First, China's plasticizer market is facing environmental pressure
Plasticizer is one of the world's largest plastics auxiliaries for production and consumption. In recent years, China has become the country with the largest amount of plasticizer production and consumption in Asia. With the increasing awareness of environmental protection in the world, medicine and food packaging, Daily necessities, toys and other plastic products put forward higher purity and hygiene requirements for the main plasticizer DOP, etc. However, the main plasticizers produced by domestic enterprises are particularly difficult to meet environmental protection requirements in many performances, such as hygiene and low toxicity. .
The European Union and Russia have discovered from plastic toys imported from China that some plastic toys originating in China have been found to contain toxic polyvinyl chloride plasticized N-monophthalic acid diisodecyl phthalate (DINP) and phthalic acid diethyl phthalate. Hexyl hexyl ester (DEHP, or DOP).
Plasticizers have long been dominated by o-benzene products, but with the increasing use of DOP in the food and pharmaceutical industries, people are paying more and more attention to its toxicity. It has been found that when people enter the poly After the blood stored in the vinyl chloride plastic bag, DOP products are found in the human body, especially in the lungs.
In 1982, the authoritative National Cancer Institute conducted a bioassay on the carcinogenicity of DOP, 'The conclusion is: DOP is a carcinogen in rats and mice, which can cause cancer in the liver of a rodent. So, about DOP I students have attracted global attention. Although the argument that it will cause cancer is still arguing, due to its potential cancer-causing suspicion, countries have taken corresponding measures.
According to the results of the National Cancer Institute, the US Environmental Protection Agency has stopped production of six new phthalate industries. DOP is limited to high-water content food packaging. Meat packaging must use other non-toxic products. Replacement of plasticizer products; the Swiss government has decided to ban DOP in children's toys: Germany prohibits the addition of DOP in all plastic products related to human health and food: Japan prohibits the addition of DOP in medical device-related products, only in Application in industrial plastic products.
According to the research results and standards issued by countries such as Europe, Japan, Korea and Korea, DOP (DEHP) is more harmful than DOA (DEHA). For example, the European Food Safety Agency EFSA stipulates that the concentration of DEHA in the human body is 0.3 mg/kg or more. Safe, and DEHP concentration of 0.05 mg / kg or more is considered to be unsafe. DOA, DOP is a variety of plasticizers widely used in domestic PVC food wrap. Special DOP is the largest increase Plastics, and humans are used in food packaging products.
Among the ten main plasticizers allowed in China's PVC wrap film, the first one is adipic acid dioctanoic acid (ie, DEHA, referred to as DOA), and the latter three are phthalates DBP, DOP, DIOP, Their toxicity is relatively high in human DEHA. Due to the high production cost of DOA, most of the domestic PVC cling film manufacturers use DOP and DBP as the main plasticizer, so the plastic wrap produced is especially used in fat. On higher meat products, or when it is used to wrap food in a microwave oven, the chances of plasticizers migrating into the packaged food will be more, potentially harmful to human health.
However, it is relatively safe to use in vegetables, especially before eating or before making food.
Although there is still debate in the world about whether DOP is carcinogenic, there is a potential carcinogenic risk to DOP, and international measures have been taken to limit the scope of use of DOP.
According to the National Cancer Institute, the US Environmental Protection Agency has stopped industrial production of six phthalates; the Swiss government has decided to ban the use of DOP in children's toys; Germany is already in the human body, health foods DOP is forbidden in plastic products: In Japan, DOP is used as a plastics additive only in the application of plastic products in the factory. At present, the research and development of non-toxic plasticizer products has been accelerated globally, especially for plastic products with high hygiene requirements. Basic application research.
In China, plasticizers such as DOP, which have been eliminated by foreign countries, still have a large market, and plasticizer manufacturers have not paid enough attention to the development and promotion of non-toxic new plasticizers. 80% plasticization in the domestic market. The agents are all plasticizers such as DOP, DBP (dibutyl phthalate), and the low price is the most critical factor. National standard food containers, additives for packaging materials make the Sichuan Health Standards also list DOP as available. One of the plasticizer varieties for food packaging.
The latest test results of Tongji University show that the cooking oil is dissolved in plastic drums, and the plasticizers that are harmful to the human body will be dissolved in the edible oil. The research team led by Prof. Li Shuguang of the Basic Medical College of Tongji University has collected different brands and different factories in the market. Dates of plastic barreled soy salad oil, blended oil, peanut oil, and bulk soybean oil sold on the market, solid shortening for a fast food restaurant frying food, condensed oil collected by a resident kitchen range hood, etc.
The research team measured these samples and found that all brands of plastic barreled edible oils contain 'phthalic acid diester (DBP)' and 'dioctyl phthalate (DOP)'. Two plasticizers are phthalate plasticizers commonly used in the plastics industry, and bulk plastics and solid shortenings that are not used in plastic containers contain almost no plasticizer.
It is presumed that the plasticizer detected in edible oil is mainly derived from its plastic container. At present, most of the oils consumed by thousands of families in China for three meals a day are consumed in plastic drums purchased from the market. Oil. However, in the current national standards, plasticizers have not been included in the physical and chemical indicators of edible oil testing, and there is no regulation and requirement for plasticizer content. Due to the lag of China's relevant standards, this is actually only plasticizer pollution. The 'tip of the iceberg'. The wide range of plasticizers used, the large area of pollution, the number of people affected, more than pesticides, DDT and so on.
Second, environmentally friendly plasticizer new products
Enterprises should increase the intensity of research and development, develop new varieties of plasticizers, bypass technical barriers, and reoccupy the international market. At present, the development of environmentally friendly plasticizers in the world lags behind the needs of production and life, with the advancement of technology. Some traditional materials may be eliminated, and new environmentally friendly plasticizers with advantages such as harmless research and development, low cost, and good auxiliary effects are the key materials for the development of the current plastic products industry.
Citric acid ester
As a new type of green plastic plasticizer, citric acid ester is non-toxic and tasteless. It can replace traditional phthalate plasticizers. It is widely used in food and medical equipment packaging, cosmetics, daily necessities, toys, military products. In the field, it is also an important chemical intermediate. Among them, acetyl citrate is superior in performance and more versatile. It is not only a non-toxic and odorless green plastic plasticizer, but also a polyvinylidene chloride stabilizer, film and metal. Adhesive modifier, the adhesive has a strong adhesion after being immersed in water for a long time.
The United States, the European Union and other developed countries have issued regulations that allow citrate ester products to be used as one of children's toys, hygiene products, medical equipment, artificial leather and other human-related products with high hygiene requirements. Started research and development of citrate esters in the mid-1990s. Jiangsu Raymond Chemical Technology Co., Ltd. grasps the market development trend and has long been engaged in the production and development of plasticizer products. The company has built an annual production of 5,000 tons of citrate ester equipment in China. 40% of products enter the United States, Japan, Europe and other places.
China's conditionally mass-produced citrate esters, such as tributyl citrate (TBC), trioctyl citrate (TOC), acetyl tributyl citrate (ATBC), acetyl trisulphate ~ (ATOC), They are considered to be the safest plasticizers and can be used in various PVC products, but they are easier to precipitate than DOP. At present, China has developed its own environmentally friendly plasticizer TBC, which has been applied in pharmaceutical products. In the future, it can be gradually promoted in other production industries.
2.1, 2-cyclohexanedicarboxylic acid diisopropyl ester
l, 2-cyclohexanedicarboxylic acid diisopropyl ester is small migration, is a colorless, transparent and slightly odorless anhydrous liquid, soluble in many solvents, and is compatible with many PVC commonly used plasticizer monomers. Good compatibility, almost insoluble in water, can be used in many soft medical products such as stomach tube and infusion bag, can provide ideal solution for toy manufacturers to meet safety requirements, and meet the new EU regulations.
3.Eastman168 plasticizer
Eastman's new Eastmanl68 plasticizer has been widely welcomed by the market due to the absence of phthalate harmful substances. This new plasticizer is non-toxic and contains no estrogen and anti-estrogen. Androgen, no carcinogen, does not cause peroxisome proliferation. Eastman 168 plasticizer is the least risky for those looking for other plasticizers to produce in children's toys. Choice, is a simple alternative to plasticizers.
This plasticizer meets the highest standards of regulatory requirements, and its non-toxic properties make many toy manufacturers feel comfortable with consumers. The plasticizer does not need to be reconfigured, reducing the costly product recall due to secondary configuration errors. Risk of complaints from customers. Due to its low initial tack and excellent viscosity stability and processability, the plasticizer can meet high-speed mold production efficiency and cycle time requirements, and can ensure consistent surface thickness.
4. Plasticizer for biodegradable plastics
A project funded by the UK government successfully developed a plasticizer for biodegradable plastics in the form of polylactic acid (PLA) for film and other flexible packaging, which can greatly improve the mechanical properties of PLA.
The project is supported by the UK Government's Sustainability Technology Initiative, which improves the flexibility of conventional hard PLAs and increases their elongation from 5% to 320%. These plasticizers are biodegradable and they are 10%~ 20% of the amount of additives in the product.
This modifier is based on a block copolymer formed between PLA and polyethylene glycol. The modified PLA can disappear in the mixture for 20 to 25 days. Currently, this type of additive has been industrially scaled. .
Third, promote the healthy development of plasticizers in China
1. Solve the problem of plasticizer standard lag
At present, China's foreign trade exports are facing a more severe external environment. What needs special attention is that importing countries have increased the quarantine standards, increased testing programs as means, and restricted the export of Chinese products with technical trade barriers. The trend of protecting domestic industries is becoming more and more obvious.
At present, Europe, Japan, South Korea and other countries have used citric acid esters, epoxide esters and other safe and environmentally friendly plasticizers as replacement products, and have introduced DOA in food packaging, medical supplies, children's toys and other products in contact with human body. , DOP standard legislation, and in our national standards, it is also expressly allowed to use DOA, DOP. Although these plasticizer varieties are not conclusive, but due to the lag of China's relevant standards, resulting in many domestic plastics The export of products is blocked, and the products containing obsolete plasticizers have entered the market in a series of problems. It is extremely urgent to solve the problem of the lag of plasticizers in China.
2. Promote the development of risk assessment work
European Plasticizers and Intermediates Committee (ECP1) Technology: Chairman of the Working Group, ikePenman, ExxonMobil Petroleum and Chemicals Senior Toxicology Consultant, said the determinant of the availability of a plasticizer is the risk assessment, not the toxicity. Test results. Si Junjie, chairman of the China Plasticizer Industry Association, also believes that there is no scientific basis for follow-up and speculation, which will undermine the healthy development of China's plasticizer and plastics industry, and strengthen China's plasticizer toxicity test and risk assessment work. necessary.
To determine whether a plasticizer is available or not, the key is not the animal toxicity test results, but to investigate the relationship between dose and toxicity, the relationship between exposure and hazard, mass migration and migration speed and contact. The relationship between quantity and then the relevant risk control measures, through scientific analysis and means to minimize the harm to the public environment. It is sloppy and unscientific to take restrictive measures based solely on the results of hazard identification. International management of chemicals, including plasticizers, will continue to be more stringent and scientific.
The EU registration, assessment, authorization and restriction system for chemicals will be implemented by 2008, and the risk assessment will be accepted by more and more people and become the basis for the development of various relevant laws. China's plasticizer toxicity test and The work on risk assessment is still very weak, which is very unfavorable for the healthy development of the industry. Relevant domestic stakeholders should pay attention to the risk assessment work.
3. Promote the structural adjustment of the plasticizer industry
The role of plasticizers in providing high-quality plastic products for humans is indispensable. However, the variety structure is constantly changing and changing, the development speed of new technologies is accelerating, new varieties are emerging, detection methods are more advanced, and evaluation methods are more reasonable. Plasticizers are constantly evolving in such a cycle of 'development one application, one toxicology test, one risk assessment one by one.'
Therefore, the correct use of plasticizers is the key to the healthy development of the industry. To do this, plasticizer companies should work hard on structural adjustment. Foreign countries are promoting the promotion of non-toxic or environmentally friendly and bio-organisms. Degradable plasticizer. The so-called non-toxic and environmentally friendly is also relatively speaking. For example, DIHCN (diisononyl cyclohexanedicarboxylate), E-l68 plasticizer, EBN BET (polyoctanoic acid and benzoic acid polyol) Mixed ester) plasticizer, adipic acid and polyol condensed polyester type plasticizer, etc.
At present, the production of environmentally friendly non-toxic plasticizers in China is facing two major problems. First, there are many by-products, and the yield is not high: Second, low output, high cost, good products such as citrate, due to the high price of the catalyst used. The cost of plasticizers is quite high. In addition, some companies have produced citrate plasticizers, but because they do not pay attention to the marketing of products, users know nothing about their products, they will still choose cheaper. Familiar plasticizer products. As the accelerated elimination of toxic plasticizers and the development and promotion of new non-toxic plasticizers have become an inevitable trend, domestic manufacturers must make great efforts to study new catalysts, separation processes, and cost-effectiveness as soon as possible. Higher, safer, and environmentally friendly next-generation plasticizer products are on the market.
4. Segment the market according to the application field
Plasticizer is one of the largest varieties of plastic additives. At present, there are more than 200 kinds of plasticizers in the world, each of which has its own physical and chemical properties, and its application fields are different. China's plasticizer industry has undergone After ten years of development, the industrial base has been quite large, and the production technology is not backward. The requirements for the safety and safety performance of different products are not the same. Therefore, the market segmentation according to the application field is to avoid the plasticizer 'cracking'. Important means.
While increasing the production of plasticizers in China, we should pay more attention to the study of the adaptability of different varieties of plasticizers in various products. The advantages of the two benefits are taken into account, and the two harmful rights are taken lightly to provide guidance to users. Sexual advice, using practice and facts to prove to consumers that the rational use of plasticizers will be safe.