Analysis of Trends in Organic Fluorosilicon Products in the Fine Chemicals Sector in 2009

The third category is regional support or internal supply within the group. A typical example is Haohua Group, which brought Sichuan Honghe Fine Chemicals under its umbrella to supply methyl chlorides and R22 to ChenGuang Research Institute, which is located in the same city. In addition, the Fluorine Chemical Industry Park in Changshu, Jiangsu, also has specialized enterprises for the production of chloromethanes. The fourth category has evolved from the initial comprehensive recycling and utilization of resources. A typical representative is Zhejiang Xinan Chemical Group. The group started out by producing glyphosate, and initially introduced small-scale silicone production to deal with the large amount of hydrochloric acid generated as a by-product. The hydrochloric acid produced as a by-product of silicones is then used as a raw material for pesticides, thus creating a unique circular economy chain involving chlorine atoms. Now, silicone has become the star product of Xinan Chemical. Foreign companies have a practice: those that deal in organic fluorines rarely engage in organic silicon production ； Similarly, those who work with silicone rarely work with organofluorine compounds. Many experts explain that the main difficulties in developing these two industries lie in the development of downstream products, rather than the monomers themselves. Once development moves into the downstream phase, it becomes very difficult to succeed in any particular industrial chain. So why are there so many enterprises in China that develop organic fluorosilicon technologies integratedly? Firstly, China is rich in fluorosilicon resources, which often occur in the same areas. Secondly, compared with developed countries, although China’s organic fluorine and silicon industries are developing rapidly at present, the overall level of these industries remains at the stage of monomers and primary polymers. It is at this stage that raw material costs and the efficiency of by-product recycling become particularly important. It is said that the greatest advantage of the integrated development of organic fluorine and silicon is the ability to recycle chlorine atoms; more specifically, it enables the recycling of the by-product hydrochloric acid. In this regard, the utilization rate in our country is significantly low, and this issue must be addressed.

According to a technical staff member at Shandong Dongyue Group, the company’s chloromethane production facility currently mainly produces chloroform, and carbon tetrachloride is generated as a byproduct. Now, carbon tetrachloride can no longer be sold to external companies; it must be converted into chloromethane using a 12,000-ton/year carbon tetrachloride conversion facility, which is neither profitable nor easy to manage effectively. Once the 60,000-ton silicone project comes online this year, this output will precisely cover the portion of monochloromethane that is needed to supplement silicone production. Due to the self-sufficient supply capabilities of domestic fluorosilicon enterprises and the entry of external ones, competition in China’s methane chloride and organic fluorosilicon industries has further intensified. Faced with the substantial amount of hydrochloric acid generated as a by-product, domestic companies are now seeking ways to utilize it effectively, rather than disposing of it as a by-product.

The Current Status of Organic Fluorine Fine Chemicals and Fluorine Chemical Industries in Our Country. Publication date: 2009-2-10 10:27:00. Source: HuiCong Chemical Channel. Organic fluorine chemicals mainly include basic fluorocarbons, fluoropolymers, organic fluorine fine chemicals, as well as hydrofluoric acid, which is an important raw material for production. Basic fluorocarbons include fluorinated alkanes such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), which are primarily used as refrigerants in refrigerators and air conditioners, as blowing agents in plastics, as cleaning agents for electronics, in aerosols, and as Halon fire extinguishing agents. In 1995, China’s production capacity for basic fluorocarbons was 120,000 tons per year, with an actual output of 60,000 tons per year; of this amount, approximately 50,000 tons were chlorofluorocarbon refrigerants. Currently, the domestic demand for chlorofluorocarbon refrigerants is approximately 100,000 tons per year. As the use of Freon was gradually phased out, China built a large number of production facilities for ODS substitutes during the Ninth Five-Year Plan period, with production reaching over 80,000 tons in 1999. Fluoropolymers mainly include fluororesins and fluororubbers. In 1995, China’s production capacity for fluoropolymers was 0.6 million tons per year, with a production volume of around 0.40 million tons per year. The main product was PTFE, accounting for about 80% of the total output; these products were mainly in the form of medium-grained suspensions of medium to low quality ； Fluororubber accounts for 3%. At present, neither the variety nor the quantity of fluoropolymers can meet domestic demand. Based on conservative estimates, the current domestic demand for fluoropolymers is 5,000 tons of PTFE, 500 tons of PVDF, 600 tons of FEP, 200 tons of ETFE, 200 tons of PFA, 10,000 tons of fluororubber, and other fluoropolymers; the potential market for these materials is extremely large. In the development of fluoropolymers, institutions such as the Shanghai Institute of Organic Chemistry of the Chinese Academy of Sciences, the Shanghai Institute of Organic Fluorine Materials, and the Sichuan Chenguang Chemical Research Institute have carried out extensive work and achieved many results from industrial-scale tests; some of these are now moving towards commercialization. Organofluorine fine chemicals include fluorine pesticides, fluorine-based pharmaceuticals, fluorine dyes, fluorinated aromatic intermediates, fluorinated surfactants, and fluorine inert fluids, among others. (1) Fluoropharmaceuticals are the most actively developed, as fluorinated organic compounds possess specific biological activities and compatibility with living organisms, resulting in drugs containing fluorine having several times greater efficacy than ordinary drugs. Currently, there are nearly a hundred fluorine-containing pharmaceuticals that have been commercialized or are under development worldwide. Some important products include the sedative haloperidol ； Antitumor drug fluorouracil ； Anti-inflammatory drug diflunisal ； Hormonal drugs: fludrocortisone, flucinonide, fluhydrocortisone, fludicasone ； Antiarrhythmic drug flecainide ； Antifungal drugs fluconazole, flucytosine ； The anticancer drug fludarabine phosphate ； The hypnotic drug flumazenil ； The anti-asthma drug flunisolone ； The antidepressant fluoxetine (Prozac, the best-selling antidepressant in the world) ； The weight loss drug fluoxetine. (2) Fluorine pesticides: Since the 1970s, China has begun research on fluorine-containing pesticides. Herbicides such as pretilachlor, fluazifop-p-butyl, and ethofenpropargate, as well as insecticides such as flufenoxuron, chlorantraniliprole, and fluorinated pyrethroids have been developed. Among these, fluazifop-p-butyl has been put into industrial production, while compounds such as gor, hexaflumuron, and chlorantraniliprole are also produced on a large scale. Pesticides derived from heterocyclic compounds already possess strong properties, and the introduction of fluorine further enhances these properties. For example, the performance of the herbicide pyrifluzifol (Stablecide), which is made from fluorinated pyridine derivatives, has increased by more than a factor of two ； The insecticide chlorfluoruron (Dingchonglong) has both insecticidal and sterilizing effects. At present, the variety and quantity of fluorine-containing pesticides in the country cannot meet market demand, so there is a heavy reliance on imports. 　　 (3) The introduction of fluorine from fluorine dyes can enhance the luster and brightness of the dyes, as well as improve their resistance to sunlight, water, and organic solvents. When F-type reactive dyes containing fluorochloropyrimidine-type active groups replace K-type and KN-type screen printing dyes, their reactivity, color fastness, and other properties improve significantly. **The dye intermediate 2,6-difluoro-3-nitropyridine also has antibacterial properties and can be used as a additive in chewing gum. In terms of fluorine-containing dyes, various types have been synthesized in China, including bright red-based VD, orange-red-based RD, fluorine-containing lake pigments, polyfluorocyanine, thermosensitive dyes, and FT2. Beijing Institute of Fashion Technology offers technologies such as polyfluorocyanuric acid and thermosensitive dyes. (4) Organic fluorine intermediates Organic fluorine intermediates mainly include aromatic fluorides and aliphatic fluorides, among which aromatic fluorides predominate. Aromatic fluorides include: polyfluorobenzenes ； Chloro, bromo, iodofluorobenzenes ； Fluorine*** compounds ； Fluoroanilines ； Fluorophenols ； Fluorobenzaldehydes ； Fluorophenylpropanoids ； Fluorobenzoic acids ； Chlorinated benzoals ； Fluorotoluenes and other fluorobenzenes ； and monotrifluorotoluenes ； Bis(trifluorotoluene) derivatives ； Flupyridines ； Trifluoromethylpyridines and the like. Aromatic fluorides are important intermediates in the synthesis of pharmaceuticals, pesticides, and dyes; for example, 2,4-dichlorofluorobenzene is used in the synthesis of anti-infective quinolone drugs such as ciprofloxacin, ofloxacin, and norfloxacin ； Use of p-fluorophenol in the synthesis of the anti-inflammatory and antirheumatic drug thiazindic acid and the aldose reductase inhibitor sobinil ； Fluorobenzoyl chloride is used in the synthesis of cardiovascular drugs such as fluvastatin sodium ； 3-Chloro-4-fluoroaniline is used in the synthesis of fluoroquinolone-class antibacterial drugs ； 4-Bromo-2-fluoroaniline is used in the synthesis of the anti-inflammatory drug ibuprofen ； 4-Chloro-4-fluorobenzene is also used in the synthesis of the medical anthelmintic flubenazole ； Furthermore, the aliphatic fluoride bromofluoromethane is an important intermediate for the cephalosporin drug cefluzamide. 　　　 All of the above are currently emerging or best-selling products with promising market prospects; therefore, despite the high prices of their corresponding intermediates, they remain highly competitive in the market. To reduce costs, the international market for intermediates is being shifted to Asia. Among them, the domestic and international market prospects for 2,4-dichlorofluorobenzene, 3-chloro-4-fluoroaniline, and trifluorotoluene are quite optimistic, with large production scales as well. In China, the domestic demand for 2,4-dichlorofluorobenzene, which is used as a raw material for ciprofloxacin, amounts to 2,000–3,000 tons; the United States, Japan, Germany, and Italy all rely on imports for this substance ； There is also a significant shortage of 3-chloro-4-fluoroaniline, an important intermediate for quinolone drugs. (5) Fluorinated surfactants and fluorinated compound treatment agents Fluorinated surfactants are widely used as cleaning agents for electronic components, anti-fogging agents, release agents, as well as color uniformizing agents in the silk textile industry and as additives for giving metals a glossy finish ； Furthermore, it can also be used as an additive in fire extinguishants, pesticide additives, paint additives, etc. Fluorine-containing chromium-suppressing mist agents can effectively suppress the chromium mist generated during the chromium plating process, thereby protecting workers’ health. Fluorine-containing compound treatment agents are divided into leather treatment agents, fabric treatment agents, and paper treatment agents; they have a wide range of applications, with global market consumption reaching 5,000 tons per year, and there are many different types available. The country of production for the above products is almost blank. (6) Fluorine-inert fluids (fluorine oils, fluorine greases): Fluoroalkyl compounds possess high chemical and thermal stability. Fluorine oils can withstand temperatures of 250–360°C, and they also feature low-temperature fluidity, high density, good lubricity, non-flammability, and low surface tension. Their main applications include lubricating valves that are exposed to strong oxidizing agents in the nuclear industry and aerospace technology, lubricating valves used with corrosive fluids, serving as oil for special diffusion pumps, as fluids for flowmeters and pressure gauges, as shock-absorbing fluids for rocket gyroscopes, as dielectrics and coolants in the electrical industry, and as testing liquids in the electronics industry.

Could the original poster please describe the trends in inorganic fluoride salt materials in the fine fluorine chemicals industry? Thank you

Could the original poster please describe the trends in inorganic fluoride salt materials in the fine fluorine chemicals industry? Thank you