Application of 7. high temperature nylon

Because HTPA can provide a heat distortion temperature of more than 270 ℃, it is an ideal engineering plastic for heat-resistant parts in the automotive, mechanical, electronic/electrical industries. At the same time, HTPA is also an ideal choice for parts that must maintain structural integrity at high temperatures for short periods of time.

Application of 7.1 in Electrical and Electronic Industry

Because under certain conditions, due to the trend of miniaturization of electrical equipment or the increase of operating current, the temperature of its internal components will rise quite high. Therefore, the material is required to have a high long-term use temperature and low creep at high temperature. In the motor parts, circuit breaker internal components, winding components, such as: frame and switch, high temperature nylon has the advantages of economic and practical, in terms of cost performance can compete with PPS, PEI, PES and LCP and other materials.

The continuing trend towards miniaturization of integrated circuit boards has led to smaller, thinner-walled surface mount components. These electronic components are sensitive to high peak temperatures in modern reflow soldering processes, requiring the use of materials with high heat distortion temperatures.

In particular, the development of surface mount technology (Surface Mount Technology referred to as SMT), connectors, switches, relays, capacitors and other electrical components are installed and connected on the circuit board at the same time, promoting the miniaturization and intensification of electronic components, and reducing the engineering cost by 20-30% compared with previous products.

However, the use of SMT technology, each electrical component and circuit substrate to be heated in the infrared heating device at the same time, the material made of each component and circuit board reflow resistance and dimensional stability put forward higher requirements. In order to reduce environmental pollution, the use of lead-free solder is now strongly advocated, and lead-free processes are widely implemented.

Before the lead-tin solder melting point at 183 ℃, the new type of solder for tin-copper-silver solder, melting point of 215 ℃, the melting point of the previous material increased by 30 ℃, then PA66, PBT and other materials can not meet the requirements of heat resistance, so the development of higher heat resistance materials become inevitable. High temperature nylon has high temperature stability, excellent toughness and excellent fluidity and high crystallinity, so it can provide economical material solutions and meet the latest design requirements of all such end markets.

The high heat distortion temperature allows the plastic element to maintain dimensional stability during the welding process. High-temperature nylon connectors can maintain their dimensional consistency at soldering temperatures up to 260°C, while other high-performance plastics do.

If a motor of equal power or greater power is miniaturized, its temperature may rise significantly depending on the design. Overload or rotor lock will cause a sharp rise in temperature, more than 250 ℃. In order to give full play to the effect, the motor is required to have a certain degree of safety.

High temperature nylon can ensure that it can withstand the heat generated by the normal operation of the motor and overload conditions, and has been successfully applied to various parts of the motor, including: end laminations, brush brackets, gears and end brackets. Due to its outstanding intrinsic properties, high temperature nylon has been successfully used in the following fields and markets:

1. Connector

2. Circuit breaker

3. Winding

4. SMD components

5. Micro switch

6. Motor parts

7, Computers and Auxiliary Equipment

8. The Communications Industry

9, Electrical Products and Household Appliances

10, Consumer Electronics

Application of 7.2 in Automobile Industry

In the automotive industry, heat-resistant plastics are rapidly replacing traditional engineering plastics. The driving force behind this development is mainly derived from the requirements of the three major development trends in the automotive industry:

1. Improve safety, comfort and motor management;

2, require a longer warranty period and service life;

3. Solve the problem of high temperature in the engine area.

In particular, the solution to environmental problems such as the reduction of CO2 emissions and the improvement of fuel consumption in the automotive industry is to increase the combustion temperature of the engine to fully burn the fuel. This will inevitably increase the temperature in the engine room and increase the resistance of all plastic materials. Heat requirements.

At the same time, the plasticization of metal parts such as the fuel system, exhaust system, and cooling system near the engine has been replaced by thermosetting resin for the purpose of recycling, and the requirements for materials are more stringent. The heat resistance, durability and chemical resistance of the previous general engineering plastics have not reached the requirements.

From an economic point of view, the high-temperature nylon series has proven to be an ideal metal replacement material. It has very good creep resistance, mechanical strength, rigidity and fatigue resistance at high temperatures, while maintaining the well-known advantages of plastics, namely easy processing, limited post-finishing requirements and freedom to develop complex and integrated functional parts to reduce weight and reduce noise and corrosion resistance.

On the other hand, because high-temperature nylon can withstand high strength, high load, high temperature resistance and work in harsh environments, it is very suitable for engine areas (such as engine covers, switches and connectors) and transmission systems (such as bearing retainers), Air systems (such as exhaust control systems) and air intake devices.

In short, the excellent characteristics of high-temperature nylon can bring many benefits to users, and when converting from PA6, PA66 or PET/PBT materials to HTPA, there is basically no need to modify the mold, etc., so it has a broad prospect in various applications requiring high temperature resistance.

Development of high temperature nylon abroad in 8.

8.1 DuPont Zytel HTN

DuPont Zytel HTN is 51G, 52G, 53G and 54G series, of which 51G, 52G and 54G are modified products belonging to 6T and belong to semi-aromatic nylon PPA, while 53G series is classified as high-performance nylon due to its less benzene ring content in the molecule. The melting point is 310 ℃, the glass transition temperature is 140 ℃, and the heat distortion temperature HDT is 288 ℃.

DuPont HTN between the four series of performance characteristics are different, the following is a specific description:

HTN 51 Grades,PA6T/DT, extremely high temperature resistance, long-term use temperature at about 150 ℃, excellent chemical resistance to oil hot mold.

HTN 52 Grades,PA6T/66, taking into account both performance and processability, has good mechanical retention under thermal, chemical and humid conditions, thermal deformation temperature can reach more than 280 degrees, SMT compatibility is better than reflow soldering ability, and electrical performance is superior.

HTN 53 Grades,PPA, provides better hardness and toughness under moderate temperature conditions (long-term temperature resistance is only about 65 degrees). The mold can be controlled by water temperature and has excellent surface properties.

HTN 54 Grades,PA6T/XT PA6T/66, improved from 52G series to increase toughness and improve mechanical properties under wet conditions.

8.2 Switzerland Far East EMS

EMS has introduced a semi-aromatic nylon resin with the registered trademark "Grivory", which is a semi-crystalline resin made by the polymerization of aromatic acids such as hexamethylenediamine, terephthalic acid or isophthalic acid. These new resins are not affected by moisture (nylon is usually hygroscopic), have excellent high barrier properties, and are suitable for multi-layer packaging materials; have high stiffness, and can be used as metal replacement materials; have high heat resistance, at 120 ℃ It does not affect its stiffness and strength, and can be used for processing electronic component connectors; and for processing various parts under the automobile engine cover.

Grivory series of GrivoryG4V grades, the use of 6I/6T mixture of terephthalic acid and isophthalic acid mixture mixed with 20% ~ 60% of the glass fiber manufacturing, is a tough, high liquidity grade materials, processing products have excellent surface texture. The G4V grade is comparable to reinforced MXD6 nylon materials such as Mitsubishi's Reny and Sonyville's Ixef. Under the condition of mold temperature of 176 degrees Fahrenheit, G4V grade material reinforced with 50% glass fiber shows 70% gloss, while MXD6 has only 30% gloss.

In addition, G4V also has better impact strength. Applications include office equipment, automotive interior and exterior parts. Other new grades of semi-aromatic nylon series materials include an ultraviolet stable grade and a flame retardant grade. The latter is added with high-temperature polyphthalamide (PPA) material, of which PPA is Zytel HTN produced by DuPont or Amodel produced by Sonyville. GrivoryXE3876 grade nylon is a 30% glass fiber reinforced 6T/66 copolymer, free of halogen and red phosphorus. Can be applied to lead-free soldering.

GrivoryGV-5HL grade is anti-ultraviolet grade, made of 6I/6T copolymer containing 50% glass fiber reinforcement, which has the advantages of weather resistance and outdoor gloss retention. Applications for this grade include housings for communications equipment, as well as lawn and garden guardrails and benches.

Mitsui Mitsui 8.3 Japan

ARLEN is a high temperature resistant nylon developed by Mitsui Chemical Company of Japan. ARLEN A series products are divided into PA6T/6I and C series products are divided into PA6T/66.

ARLEN's main characteristics are excellent high-temperature rigidity, dimensional stability and chemical resistance. It also has thermoplastic plastic properties. It is easy to form during injection and is not easy to burr. It also makes it a super engineering plastic with high added value. It can add carbon fiber, glass fiber and change colors to meet the needs of customers. Tm reaches 310 ℃. Tg is 85~125 ℃.

Excellent characteristics make it widely used in motor/electronic parts (SMT process), various parts under the hood of the car. The application of ARLEN to electronic connectors is affirmed by customers for its low water absorption. Compared with PA46,ARLEN has low water absorption, and ARLEN has higher reflow resistance temperature when passing SMT. In addition, the rubber core of electronic connector is usually inserted into the terminal, which is more important in mechanical strength and toughness. Compared with PA9T,ARLEN has better toughness than 9T, and PA9T is easier to crack.

8.4 Germany BASF

BASF's Ultramid T series is a polyamide molding compound based on PA6/6T. It has excellent mechanical and electrical properties and low water absorption.

Due to their good properties, these materials have become indispensable materials for many components and machine parts in almost all engineering fields (e. g. as high-quality electrical insulation materials) and many special applications. A semi-aromatic high temperature polyamide product Ultramid T KR4357 G6 is currently being used in new fields.

A Raymond, an international supplier of curing systems for the automotive industry based in France, is currently using special chemicals (PA6/6T) from BASF for quick connectors in fuel pipes. These connectors are equipped with outflow barriers. Almost any car or truck manufacturer in Europe uses this quick connector. Such small parts are being manufactured by high precision injection molding processes. These parts, weighing only 15 grams, are fuel and zinc chloride resistant at high temperatures (130°C).

The special advantage of Ultramid T KR in this application is not only its low creep but also its excellent rigidity and toughness, which means that it can even withstand the impact of flying stones. These properties make it clearly superior to polyamide 66 and has the potential to replace polyamide 12.

In addition, BASF's halogen-free and high-temperature resistant nylon Ultramid T KR4365 G5 product uses red phosphorus for fire prevention. It is mainly used for applications that require good mechanical properties and high electrical tracking resistance, and accept plastic inherent red or tend to choose black. It is especially suitable for welding in high temperature environments.

Solvay 8.5 United States

Amodel PPA (poly p-phenylene terephthalamide) introduced by Solvay Company in the United States was commercialized in 1991. It is a high-temperature nylon with excellent mechanical properties. Its thermal deformation temperature is 280 ℃ and its continuous service temperature can reach 170 ℃, which can meet the required short-term and long-term thermal properties.

It can maintain its excellent mechanical properties-strength, stiffness, fatigue resistance and creep resistance-in a wide temperature range and high humidity environment. It also has excellent chemical resistance and low water absorption. Can provide low temperature impact resistance, flame retardant, ethylene glycol resistance, can be sprayed and can be plated and other special grade. It can be used in automobiles, kitchenware, home appliances, various thin-walled electronics, electrical components, etc. Its excellent performance of high temperature resistance and ethylene glycol resistance is especially suitable for thermostat housings.

It is worth mentioning that SOLVAY (Suwei) company launched the AMDEL; halogen-free flame retardant specifications FR-4133 better reflected in the market.

8.6 Germany Evonik VESTAMID®HTplus

VESTAMID of the new members of Evonik's VESTAMID series of materials®HTplus has been specially developed as a substitute for metal materials in traditional metal products. VESTAMID HTplus material is a polyphthalamide (PPA)-based semi-crystalline material VESTAMID of the new members of Evonik's VESTAMID series of materials.®HTplus has been specially developed as a substitute for metal materials in traditional metal products, especially suitable for high temperature use, with high cost performance.

IX. Development Status of High Temperature Nylon in China

Part of the domestic high temperature nylon research in the laboratory is almost synchronized with the world, due to various objective reasons have been unable to achieve industrialization. The catalysis of the rapid development of the market in recent years has made many companies look to this field.

9.1 Pingmei Shenma

At present, the leading enterprise in the domestic nylon market is mainly Pingmei Shenma. The company has formed a whole industrial chain from coking benzene to nylon 66 salt to downstream cord cloth and nylon resin, and maintains a good cooperative relationship with Invida of the United States. At present, the company has an annual production capacity of 300000 tons of nylon 66 salt, 130000 tons of nylon industrial yarn and cord fabric, 150000 tons of engineering plastics and 11000 tons of airbag wire.

As the core raw material of PA66 adiponitrile has been monopolized by the British and American countries, there is no domestic production capacity. Shenma's adiponitrile has been imported. In 2012, it suffered a large loss. Apart from chlor-alkali loss of more than 0.2 billion, the high price of adiponitrile caused PA66 to lose nearly 0.1 billion.

At the beginning of 2013, Zhongping Energy Group signed a strategic cooperation agreement with the world's number one hexanedinitrile manufacturer, Invista, which completely prevented the recurrence of flour being more expensive than bread in 2012 and fundamentally guaranteed Shenma PA66 profit.

The preparation methods of adiponitrile are mainly acrylonitrile electrolysis method and butadiene method. Acrylonitrile electrolysis is a relatively old technology, energy consumption is relatively large, purification is more difficult. Shandong Runxing solved the problem of purification, but could not achieve industrial mass production. The butadiene method is a method used by leading manufacturers such as Invida, which is known as green and environmentally friendly, with low energy consumption and low cost.

For a company like Shenma that lives on hexanedinitrile, the butadiene method is the only choice. Because of the technical difficulty, the patent of the technology has been registered by foreign enterprises in China. Therefore, the breakthrough in this technology must take more time to find a new way.

At present, Shandong Runxing Chemical Technology Co., Ltd. has an annual output of 100000 tons of hexanedinitrile project. The overall project delivery ceremony was held as scheduled in May this year. The project is the first set of technology in China, filling the gap in domestic production, and the overall technology has reached the international advanced level.

In addition, Chongqing Ziguang has also applied for a pilot project of adiponitrile, including a 500-ton/year adiponitrile plant (trial production stage) and a 250-ton/year acrylonitrile electrolysis adiponitrile plant (trial production stage).

The breakthrough of adiponitrile technology is of great value to Shenma or the whole nylon chemical industry in China. For Shenma, you can enjoy the amplification of their own PA66 production capacity, reduce costs, to seize more international markets.

Even according to the lowest estimate, the cost of PA66 is reduced by 10% after adiponitrile breakthrough, that is, 2500 to 3000 yuan, and 350000 production capacity means an increase of 8 to 1 billion in profits. In 2015, with the release of 200000 tons of adiponitrile production capacity in Shanghai and 200000 tons of Shandong Runxing production capacity will significantly lower the price of domestic adiponitrile, Shenma's profits will only get better and better, I believe in the field of high-temperature nylon can also go further and further.

9.2 Shanghai Jiesijie

Shanghai Jieshijie Company has introduced HPN, which is a semi-aromatic polyamide made by polycondensation of terephthalic acid and 1,6-hexanediamine. HPN products have obvious leading advantages in heat resistance. The thermal deformation temperature of enhanced modified products is 270~295 ℃. The characteristics of HPN products are as follows:

1, green biological materials, renewable rate of 50%;

High heat resistance, the maximum heat resistance temperature of 295 ℃;

3, rapid crystallization, shorten the molding time, improve production efficiency;

4, low moisture absorption, good dimensional stability;

5, excellent mechanical properties, with obvious high strength, high rigidity and other performance advantages;

6, chemical resistance, especially with chemical resistance, freezing liquid and other properties;

7. Good fluidity in molten state, easy to process, excellent apparent quality of processed products, and small size parts can be made;

8. Good flame retardancy, can produce halogen and halogen-free flame retardant products, GWIT up to 960/2.0.

In addition, the company has also developed HPN resin, HPN enhanced modified products, HPN enhanced flame retardant products and other brands of products, these products have good high temperature resistance, and have high strength, low moisture absorption, good dimensional stability characteristics, can be applied to automotive engine peripheral parts, electronic and electrical products connectors, connectors, circuit breakers and other components.

9.3 Blonde Technology

The special engineering plastic product (PA10T) developed by Kingfa Technology is a new generation of nylon products with high temperature resistance and low water absorption. It has taken the lead in the commercialization of PA10T in the world and formed a relatively complete industrial chain from resin synthesis to modification. It has been widely used in the fields of electronic appliances, automobiles, home appliances and tools.

At present, the domestic demand for this product is about 70000 tons, and the global demand is about 200000 tons. The company's sales volume in 2014 is about 2000 tons. The company's products are still mainly aimed at the domestic market and have certain cost and price advantages. High temperature resistant nylon PA10T material gross profit is higher, about more than 30%, due to the monopoly of foreign manufacturers, the company successfully developed the product is expected to replace imports, and now the company has successfully expanded production.

Some other enterprises have also invested in the development of halogen-free flame retardant high-temperature nylon, and have achieved effective results in PA6T and PPA, but only in mixing modification, and the matrix resin comes from overseas suppliers.

Development Trend of High Temperature Nylon in 10.

Market demand can promote the development of an industry, there is demand will have the power of production, so as to promote the progress of the industry. As the demand for high-temperature nylon in China continues to rise, the amount is increasing year by year, and it is expected that China's demand for high-temperature nylon will grow at a rate of 15% to 25% in the next few years.

Moreover, China's nylon market is very broad and has considerable development prospects in the future, but the market share of domestic products is not very high, mainly due to technical barriers and brand building. As a local enterprise, in the future development to be committed to the development of new product performance and to other areas of development.