High temperature resistant nylon refers to the nylon material that can be used in the environment above 150℃ for a long time. The melting point is generally 290℃~320℃, and it maintains excellent mechanical properties in a wide temperature range and high humidity environment. High temperature resistant nylon has good wear resistance, heat resistance, oil resistance and chemical resistance. Compared with ordinary nylon, the water absorption and shrinkage of raw materials are also significantly reduced, showing excellent dimensional stability and excellent mechanical strength. With the rapid development of 5G related industries, high-temperature resistant nylon is expected to further expand the application in downstream markets.
Automobiles are the traditional application area, while 5G is the growth area
Among the common high temperature resistant nylon, PA46(aromatic), PA6T and its copolymer, PA9T are common. As a product developed by Jinjin, PA10T is not common in other enterprises, but its capacity of 10,000 tons makes it still occupy a relatively important position in high temperature resistant nylon.
Because high temperature nylon can withstand high strength, high load, high temperature resistance and other harsh environments, so it is very suitable for engine areas (such as bonnet, switches and connectors) and transmission systems (such as bearing cages), air systems (such as exhaust control systems) and intake devices and other parts of the application. This is currently the main application field of high temperature resistant nylon.
With the spread of 5G application in China, the application of high temperature resistant nylon has been paid more attention. For example, 5G Acer station generally has three sides of AUU, one side of AAU vibrator number is 64-128, the number of vibrator demand is greatly increased. The plastic antenna vibrator is made of high temperature resistant electroplating engineering plastics as raw materials by integrated injection molding to produce the vibrator body with a predetermined structure. It is necessary to configure high precision and high speed machine to achieve good injection molding of plastic vibrator. Plastic vibrator has the advantages of high precision, high integration, strong plasticity, low weight and low cost. As a new type of vibrator, it is applied in 5G acer station to reduce the weight of antenna and improve production efficiency.
In the design of the new antenna vibrator, there are two solutions. One is the combination of LDS materials and metal materials. The antenna vibrator is made of LDS material, and the back is made of metal material to reduce the cost. There is no need to do electroless plating in all places. Second, the use of PPS or LCP electroplating requires SMT reflow welding, so the selection is basically high temperature engineering plastics, which requires high temperature resistant nylon to play a role in it.
High temperature resistant nylon is expected to replace metal materials in automobiles
The bending modulus of PPA material is 20% higher than that of nylon, and the hardness is higher, which can withstand long-term tensile creep. PPA is more resistant to gasoline, oils and coolants than PA.
PPA can be reinforced with carbon fiber and glass fiber for better material properties. The advantage of these new materials is that they can safely replace aluminium and magnesium without loss of stiffness and strength, and have electrical conductivity.
If PPA is reinforced by carbon fiber, after modification, due to low water absorption, high dimensional stability, good chemical hydrolysis resistance, high strength and modulus, it can be used to manufacture automotive structure parts of body, chassis and power system, pumps, fans, gears and compressors in industrial applications, as well as stable ultra-light parts in consumer electronics.
The mechanical properties of PPA can be adjusted through the selection, content and additive technology of carbon fiber and glass fiber. Nappan Shinwood PPA grade A201X35 contains 35% glass fiber filling with high toughness, high stiffness, high mobility, and superior strength and modulus to magnesium or aluminum at 80°C(conditions). Producing parts from magnesium or aluminum requires additional post-processing and tools, which increases the cost of materials. The new PPA material has the opportunity to reduce weight by 25-30%.
These properties of PPA materials facilitate functional integration and weight reduction in different industries. For example, by reducing the weight of structural components or powertrain, it can improve the endurance of vehicles equipped with electronic drive or fuel cell engines; Thin and precise structures in consumer electronics benefit from the high stiffness and strength of PPA materials, excellent dimensional stability, very low weight and excellent machining performance; Due to the CF enhanced PPA has good dimensional stability and high chemical resistance, heat resistance and wear resistance, it can easily produce pumps, compressors and other heavy, high load, durable industrial equipment.
The development direction of electrical components is miniaturization and high-temperature unity, the superior performance of PPA can be used. Flame-retardant PPA has excellent electrical properties, high HDT value, high temperature bending modulus, thin wall parts can be processed with minimal overflow, suitable for switchgear, connector, brush holder and motor bracket production.
Mineral filler grade PPA is used for reflective surfaces and gold plating, including automotive headlights, decorative fittings and hardware. Unenhanced impact modified PPA has excellent mechanical equilibrium and high temperature properties, exceptional toughness and these properties are very little affected by humidity, including oilfield components, military supplies, sporting goods, fan impellers, gears and personal safety products.
High temperature resistant nylon variety
PA46
PA46 is an aliphatic polyamide formed from the condensation of butylenediamine and adipic acid. Compared with PA6 and PA66, PA46 has more amides in each chain of a given length and more symmetrical chain structure, which makes its crystallinity up to 70% and gives it a very fast crystallization rate.
The melting point of PA46 is 295℃, the HDT(thermal deformation temperature) of unreinforced PA46 is 160℃, and after the glass fiber reinforcement, the HDT can reach 290℃, and the long-term service temperature is 163℃. The unique structure of PA46 gives it unique properties that no other material can achieve.
As the full owner of PA46, DSM is gradually transforming its excellent performance into industrialization through continuous modification. While ensuring its high temperature resistance, a variety of special applications such as ultra-wear resistance, ultra-rigid, ultra-high mobility, etc., have been developed. In terms of high temperature resistance, DSM introduced its new high-performance STANYL Diablo on China-plas in 2008. It has long-term heat resistance stability and can work normally at 230℃ for more than 3000 h, while the mechanical properties are reduced by no more than 15%.
PA6T
PA6T is a typical representative of semi-aromatic nylon, which is formed by polycondensation of hexadiamine and terephthalic acid. The melting point of pure PA6T is as high as 370℃, at which temperature nylon has degraded and cannot be thermoplastic formed. Therefore, the PA6T in the market is copolymer or complex with lower melting point after copolymerization with other monomers.
PA6T introduces a large number of benzene rings on the basis of fat chain. Compared with traditional PA6 and PA66, PA6T has higher Tg, lower water absorption, dimensional stability and good heat resistance.
Since PA6T needs to introduce other monomers for copolymerization to reduce the melting process temperature, different monomer proportions become the key to the modification of PA6T. Therefore, it can be said that the high-temperature modification of PA6T has a large development space. Shanghai Jieshijie Company has also successfully developed PA6T series of high temperature resistant nylon, and has been put into production.
PA9T
PA9T, developed solely by KURARAY, is a polycondensation of nonenediamine and terephthalic acid under the trade name Genestar.
Although PA9T is both semi-aromatic nylon, it does not need to be modified by copolymerization to reduce the melting point like PA6T before processing. The melting point of pure PA9T is 306 ℃. The high glass transition temperature (125℃) and high crystallinity of PA9T give it good toughness in high temperature environment. At the same time, it also has incomparable chemical resistance of other PA materials, second only to PPS, and its water absorption rate is only 0.17%, which is the lowest among all PA. The comprehensive performance of PA9T is undoubtedly a better kind of traditional heat-resistant nylon, and with the continuous expansion of production scale, its cost will be close to the cost of ordinary PA, so PA9T is a variety with great development potential.
PA10T
PA10T is made of terephthalic acid and sebacediamine as monomer, after condensation polymerization, has excellent heat resistance, its melting point at 316℃, chemical corrosion resistance, low water absorption, good dimensional stability, glass fiber reinforced modified resistance to lead free solder temperature more than 280℃, excellent comprehensive performance.
Compared with other short chain high temperature nylon, such as PA46, PA4T, PA6T, PA6I, etc., PA10T has a long flexible diamine long chain, which makes the macromolecule have a certain degree of flexibility, and thus has a higher crystallization rate and crystallinity. It is suitable for rapid prototyping and the production of some small electronic components, such as LED reflection bracket and connector.
Moreover, due to the rigidity and corrosion resistance brought by the benzene ring structure in its molecular main chain, the modified products of PA10T can also be applied to some chemical reagents and/or heat resistant environment, such as water treatment, nano injection NMT, engine periphery, etc.
The commercialization of PA10T products has filled the gap of our independent research and development on high temperature nylon new material. The main domestic manufacturers are Shanghai Jieshijie and Jinfa Technology.
PA4T
PA4T is the first synthetic high temperature nylon in the 21st century. It was developed by DSM, which holds the world's only butylenediamine industrialization program. Similar to PA6T, it has a very high melting point (430℃) and is usually copolymerized with other nylon, such as nylon 66 or nylon 6.
This new polymer, the first of its kind in the 21st century, offers excellent spatial stability, lead-free welding compatibility, high melting point, high hardness and mechanical strength at rising temperatures, and exhibits ultra-low water absorption compared to DSM's original PA46 product, or even PA9T.
PA 5T
The melting point of PA5T will be lower than that of PA6T. The main reason restricting its development before is that the industrialization of glutarenediamine is still in the research stage. However, in the second half of 2018, Kaisai Biotechnology in China has successfully put into production 50,000 tons of bioylglutarenediamine, which indicates that the industrialization of PA5T is a step closer.
PA12T
PA12T is a product of dodecarbonate binary amine and terephthalic acid polymerization. China's Henan Junheng has built a demonstration device for PA12T production of 1000 tons/year, and is building a production line for 10,000 tons/long chain dibasic acid.
Synthesis method of high temperature resistant nylon
At present, there are five main synthetic processes in the high temperature nylon industry: high temperature and high pressure solution polycondensation, low temperature solution polycondensation, polyester polycondensation, interfacial polycondensation and direct melt polycondensation.
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