The production technology of low-GWP foaming agents is in the hands of foreign companies, and it is difficult for domestic companies to produce it.

GWP value refers to the global warming potential value. As countries around the world pay more and more attention to environmental protection issues, the chemical industry is developing in the direction of environmental protection. The market demand for low-GWP foaming agents continues to rise, and the industry has good development prospects. Currently, the foaming agent products with low GWP value that have been successfully developed and used include 1,1,1,4,4,4-hexafluoro-2-butene, 1-chloro-3,3,3-fluoropropene, 2 , 3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene.

According to the “Research Report on Market Segment Demand and Development Opportunities of China’s Low GWP Foaming Agent Industry from 2021 to 2026” released by the Industrial Research Center shows that 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) has a GWP value of about 9 and a short atmospheric life. It is a new environmentally friendly product and is mainly used It is used as a foaming agent to replace HCFC-141b, and also has high application prospects in the field of refrigerants. There are many patents targeting HFO-1336mzz in the world, with more than 1,300 patents covering many countries.

In terms of patent applications, HFO-1336mzz patents are currently mainly concentrated in Chemours and Honeywell, with Chemours’ patent applications accounting for about 48% of the total number of patents. There is little research on HFO-1336mzz in my country, and the number of patents accounts for about 11% of the total number of patents. In terms of production, Sanai Fuzhonghao Chemical New Materials currently has a 5,000-ton production facility, but it is an authorized agent of The Chemours Company. HFO-1336mzz has high production technology and patent thresholds, making market entry difficult.

1-Chloro-3,3,3-fluoropropene (HCFO-1233zd) has a GWP value of less than 7 and a short residence time in the atmosphere. It is an important hydrofluoroolefin. HCFO-1233zd is mainly used as a foaming agent and has high application demand in refrigerators, construction and other fields. As a substitute for HCFC-141b and HFC-245fa, it has environmental protection properties and is non-flammable, so it has good future application prospects.

In terms of production, currently only Arkema and Honeywell in the world have achieved industrial production of HCFO-1233zd. There are two sets of production equipment in China, namely the Blue Sky Honeywell production line with an annual output of 10,000 tons, and the Zhejiang Environmental Protection Equipment Co., Ltd. The new fluorine material enterprise has a production device with an annual output of 7,000 tons. The market prospect of HCFO-1233zd is promising, but it is difficult to enter the market due to high technical barriers and high raw material costs.

The GWP value of 2,3,3,3-tetrafluoropropene (HFO-1234yf) is 5, and its residence time in the atmosphere is only about ten days. Globally, the current HFO-1234yf production technology is controlled by France, the United States and Japan, and the current patent field is occupied by companies such as Chemours, Arkema, and Honeywell. Domestic companies lack patent support and have greater difficulty in development.

Currently, domestic HFO-1234yf production mainly uses Honeywell’s patented technology, and Sinochem Blue Sky and Juhua Group are still actively developing technologies with independent intellectual property rights. Currently, there are four sets of HFO-1234yf production equipment in China, but they are all authorized processing enterprises by foreign companies, with a total production capacity of approximately more than 30,000 tons. At present, domestic independent production technology of HFO-1234yf has achieved a breakthrough, and Jianghuan New Fluorine Materials has achieved trial production.

The GWP value of 1,3,3,3-tetrafluoropropene (HFO-1234ze) is equal to 6, with high chemical stability and short residence time in the atmosphere. It is an ideal substitute material for HFC-134a and HFC-152a. In terms of application, HFO-1234ze exists in cis and trans isomers, so it cannot be used as a refrigerant alone and mostly exists in mixed form. Currently, HFO-1234ze has been used as a foaming agent and solvent in aerospace, firefighting and other fields.

In terms of production, the current production methods of HFO-1234ze include fluorine-chlorine exchange method, dehydrofluorination method, telomerization fluorination method, and carbene reaction method. Among them, the fluorine-chlorine exchange method has industrial prospects, but it is difficult to obtain raw materials for this method. In the world, only Honeywell has realized the production of HFO-1234ze, and there are no reports on the industrialization of HFO-1234ze in my country.

Industrial analysts said that foaming agents with low GWP values ​​are environmentally friendly and have good application prospects, attracting many companies to deploy. Currently, there are four low-GWP value foaming agent products that have been industrialized. The production technology requirements of the four products are relatively high. The patented technology is mainly in the hands of foreign companies, making it difficult for Chinese companies to develop.