Can someone tell me the current situation of the flame retardant market?

With the development of China's synthetic materials industry and the continuous expansion of its application fields, flame retardants have broad market prospects in chemical building materials, electronic appliances, transportation, aerospace, household furniture, interior decoration, food, clothing, housing, transportation and other fields. In addition, coal fields, oil fields, forest fire fighting and other fields have also promoted the rapid development of flame retardant and fire extinguishing agent production in China. China's flame retardant has developed into the second largest polymer material modification additive after plasticizer. At present, the production capacity is about 200,000 t/a, the annual output is between 6.5438+500,000 t-6.5438+700,000 t, and the annual consumption is about 200,000 t. The insufficient part is mainly imported from the United States and Israel, and the main imported varieties are organic bromine and halogen phosphorus flame retardants. There are more than 60 flame retardant manufacturers in China, which can produce more than 50 kinds of products, mainly bromine and phosphorus, among which bromine flame retardant is the most important series, accounting for about 30% of organic flame retardants in China.

The varieties and consumption of domestic flame retardants are still dominated by organic flame retardants, while the production and consumption of inorganic flame retardants are still less, but in recent years, the development momentum is good and the market potential is great. Halogen flame retardant is the most commonly used flame retardant, which has incomparable efficiency with other flame retardants, but its harm to the environment and people can not be ignored. Environmental protection is the focus of the development and application of additives, so the product structure of flame retardants has been adjusted at home and abroad, and the development of efficient and environmentally friendly flame retardants has been intensified.

1. Application and production status of environment-friendly flame retardant

With people's growing awareness of environmental protection, safety and health, countries around the world began to pay attention to the research, development and application of environmentally friendly flame retardants, and achieved certain results. Flame retardants can be divided into phosphorus flame retardants, chlorine flame retardants, bromine flame retardants and antimony flame retardants, aluminum flame retardants and boron flame retardants according to effective elements. In this paper, according to the effective flame retardant elements, flame retardants are divided into four categories: halogen-free flame retardants, bromine flame retardants, halogen-phosphorus synergistic flame retardants and other flame retardants, and several of them are introduced respectively.

1. 1 halogen-free flame retardant

Halogen-free, low-smoke, low-toxic environmental flame retardant has always been the goal people pursue. In recent years, some global flame retardant suppliers and users have shown great enthusiasm for halogen-free flame retardants, and have also invested a lot of energy in the development of halogen-free flame retardants and flame retardant materials. According to the analysis, the main varieties of halogen-free flame retardants are phosphorus flame retardants and inorganic hydrates. The former mainly includes red phosphorus flame retardant, inorganic phosphorus ammonium polyphosphate (APP), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphate ester and so on. And organic phosphorus halogen-free phosphate. The latter mainly includes modified materials such as magnesium hydroxide, aluminum hydroxide and hydrotalcite. Ammonium polyphosphate and hydrotalcite are the representative products of this series, which have good environmental protection and market prospects. The following is an analysis of these two products.

1. 1. 1 ammonium polyphosphate

Ammonium polyphosphate (APP) is a long-chain inorganic polymer containing phosphorus and nitrogen. The general molecular formula is: (NH4P03) N. Because of its good chemical stability, low hygroscopicity, excellent dispersibility, low specific gravity and low toxicity, APP has been widely used as a flame retardant treatment agent for plastics, rubber and fibers in recent years. It can also be used to prepare intumescent fire retardant coatings for fire prevention treatment of ships, trains, cables and high-rise buildings; It is also used to produce dry powder fire extinguishing agent, which is used for large-scale fire extinguishing in coalfields, oil wells and forests; In addition, it can also be used as fertilizer. The polymerization degree of ammonium polyphosphate is the key to determine the quality of its flame retardant products. The higher the degree of polymerization, the better the flame retardant and fireproof effect. There are already products with polymerization degree over 100 in China, but it is common for APP (ammonium polyphosphate) to have polymerization degree over 500 abroad. The development of ammonium polyphosphate in China began with 1978. After more than 20 years of development, the production of ammonium polyphosphate in China has a certain foundation, which basically meets the domestic market demand. In 2005, the output of ammonium polyphosphate in China exceeded 20,000 t, and a small amount was exported besides meeting domestic demand. China's ammonium polyphosphate production capacity is mainly concentrated in the southwest, east China and south-central regions, of which the southwest region has the largest output, followed by east China and south-central regions. The output of ammonium polyphosphate in North China, Northeast China and Northwest China is very small. The domestic ammonium polyphosphate production facilities are relatively small, the largest being Xinyuan Phosphating Co., Ltd. of Zunyi County and shifang city Changfeng Chemical Co., Ltd., with a plant scale of 3,000 t/a, and the plant scale of Rong Tai has reached 3,000 t/a, followed by Shanghai Xinhua Flame Retardant General Factory with a production scale of 2,000 t/a. The general plant scale is 400- 1000 t/a, and the minimum production scale is only 3,000 t/a.

1. 1.2 hydrotalcite

In the application of inorganic flame retardants, anionic layered functional materials have developed rapidly as flame retardants. It is an inorganic compound with a special structure. M2+ is a divalent ion, usually magnesium, M3+ is a trivalent metal ion, and An- is an anion. This material is called hydrotalcite (LDHs) for short. Because of its unique layered structure, layered composition and adjustable interlayer anions, hydrotalcite has been widely used as inorganic functional materials in catalysis, ion exchange, adsorption, medicine and other fields. As a halogen-free flame retardant with high smoke suppression, hydrotalcite can be widely used in plastics, rubber, coatings and other fields. The development of magnesium anion layered functional materials in China began in the late 1990s. Although the development history is short, it has developed rapidly. 1999 beijing university of chemical technology cooperated with Yixing auxiliary chemical plant to build a 500t/a hydrotalcite production line in Yixing, Jiangsu, becoming the first hydrotalcite production plant in China, forming a set of production technologies with independent intellectual property rights. On this basis, relying on China's superior marine chemical brine resources, a 1000t/a hydrotalcite production line was built in Dalian in 2000, which laid the foundation for further building a larger production plant. From the present situation of magnesium resources in China and the urgent demand and great potential of new flame retardant market, it is not difficult to judge that the time is ripe for the rapid development of magnesium anion layered functional materials in China. In the next five years, China's magnesium anion layered functional materials will enter the peak of development as a substitute for bromine flame retardants.

1.2 Australian flame retardant

Bromine-based flame retardants have been produced and used for more than 30 years. At present, there are about 70 kinds of brominated flame retardants, the most important of which are decabromodiphenyl ether, tetrabromobisphenol A and hexabromocyclododecane (HBCD). The output of the first two products accounts for about 50% of the brominated flame retardants. Under the pressure of increasingly strict environmental protection requirements, some traditional bromine-based flame retardants force users to find substitutes for bromine-based flame retardants, which promotes the advent of new flame retardant systems. The shrinking market of traditional brominated flame retardants such as polybrominated diphenyl ether provides market space for environmentally friendly brominated flame retardants such as brominated epoxy resin and decabromodiphenyl ethane.

1.2. 1 decabromodiphenyl ethane

Decabromodiphenyl ethane (DBPE) was first developed by Albermale Company in the United States. Its relative molecular weight, thermal stability and bromine content are similar to those of DBDPO, but it is not a flame retardant for PBDEs, and it does not produce PBDD and PBDF when burned, which also conforms to the German regulations on dioxin and the regulations of the US Environmental Protection Agency. Moreover, decabromodiphenyl ethane is superior to decabromodiphenyl ether in heat resistance, light resistance and non-dialysis. Its flame-retardant plastics can be recycled, which is a characteristic that many bromine-based flame retardants do not have. At present, the product has been applied in ABS, PBT, PA, HIPS and other engineering plastics, and the effect is good.

The production technology of decabromodiphenyl ethane in China was successfully tested in industrial scale at the end of 2004 and put into the market in 2005. The main producers are Shandong Weidong Chemical Co., Ltd. (5000t/a), Shandong Weifang Dacheng Salinization Company, Shouguang Ocean Chemical Co., Ltd., Jiangsu Shuangling Chemical Group Co., Ltd., Jinan Taixing Fine Chemical Co., Ltd., Suzhou Jinghua Chemical Co., Ltd., Laizhou Laiyu Chemical Co., Ltd., etc. The total production capacity is about11000 t/a. Decabromodiphenyl ethane has a broad prospect in the flame retardant market at home and abroad because of its excellent properties and characteristics.

1.2.2 brominated epoxy resin

Brominated epoxy resin is widely used in flame retardant treatment of engineering plastics such as PBT, PET, ABS, nylon -66, thermoplastic and PC/ABS plastic alloy because of its excellent melt flow rate, high flame retardant efficiency, excellent thermal stability and light stability, and good physical and mechanical properties of flame retardant materials. Brominated epoxy resin can be divided into three types according to the relative molecular weight, low, medium and high, and can be divided into EP type and EC type according to the end group structure, which are used in different plastic materials respectively.

In recent years, brominated epoxy resin has developed rapidly in China, especially because of its low bromine content and small molecular weight, so it can only be used as insulating potting material. At present, brominated epoxy resin technology in China can produce matching products according to the relative molecular weight of flame retardant polymers, thus achieving the best flame retardant effect and excellent flame retardant performance. The main manufacturers are Dongying Guangrao Haifeng Salt Chemical Co., Ltd. (1000t/a), Jinan Taixing Fine Chemical Co., Ltd. and Laizhou Laiyu Chemical Co., Ltd., with a total production capacity of about 3,500 t/a. Among brominated flame retardants, brominated epoxy resin, as a new type of flame retardant, has attracted more and more attention from domestic and foreign markets.

1.2.3 brominated polystyrene

Brominated polystyrene (BPS) is a bromine-based organic flame retardant, which has good mechanical, physical and chemical properties such as high flame retardancy, thermal stability and light stability, and is widely used in engineering plastics such as polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether and nylon -66. The main manufacturers are Shandong Dongying Wanda Group Co., Ltd., Shandong Shouguang Ocean Chemical Co., Ltd. and Jiangsu Zhangjiagang Xinyi Chemical Co., Ltd.. The total production capacity is about 1 1,000 t/a, and basically no industrial scale production has been formed. With the rapid development of domestic engineering plastics industry, the demand for brominated polystyrene will increase greatly and the market prospect will be broad.

1.3 halogen phosphorus flame retardant

This kind of flame retardant is characterized by containing bromine and phosphorus or bromine, phosphorus and nitrogen atoms in the molecule. Play a synergistic role in flame retardancy; The bromine content in the molecule is low, and the combustion process is accompanied by less smoke and less harmful gas volatiles; A certain bromine content can improve the shortcomings of common phosphate flame retardants, such as high volatility, poor migration resistance and poor thermal aging resistance. The main products include dibromooctanediol (DBNPG), dibromooctanediol phosphate and dibromooctanediol phosphate monoammonium salt. Halogen-phosphorus flame retardants complement each other by using different action mechanisms to achieve synergistic effect.

1.4 Other

In recent years, many new flame retardants or flame retardant systems have appeared in the international market. For example, Clariant Company in Germany has developed two kinds of phosphinic acid-based flame retardants, the brands of which are Exotop131and Exotop1312m1. Industrial production began at the end of 2004. Reogard 1000 intumescent flame retardant introduced by GreatLake Company of the United States, new melamine phosphate flame retardant introduced by DSM Company, Safron series of Dead Sea Bromide Company, FlamestabNORll6 and Tin2uviFR of Swiss Ciba Company, etc. There is no industrial production of this product in China.

To sum up, although there is a certain output of environmental-friendly flame retardant in China, it has not yet formed a scale and accounts for a small proportion in flame retardant products (see table 1). The development of flame retardants in China should be guided by environmentally-friendly and efficient varieties, and the research and development of new environmentally-friendly flame retardants should be strengthened. Only by adjusting the product structure and expanding the proportion of environmentally friendly flame retardants can we be in an invincible position in the future competition.

2. Prospect analysis of environment-friendly flame retardant

In 2004, the global plastic output reached 2 1 100 million t, and in 2005 it was 21-220 million, which was the highest growth rate in all continents. At present, there are five countries with annual output of plastics exceeding 654.38+000000000 t, namely China, the United States, Germany, Japan and South Korea. The consumption of flame retardant in flame retardant plastics is generally around 8%, which shows that the global demand for flame retardant is amazing. China's plastic production is growing very rapidly, and it is the second largest plastic consumer in the world after the United States. From the output of 22 million in 2005 to 2003, the sales volume of the three major flame retardants in the United States, Western Europe and Asia was 6.5438+0.32 million-6.5438+0.35 million t, and it is estimated that it will be 6.5438+0.400 million-6.5438+0.45 million t in 2005. From 1998 to 2005, the average annual growth rate of sales was about 3%. In 2005, the total consumption of flame retardants in the United States was 570,000-580,000 t, and in the past 10, the average growth rate in the next year was 2.8%-3.6%. Therefore, the overall market prospect of flame retardant at home and abroad is good.

Bromine flame retardant is a traditional variety in the field of flame retardant, which has a significant position, historical background and advantages in performance and price. Although there is a debate on bromine-based flame retardants, it may take some time for this debate to form a global consensus or a government ban. Researchers at home and abroad are still enthusiastic about the development of new products of bromine flame retardants. Therefore, the traditional bromine-based flame retardants still have a certain space in a certain period of time, and more and better new environmental protection bromine-based flame retardants will continue to appear to meet the market demand.

Due to the extensive use of inorganic flame retardants, it is bound to have a great impact on the physical and mechanical properties of polymers, which requires the treatment of inorganic flame retardants. However, with people's increasing attention to the environment, halogen-free flame retardants will become the first choice, especially some new inorganic flame retardants or synergistic flame retardants with excellent dispersibility and special properties will have good development prospects and market space.

3. Concluding remarks

China flame retardant industry is in the period of production structure adjustment and transformation. Some flame retardants will retire from the historical stage, while others will come out. Bromine-based flame retardants will still be widely used in more than ten years, but with the increase of environmental pressure, new green flame retardants will become the focus of future research and development, and with the increase of downstream market demand, China's flame retardant industry will usher in a period of prosperity and development.