Comparison of polyimide films at home and abroad

Market and technical analysis of polyimide

In 2007, the global annual consumption of polyimide (PI) was about 60,000 tons, and the United States, Japan and Europe were the most important PI consumption markets in the world. In 2007, the consumption of polyimide in the United States, Japan and Europe was about 6.5438+0.8 million tons, 6.5438+0.6 million tons and 0.7 million tons respectively. Experts predict that the global demand for polyimide will increase by 6% every year, and the total consumption will reach about 80,000 tons by 20 12.

In 2007, the global annual consumption of polyimide (PI) was about 60,000 tons, and the United States, Europe and Japan were the most important PI consumption markets in the world. In 2007, the consumption of polyimide in the United States, Europe and Japan was about 6.5438+0.8 million tons, 6.5438+0.6 million tons and 0.7 million tons respectively.

Experts predict that the global demand for polyimide will increase by 6% every year, and the total consumption will reach about 80,000 tons by 20 12.

PI is one of the organic polymer materials with the best comprehensive performance, which has been widely used in aviation, aerospace, microelectronics, nanotechnology, liquid crystal, separation membrane, laser and other fields. The research, development and utilization of polyimide are listed as one of the most promising engineering plastics in 2 1 century by various countries. Because of the characteristics of polyimide in performance and synthetic chemistry, polyimide is also widely used. There are dozens of polyimides, including engineering plastics, fibers, films, advanced composite materials, foam plastics, adhesives, separation films, alignment agents for liquid crystal display, etc.

At present, the consumption composition of polyimide is different in different countries and regions. The main consumption field in the United States is plastics, accounting for about 80% of the consumption. The main consumption area in Europe is enameled wire paint, accounting for 70% ~ 80% of the consumption; Japan's main consumption areas are films and plastics, accounting for about 95% of the total consumption.

The high-end fiber market has great potential.

Among many kinds of special engineering plastics, polyimide is relatively expensive because of its superior high temperature resistance and tensile strength. However, it is still difficult to replace other materials with PI in areas with low performance requirements.

According to incomplete statistics, there are about 50 major polyimide manufacturers in the world, including DuPont, Mitsui East Asia and Ube.

It is understood that the main fiber varieties competing with polyimide fibers are PTFE (polytetrafluoroethylene), PPS (polyphenylene sulfide), glass fiber and Nomex (aramid fiber). Due to the different properties of each fiber, the application fields and application environments are also different, but from the related properties, PI fiber has obvious competitive advantages.

High-temperature filter material is mainly used in the field of bag dust removal in environmental protection industry, which is closely related to steel, metallurgy, cement, chemical industry, electric power, garbage incinerator and so on. It is the general trend that bag dust removal replaces electric dust removal.

With the country's increasing attention to environmental protection, the government and private capital have invested more and more in this field, and the environmental protection industry has therefore shown a trend of rapid development. Compared with 2008, in 2009, the high-temperature filter materials increased greatly, especially the high-end products developed rapidly. In 2008, among the total output of filter media in China, low-end filter media accounted for about 40%, middle-end filter media accounted for about 40%, and high-end filter media accounted for about 20%. There is huge room for future development.

The film market will continue to grow at a high speed.

In China, more than 90% of PI products are films. By 2009, the scale of Pl membrane has reached about 4,700 tons/year, and there are more than 40 manufacturers with an annual output of 2,000-3,000 tons. More than 90% domestic enterprises adopt ordinary tape casting method, and the products are low-end, which are mainly used in two major fields: insulating materials and flexible copper clad laminate (FCCL).

At present, more than 90% of Pl films in China are used in the field of insulating materials, and the annual consumption is 2000-3000 tons. Application fields include locomotive, motor, nuclear power equipment insulation, high-temperature wire and cable, speaker voice coil skeleton, electromagnetic wire, high-temperature conductor, high-temperature pressure-sensitive adhesive tape, insulation composite material and so on. And the quality requirement of PI film is not high.

Flexible copper clad laminate is the main material of flexible printed circuit board (FPC), which is widely used in electronic industry, automobile industry, information industry and various national defense industries. In this field, polyimide film is mainly used as insulating base film and FPC high temperature adhesive tape. The rapid growth of home appliances to the countryside, 3G communication, information home appliances and automotive electronics has become the driving force for the development of FCCL market.

However, more than 85% of polyimide films used in FCCL field in China are imported, and the annual import volume is 800~900 tons. Only Piaoyang Huajing, Jiangyin Tianhua Technology, Wuxi Gaotuo and Shandong Wanda Microelectronics Materials Company can produce it in China.

Take 12.5nmPI biaxially stretched film in electronic field as an example. The highest quotation of enterprises in China is about per kilogram 1500 yuan, and the general quotation is only a few hundred yuan, while the quotations of Japanese DuPont and Ube Co., Ltd. are all above 3,000 yuan. In the field of thermal insulation materials, the price of domestic PI film is generally per kilogram 10 ~ 30 yuan, while the price of imported products is 1800~3000 yuan.

With the rapid development of electronics industry in China, it is predicted that the PI film market in China will grow at an average annual rate of more than 12% in the next few years, and the demand for PI films in China will reach about 5,000 tons in 20 13 years.

Insufficient production capacity and high cost

There are many kinds and forms of polyimide, and there are many synthetic methods, which can be selected according to various application purposes. This flexibility in synthesis is also difficult for other polymer materials.

From the research of historical documents, the cost data is not transparent because of the limited details of polyimide in various countries. It can be seen from the relevant data of Shenzhen Huicheng that the raw materials of polyimide mainly include dianhydride, diamine, isomeric dianhydride, dimethylacetamide, deionized water and so on.

Among them, at present, pyromellitic dianhydride (PMDA) is mostly produced by pyromellitic dianhydride with vanadium and titanium oxide as catalyst. Although there are several PMDA manufacturers in China, their production capacity is insufficient 1 10,000 tons. The market gap still needs to be imported, and maleic anhydride production is mainly concentrated in a few large companies such as DuPont and Hearst. It is understood that the current domestic PMDA quotation ranges from 52,000-56,000 yuan/ton, while the raw material of one ton of polyimide is about 0.5 ton.

Diamines are diphenyl ether diamines (ODA), which are mainly used as raw materials and crosslinking agents for polyimide resins, polyamide resins and epoxy resins. At present, the domestic ODA output is small, about 1 10,000 tons a year, and the price is about 78,000 yuan/ton.

In addition, isomeric dianhydride also includes isomeric BP-DA, isomeric ODPA and isomeric TDPA. Dimethylacetamide (DMAC) is a colorless and transparent flammable liquid, which is mainly used as a solvent for heat-resistant synthetic fibers, plastic films, coatings, medicines and acrylonitrile spinning. The current market price is 6.5438+0.08 million yuan/ton.

According to the above single cost estimation, the cost per ton of polyimide is about 80,000 yuan/ton.

New production technology was successfully introduced.

Polyimide products can be used in automobile and airplane engines, communication instruments, engineering machinery, industrial machinery, commercial equipment, electronic appliances and microelectronics, analytical and medical equipment, transmission and textile equipment and other fields.

Because of its high price, it still has crowding-out effect in some application fields. The new synthesis process of polyimide and its products developed by Changchun Institute of Applied Chemistry has changed the traditional synthesis method of polyimide and opened up a new reaction path for the synthesis of polyimide from chlorophthalic anhydride. Comprehensive calculation shows that the new process can reduce the production cost of polyimide by more than 30%.

At present, only American General Electric (GE) Company uses nitrophthalimide as raw material to produce polyetherimide, and the scale has reached 10,000 tons. However, there are a lot of waste acids in the route of producing polyetherimide from nitrophthalimide, and it is difficult to synthesize polyimide directly because of the purification with organic solvents. The by-product is sodium nitrite, which is not conducive to the reaction, pollutes the environment and cannot produce biphenyl dianhydride. However, all these shortcomings can be overcome by using chlorophthalic anhydride route, so it can be considered that chlorophthalic anhydride route is the most advanced and economical route to produce polyimide in the world.

Definition of polyimide

Polyimide is an aromatic heterocyclic polymer with imide groups in its molecular structure, named PI in English, which can be divided into four categories: homopolyphenylene PI, soluble PI, polyamideimide (PAI) and polyetherimide (PEI). PI is one of the organic polymer materials with the best comprehensive properties, with high temperature resistance above 400℃, long-term use temperature range of -200℃~300℃, no obvious melting point and high insulation performance. In addition, PI, as a special engineering material, has been widely used in aviation, aerospace, microelectronics, nanotechnology, liquid crystal, separation film, laser and other fields, and the research, development and utilization of polyimide are listed as one of the most promising engineering plastics in 2 1 century by all countries.

Polyimide performance

Polyimide resin has excellent comprehensive properties. It has the characteristics of corrosion resistance, fatigue resistance, high temperature resistance, wear resistance, impact resistance, low density, low noise and long service life.

Polyimide type

Because of the characteristics of polyimide in performance and synthetic chemistry, its application is also very extensive, and the forms of polyimide also reach 10. But we mainly analyze five forms: engineering plastics, fibers, films, advanced composite materials and foam plastics. Other forms include foam plastics, adhesives, separation films, and alignment agents for liquid crystal displays.

main products

Engineering plastics: Engineering plastics are divided into thermoplastic resins and thermosetting resins. Thermoplastic polyimide materials are widely used as high-performance materials because of their non-melting characteristics. Thermosetting engineering plastics have excellent processability and high performance. Among them, polyimide special engineering plastics have high glass transition temperature (243℃) and melting point (334℃), and the thermal deformation temperature under load is as high as 3 16℃, which can be used for a long time at 250℃. PI resin not only has better heat resistance than other high temperature resistant plastics, but also has high strength, high modulus, high fracture toughness and excellent dimensional stability.

Fiber: polyimide fiber, also known as aramid fiber, is divided into two categories: ordinary heat resistance and high strength. The former is used for high temperature medium, main cable sheath, fire suit and other filter materials. The mechanical properties of the latter can reach the level of carbon fiber, which is a reinforcing agent for advanced composite materials and can also be used for bulletproof vests and other protective shields. At present, it is widely and urgently used to make high-temperature filter materials. Among them, the core key of bag dust removal device widely used in domestic market-high temperature resistant filter material, PPS fiber is widely used at the bottom, and all high-end polyimide fibers are imported.

Film: 196 1 year, DuPont produced PI film for the first time. At present, the production technology of PI film in the world is mainly concentrated in three major manufacturers: DuPont Company of the United States, Ube Company of Japan and Zhongyuan Chemical Company of Japan.

Advanced composites: polyimide composites are the most heat-resistant resin-based composites, mainly used in aerospace and so on.

Foam: Polyimide foam is one of the foam materials with the best thermal stability among polymers. It can withstand the temperature of 250℃~300℃ for a long time and the high temperature of 400℃~500℃ for a short time. It has a history of nearly 40 years since it was successfully developed in 1970s. Polyimide foam can be divided into thermosetting polyimide foam and thermoplastic polyimide foam according to structure.

From a global perspective, only the Austrian company Evonic has mastered the core technology of polyimide and realized industrialization. Moreover, compared with Evonic, the process of synthesizing polyimide by dianhydride and diamine has lower cost, and the exclusiveness of technology, insufficient market competition and integration make the company scarce.