weight of the toughening modifier, wherein the toughening modifier is nylon. The polyphenylene sulfide modified material can keep better mechanical property and has better corrosion resistance to acid, alkali and organic matters.
According to an embodiment of the present invention, the polyphenylene sulfide modified material further comprises at least one selected from the group consisting of: 2-15 parts by weight of the stability reinforcing agent, wherein the stability reinforcing agent is polytetrafluoroethylene; 10-25 parts by weight of the heat-conducting auxiliary agent; and 1-3 parts by weight of the additive, wherein the heat conduction auxiliary agent comprises at least one of silicon carbide powder, carbon fibers, graphene and carbon nanotubes. The polyphenylene sulfide modified material can keep better mechanical property and thermal conductivity, and has better corrosion resistance to acid, alkali and organic matters.
According to an embodiment of the present invention, the polyphenylene sulfide modified material includes: 95-100 parts by weight of the polyphenylene sulfide base material and 4-6 parts by weight of the stability reinforcing agent, wherein the stability reinforcing agent is polytetrafluoroethylene. The polyphenylene sulfide modified material can keep better mechanical property and has better corrosion resistance to acid, alkali and organic matters.
In another aspect of the present invention, a method for preparing a polyphenylene sulfide modified material is provided. The method comprises the following steps: the method comprises the following steps of mixing raw materials at a high speed according to a ratio, and carrying out extrusion granulation on the raw materials subjected to high-speed mixing to form the polyphenylene sulfide modified material, wherein the raw materials comprise 80-100 parts by weight of a polyphenylene sulfide base material and at least one selected from the following components: 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 heat-conducting auxiliary agent; and 0.5-4 parts by weight of an additive. Therefore, the polyphenylene sulfide modified material can be obtained more simply and conveniently, and the obtained modified material has better performance.
In yet another aspect of the present invention, a thermally conductive plastic tube is provided. The heat-conducting plastic pipe comprises the polyphenylene sulfide modified material. Therefore, the heat-conducting plastic pipe has all the characteristics and advantages of the polyphenylene sulfide modified material, and the details are not repeated. Generally speaking, the heat-conducting plastic pipe can be applied to a severer chemical environment.
Detailed Description
The following examples are given by way of illustration only and are not to be construed as limiting the present invention.
In one aspect of the invention, the invention provides an acid and alkali resistant polyphenylene sulfide modified material. The polyphenylene sulfide modified material comprises a polyphenylene sulfide base material and at least one selected from a toughening modifier, a stability enhancer, a heat conduction auxiliary agent and an additive. When the polyphenylene sulfide base material is mixed with at least one of the additives, the modified material has better mechanical property and better acid-base tolerance. Therefore, the method can be applied to more severe environments. The polyphenylene sulfide modified material can contain 80-100 parts by weight of a polyphenylene sulfide base material, and can contain at least one of the following components in parts by weight: 5-30 parts of toughening modifier, 2-50 parts of stability reinforcing agent, 1-50 parts of heat conduction auxiliary agent and 0.5-4 parts of additive.
According to some embodiments of the invention, the polyphenylene sulfide modified material may contain 80 to 100 parts by weight of a polyphenylene sulfide base material, and one or both of a toughening modifier and a stability enhancer, and at least one of a heat conduction aid and an additive.
According to embodiments of the present invention, the toughening modifier may include at least one of PA and modified PA. At least one of tougheners such as ethylene propylene diene monomer, SBS, SEBS and the like can also be included. For example, glass fiber reinforced PA, glass fiber and carbon fiber co-modified PA may 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 toughening modifier can improve the mechanical property of the modified material, and the inventor surprisingly finds that the nylon, especially the glass fiber reinforced PA, can improve the acid and alkali corrosion resistance of the modified material.
According to an embodiment of the present invention, the stability enhancer includes at least one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA). Thus, the performance of the modified material can be further improved. The inventor finds that the stability reinforcing agent is not only beneficial to improving 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. When the modified material contains 80-100 parts by weight of the polyphenylene sulfide base material and 2-50 parts by weight of the stability reinforcing agent, for example, 5-15 parts by weight of the stability reinforcing agent, the corrosion resistance of the polyphenylene sulfide modified material to inorganic acids, alkalis (such as sodium hydroxide) and partial organic matters (such as toluene) can be improved. According to the embodiment of the invention, the stability reinforcing agent such as PTFE can also improve the acid and alkali resistance of the modified material. However, excessive addition results in poor processability of the modified material.
According to the embodiment of the invention, in order to further improve the heat conduction performance of the polyphenylene sulfide modified material, the polyphenylene sulfide composite material can further comprise a heat conduction auxiliary agent. The addition amount of the heat conduction auxiliary agent may be 1 to 50 parts by weight, and the heat conduction auxiliary agent may include a carbon-based material, for example, at least one of graphene, graphite, carbon nanotubes, carbon fibers, silicon carbide, and boron nitride. Therefore, the heat 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. In addition, carbon fibers, carbon nanotubes, graphene and other carbon nanomaterials with a certain two-dimensional or three-dimensional morphology can improve the thermal conductivity of the polyphenylene sulfide modified material, and can relieve the reduction of the mechanical property of the modified material due to the addition of additives. For example, the heat transfer aid may include silicon carbide. The silicon carbide can improve the heat conductivity of the modified material and can improve the acid-base weather resistance of the modified material to a certain extent. When silicon carbide is included in the heat transfer aid, the amount of silicon carbide added needs to be controlled: because the silicon carbide has a large specific gravity, the addition amount is too small, so that a good filling rate is not easy to obtain, the heat-conducting property of the material is difficult to improve, and when the addition amount is excessive, the adhesiveness of the material is influenced, and the processability is poor.
According to the embodiment of the 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 comprise 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 invention, because the chemical components and the contents of the toughening modifier, the stability enhancer and the heat conduction auxiliary agent which are selected by the invention are controlled and screened, the addition amount of the additive can be less. Therefore, the modified material can be well dispersed, and the influence of excessive addition of the additive on the performance of the modified material is avoided.
According to some embodiments of the present invention, the polyphenylene sulfide modified material may include 95 to 100 parts by weight of a polyphenylene sulfide base material and 4 to 30 parts by weight of a toughening modifier. The toughening modifier can be PA, such as 15% glass fiber modified PA. The diphenyl sulfide modified material can keep better mechanical property and has better corrosion resistance to acid, alkali and organic matters.
According to the embodiment of the invention, the polyphenylene sulfide modified material, while comprising the polyphenylene sulfide base material and the toughening modifier (for example, 15% glass fiber modified PA), may further comprise at least one of the following materials: 2-15 parts by weight of the stability reinforcing agent, wherein the stability reinforcing agent is polytetrafluoroethylene; 10-25 parts by weight of the heat-conducting auxiliary agent; and 1-3 parts by weight of the additive, wherein the heat conduction auxiliary agent comprises at least one of silicon carbide powder, carbon fibers, graphene and carbon nanotubes. The polyphenylene sulfide modified material can keep better mechanical property and thermal conductivity, and has better corrosion resistance to acid, alkali and organic matters.
According to other embodiments of the present invention, the polyphenylene sulfide modified material may also include 95 to 100 parts by weight of a polyphenylene sulfide base material and 4 to 6 parts by weight of a stability enhancer, and the stability enhancer may be polytetrafluoroethylene. The polyphenylene sulfide modified material can keep better mechanical property and has better corrosion resistance to acid, alkali and organic matters.
In another aspect of the present invention, a method for preparing a polyphenylene sulfide modified material is provided. The polyphenylene sulfide modified material prepared by the method can be the polyphenylene sulfide modified material described above. According to an embodiment of the invention, the method comprises: the raw materials are mixed at a high speed according to a ratio, and the raw materials subjected to high-speed mixing are extruded and granulated to form the polyphenylene sulfide modified material. The raw materials can be mixed according to the chemical composition of the polyphenylene sulfide modified material. For example, the raw material may include 80 to 100 parts by weight of a polyphenylene sulfide base material, and at least one selected from the group consisting of: 5-30 parts of toughening modifier, 2-50 parts of stability reinforcing agent, 1-50 parts of heat conduction auxiliary agent and 0.5-4 parts of additive. Therefore, the polyphenylene sulfide modified material can be obtained more simply and conveniently, and the obtained modified material has better performance.
According to the embodiment of the present invention, the chemical compositions of the toughening modifier, the stability enhancer, the heat conduction auxiliary agent, and the additive may have the same chemical compositions as the corresponding components in the polyphenylene sulfide modified material described above, and are not described in detail herein.
According to other embodiments of the present invention, the method for synthesizing the polyphenylene sulfide modified material can be not limited to extrusion molding or single screw extrusion granulation. For example, the polyphenylene sulfide modified material having the above composition can be formed by a molding method or apparatus such as twin screw, banburying, ten thousand horsepower, planetary screw, etc.
In yet another aspect of the present invention, a thermally conductive plastic tube is provided. The heat-conducting plastic pipe comprises the polyphenylene sulfide modified material. Therefore, the heat-conducting plastic pipe has all the characteristics and advantages of the polyphenylene sulfide modified material, and the details are not repeated. Generally speaking, the heat-conducting plastic pipe can be applied to a severer chemical environment.
The invention will now be illustrated by means of specific examples, which are provided for illustration only and should not be construed as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Example 1
100g of PPS and 5g of PA were put in a high-speed mixer and subjected to high-speed mixing for 15 min. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 2
100g of PPS and 30g of PA were put in a high-speed mixer and subjected to high-speed mixing for 15 min. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 3
100g of PPS and 10g of PA were put in a high-speed mixer and subjected to high-speed mixing for 15 min. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 4
100g of PPS and 5g of PTFE were put into a high-speed mixer and subjected to high-speed mixing for 15 minutes. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 5
100g of PPS, 5g of graphene and 2g of additive are added into a high-speed mixer and mixed for 15min at a high speed. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 6
100g of PPS, 30g of PA and 30g of silicon carbide powder were put into a high-speed mixer and mixed at a high speed for 15 minutes. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 7
100g of PPS, 30g of PA, 2g of carbon fibers, 18g of silicon carbide powder and 2g of additives were put into a high-speed mixer and mixed at a high speed for 15 minutes. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Example 8
100g of PPS, 15g of PA, 10g of PTFE, 10g of graphene, 1g of carbon nanotubes, 2g of carbon fibers, 10g of silicon carbide powder and 2g of additives were put into a high-speed mixer and mixed at a high speed for 15 minutes. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Comparative example 1
100g of PPS and 60g of PA were put in a high-speed mixer and subjected to high-speed mixing for 15 min. And (3) adding the uniformly mixed materials into a single-screw extruder for extrusion, and treating the rear end of the extruder by using a granulator to obtain the modified PPS master batch. The master batch is put into an extruder to obtain the modified PPS pipe through the processes of extrusion, pressurization and cooling.
Performance testing
The master batches obtained in examples 1 to 7 were tested for their properties. Wherein the tensile strength is tested in GB/T1040-2006. Thermal conductivity was tested in accordance with ASTM E1461. Wherein the strength retention ratio is: the retention of tensile strength after immersion of the pipe obtained in the above example in the reagent shown in table 1 below for 48 hours with the reagent heated to 93 degrees celsius was followed.
TABLE I summary of Performance of various examples
TABLE II comparative example Performance summarises
| 1 | |
| Tensile Strength (MPa) | 67 |
| Coefficient of thermal conductivity (W/m. K) | 0.2 |
| 37% hydrochloric acid | 96 |
| 30% nitric acid | 65 |
| 30% sulfuric acid | 90 |
| 30% sodium hydroxide | 83 |
| Toluene | 77 |
As can be seen from table 1, the pipes of all the examples can maintain good strength in high-temperature acid, alkali and organic environments, i.e., the pipes obtained in all the examples have good corrosion resistance. Meanwhile, the pipes of the embodiments 1 to 7 have better tensile strength and thermal conductivity, and can maintain excellent mechanical property and thermal conductivity of the PPS material. In particular, in example 7 in which the number of types of heat transfer aids was large, the heat conductivity was improved by more than 20 times as compared with the conventional PPS material.
As can be seen from table 2, when the amount of PA added is too high (see comparative example 1), although the fluidity and tensile properties of the PPS resin can be improved to some extent, PA does not contribute to the thermal conductivity of the mixed resin, and since the PA resin itself has poor acid-base resistance, a swelling reaction easily occurs in an organic solvent, which not only easily causes a decrease in the acid resistance of the modified material, but also easily causes a great decrease in the strength of the mixed resin after the acid-base weather resistance test. In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A modified PPS master batch is characterized by comprising 100g of PPS, 15g of PA, 10g of PTFE, 10g of graphene, 1g of carbon nanotubes, 2g of carbon fibers, 10g of silicon carbide powder and 2g of additives.
2. A method of preparing the modified PPS masterbatch of claim 1, comprising:
the raw materials are mixed at a high speed according to the proportion, and the raw materials subjected to high-speed mixing are extruded and granulated to form the modified PPS master batch.
3. A modified PPS pipe comprising the modified PPS masterbatch of claim 1.
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| CN102391648A (en) * | 2011-09-23 | 2012-03-28 | 博山水泵制造厂 | Polyphenylene sulfide compound material, and preparation method and application thereof |
| CN102702747A (en) * | 2012-06-14 | 2012-10-03 | 南京同辉新型材料科技有限公司 | Insulating and heat-conducting high polymer and preparation method thereof |
| JP2014091826A (en) * | 2012-11-07 | 2014-05-19 | Kaneka Corp | Thermally conductive molded body |
| CN105647037A (en) * | 2016-03-01 | 2016-06-08 | 苏州科茂电子材料科技有限公司 | Cable sheath material resistant to acid and base corrosion and preparation method of cable sheath material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391648A (en) * | 2011-09-23 | 2012-03-28 | 博山水泵制造厂 | Polyphenylene sulfide compound material, and preparation method and application thereof |
| CN102702747A (en) * | 2012-06-14 | 2012-10-03 | 南京同辉新型材料科技有限公司 | Insulating and heat-conducting high polymer and preparation method thereof |
| JP2014091826A (en) * | 2012-11-07 | 2014-05-19 | Kaneka Corp | Thermally conductive molded body |
| CN105647037A (en) * | 2016-03-01 | 2016-06-08 | 苏州科茂电子材料科技有限公司 | Cable sheath material resistant to acid and base corrosion and preparation method of cable sheath material |
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