Plasticizer is one of the world's largest production and consumption of plastic additives. In recent years, China has become the country with the largest production and consumption of plasticizers in Asia. With the improvement of environmental awareness in countries around the world, medicine and food packaging, daily necessities, toys and other plastic products have put forward higher purity and health requirements for the main plasticizer DOP, but at present, the main plasticizer produced by Chinese enterprises is difficult to meet the requirements of environmental protection in many properties, especially health and low toxicity.

EU and Russia have been imported from China in plastic toys found originating in China some plastic toys found to contain toxic polyvinyl chloride plasticizer N-isononyl phthalate (DINP) and diethylhexyl phthalate (DEHP, or DOP).

For a long time, the plasticizer is mainly based on phthalic products, but with the DOP in the food and pharmaceutical industry more and more widely used, people pay more and more attention to its toxicity. It has been found that when people enter the blood stored in polyvinyl chloride plastic bags, DOP products are found in the human body, especially in the lungs.

In 1982, the authoritative National Cancer Institute of the United States made a biological identification of the carcinogenicity of DOP. The conclusion is that DOP is a carcinogen in rats and mice, and can cause cancer in the liver of rodents. As a result, the toxicity of DOP has attracted global attention. Although whether DOP can cause human cancer is still debated, but because of its potential carcinogenic suspicion, countries have taken corresponding measures.

The United States Environmental Protection Administration according to the National Cancer Institute research results, has stopped the production of 6 new phthalate esters industry, DOP is limited to the use of high water content of food packaging, meat packaging must use other non-toxic plasticizer products to replace; The Swiss government has decided to prohibit the use of 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, and is limited to the application of industrial plastic products.

According to the research results and promulgated standards in Europe, America, Japan and South Korea and other countries, 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 up to 0.3 mg/kg or more is considered unsafe, and the concentration of DEHP up to 0.05 mg/kg or more is considered unsafe. DOA and DOP are the plasticizers widely used in PVC food cling film in China. Special DOP is the largest amount of plasticizer variety, and the number of people used in food packaging products.

China PVC plastic film allows the use of ten main plasticizers, the first one is adipate diocaptanoic acid (DEHA, referred to as DOA), the following three for phthalate DBP, DOP, DIOP, their toxicity relative to DEHA, due to the high cost of DOA production, So most of China's PVC plastic film production enterprises use DOP, DBP as the main plasticizer, so that the production of plastic film, especially used in fatty meat products, or use it to wrap food in the microwave oven heating, the plasticizer migration into the packaged food opportunities will be more, causing potential harm to human health.

However, it is relatively safe to use in vegetables, especially in the varieties that should be cleaned before eating or making food.

Although the international DOP is carcinogenic to the present is still debated, but there is a potential carcinogenic risk of DOP, the international has begun to take corresponding measures to limit the scope of use of DOP.

The United States Environmental Protection Administration has stopped the industrial production of six kinds of phthalates according to the results of the National Cancer Institute; The Swiss government's decision to ban DOP in children's toys; Germany has banned the use of DOP in all plastic products related to human body and sanitary food: in Japan, DOP as a plastic additive is limited to the application of factory plastic products. At present, the world has accelerated the research and development of non-toxic plasticizer products, especially accelerated the basic application research of plastic products with high hygiene requirements.

And in China, DOP and other plasticizers that have been eliminated abroad are still a big market, and plasticizer production enterprises for the development and promotion of non-toxic new plasticizers did not attract enough attention. 80% of the plasticizers in the Chinese market are DOP, DBP(dibutyl phthalate) and other plasticizers, low price is the most critical factor. The national standard for food containers and packaging materials additives Make Chuan Health Standard also lists DOP as one of the plasticizers that can be used for food packaging.

The latest test results of Tongji University show that with plastic barrels of edible oil, edible oil will dissolve into the plasticizer harmful to human body. The research team led by Professor Li Shuguang of the School of Basic Medicine of Tongji University collected different brands and different factory dates of plastic barrels of soybean salad oil, blended oil, peanut oil, as well as bulk soybean oil sold on the market, solid shortening of a fast food restaurant fried food, and condensed oil collected by residents' kitchen range hoods.

The research team after the determination of these samples found that almost all brands of plastic barrels of cooking oil, contain "dioctyl phthalate (DBP)" and" dioctyl phthalate (DOP)", these two plasticizers are often used in the plastics industry phthalate plasticizers, And the bulk soybean oil and solid shortening that do not use plastic containers contain almost no plasticizers.

Thus it is presumed that the plasticizer detected in the cooking oil is mainly derived from its plastic container. At present, millions of families in China eat oil for three meals a day, most of which are plastic barrels of cooking oil purchased from the market. However, at present, the national standard does not include plasticizer in the physical and chemical indicators of edible oil inspection, and there is no regulation and requirement for the content of plasticizer. Because China's relevant standards lag behind, this is actually only the "tip of the iceberg" of plasticizer pollution. Plasticizers are used in a wide range, pollute a large area, and affect a large number of people, which is worse than pesticides and DDT.

Two, environmental protection plasticizer new products

Enterprises should increase research and development efforts, develop new plasticizer varieties, bypass technical barriers, re-occupy the international market. At present, the world for environmental protection plasticizer development obviously lags behind the needs of production and life, with the progress of science and technology, some traditional materials may be eliminated, and the development of harmless, cheap, auxiliary effect of good advantages of new environmental protection plasticizer as an alternative material, is a key part of the current plastic products industry development.

1. Citric acid ester

Citric acid ester products as a new green plastic plasticizer, non-toxic and tasteless, can replace the traditional phthalate plasticizer, widely used in food and medical equipment packaging, cosmetics, daily necessities, toys, military supplies and other fields, but also an important chemical intermediates. Among them, the performance of acetyl citrate is more superior, more widely used, not only is a non-toxic and tasteless green plastic plasticizer, but also can be used as a poly-vinylidene chloride stabilizer, film and metal bonding modifier, its adhesive for a long time soaking in water still has a strong adhesive force.

Developed countries such as the United States and the European Union have issued regulations to allow citric acid ester products as children's toys, hygiene products, medical devices, artificial leather and other products closely related to the human body and one of the plastic additives with high health requirements. China began to research and develop citrate esters in the mid-1990s of last century. Jiangsu Ramon Chemical Technology Co., Ltd. grasp the market development trend, and has a long-term experience in the production and development of plasticizer products, the company built an annual output of 5000 tons of citric acid ester plant in China, 40% of the products into the United States, Japan, Europe and other places.

China has the conditions of mass production of citric acid esters, such as tributyl citrate (TBC), trioctyl citrate (TOC), acetyl tributyl citrate ~(ATBC), acetyl tri-octyl citrate ~(ATOC), are considered to be the safest plasticizer, can be used for a variety of PVC products, but it is easier to precipitate than DOP when used. 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 cyclohexane dicarboxylic acid diisopropyl ester

2 cyclohexane dicarboxylic acid diisopropyl ester is a small mobility, is a colorless transparent slightly odorless anhydrous liquid, soluble in many solvents, and many PVC commonly used plasticizer monomer mutual compatibility is good, almost insoluble in water, can be used in stomach tubes and infusion bags and many other soft medical products, Can provide toy factory to meet the safety requirements of the ideal solution, and to meet the requirements of the new regulations of the European Union.

3.Eastman168 plasticizer

Eastman Company's new Eastmanl68 plasticizer has been widely welcomed by the market because it does not contain phthalates harmful substances. This new plasticizer is non-toxic, does not contain imitation estrogen and anti-androgen substances, no carcinogens, will not cause peroxisome proliferation. Eastman168 plasticizer is the lowest risk option for manufacturers who are looking for other plasticizers to use in children's toys that can be put in the mouth. It is a simple and easy alternative to plasticizers.

This plasticizer meets the highest standards required by regulations and its non-toxic properties are reassuring to many toy manufacturers and consumers. The plasticizer does not need to be reconfigured, reducing the risk of costly product recalls and customer complaints resulting from secondary configuration errors. Due to its low initial viscosity and excellent viscosity stability and machinability, the plasticizer can meet the requirements of high-speed molding production efficiency and cycle times, and can ensure consistent surface thickness.

4. Plasticizer for biodegradable plastics

A project partially funded by the UK Government has successfully developed a plasticizer for biodegradable plastics, which is used in polylactic acid (PLA) for film and other flexible packaging. It can greatly improve the mechanical properties of PLA.

The project is supported by the British government's Sustainable Development Technology Initiative, which improves the flexibility of conventional hard PLA, and its elongation can be increased from the original 5% to 320%. Such plasticizers can be biodegradable, and they are used in products with 10% to 20% of the amount of additives.

This modifier is based on the block copolymer formed between PLA and polyethylene glycol. The modified PLA can disappear in the mix in 20 to 25 days. At present, this kind of additives has achieved industrial scale production.

Three, promote the healthy development of China's plasticizers

1. Solve the problem of lagging plasticizer standards

At present, China's foreign trade exports are facing a more severe external environment. In particular, it is necessary to pay attention to the importing countries to improve quarantine standards, increase testing items as a means to restrict the export of Chinese products with technical barriers to trade, the trend of protecting domestic industries is becoming more and more obvious.

At present, Europe, the United States, Japan and South Korea and other countries have used citric acid esters, epoxy acid esters and other safety and environmental plasticizers as replacement products, have introduced in food packaging, medical supplies, children's toys and other products in contact with the human body to ban DOA, DOP standard interest regulations, and in China's national standards, also explicitly allow the use of DOA, DOP. Although these plasticizer varieties are carcinogenic has not been determined, but due to China's relevant standards lag, which caused many Chinese plastic products exports blocked, and containing outdated plasticizer products into a series of problems, to solve the problem of China's plasticizer standards lag is imminent.

2. Promote the development of risk assessment

European Committee on Plasticizers and Intermediates (ECP1) technology: Chairman of the working group, ExxonMobil Petroleum and Chemical senior Toxicology consultant ikePenman said that the determining factor for determining whether a plasticizer is usable is the result of risk assessment, not the result of toxicity testing. China Plasticizer Industry Association chairman Si Junjie also believes that there is no scientific basis to follow the trend and hype, will be harmful to the healthy development of China's plasticizer and plastics industry, strengthen China's plasticizer toxicity experiment and risk assessment work is necessary.

To determine whether a plasticizer is available and used in what aspects, the key is not the toxicity results of animal experiments, but through in-depth investigation of the relationship between the use of dose and toxicity, the relationship between the amount of exposure and harm, the relationship between the amount of material migration and migration speed and the amount of exposure, and then develop relevant risk control measures. Through scientific analysis and means to minimize its harm to the public and the environment. However, it is hasty and unscientific to take restrictive measures simply based on the results of hazard identification. The international management of chemicals, including plasticizers, will continue to be more and more strict and more and more scientific.

The EU registration, evaluation, authorization and restriction system of chemicals will be implemented before 2008, risk assessment will be accepted by more and more people, and become the basis for the formulation of various related laws. At present, China's work on animal toxicity testing and risk assessment of plasticizers is still very weak, which is very unfavorable to the healthy development of the industry. The relevant parties in China should pay attention to the risk assessment work.

3. Promote the structural adjustment of the plasticizer industry

Plasticizer plays an indispensable role in providing high-quality plastic products for human beings. But its variety structure is constantly adjusting and changing, the development of new technologies is accelerating, new varieties are emerging in endlessly, detection means are more advanced, evaluation methods are more reasonable, plasticizer is in such a "development one application one toxicology test one risk assessment one development again and again" cycle progress.

Therefore, the correct use of plasticizer is the key to the healthy development of the industry. And to do this, plasticizer enterprises should work hard in structural adjustment. Foreign countries are vigorously promoting plasticizers known as non-toxic or environmentally friendly and biodegradable. The so-called non-toxic and environmental protection is also relatively speaking. Such as DIHCN(diisononyl cyclohexane dicarboxylate), E-l68 plasticizer, EBN Libet (polyol mixed ester of isoctanoic acid and benzoic acid) plasticizer, adipic acid and polyol condensation of polyester plasticizer and so on.

At present, China's environmentally friendly non-toxic plasticizer production is facing two major problems, one is more by-products, the yield is not high: the second is low production, high cost, good products such as citric acid esters, due to the use of high catalyst prices so that the cost of plasticizer is quite high. In addition, some enterprises although the production of citric acid ester plasticizer, but due to do not attach importance to the productThe marketing work, users know nothing about their products, will still choose cheap, familiar plasticizer products. As it has become an inevitable trend to accelerate the elimination of toxic plasticizers and the development and promotion of new non-toxic plasticizers, Chinese manufacturers should make great efforts to study new catalytic and separation processes, and bring a new generation of plasticizer products with higher cost performance, more reliable safety and environmental protection to the market as soon as possible.

4. Market segmentation 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 variety has its own physical and chemical properties, and the application field is different. China's plasticizer industry after ten years of development, the industrial base has a considerable scale, production technology is not backward, and different products on the health and safety performance requirements are not the same, so according to the application field of the market segmentation is to avoid plasticizer "trouble" an important means.

China plasticizer enterprises in the increase of production at the same time, should pay more attention to the study of different varieties of plasticizer in various products in the suitability, the two benefits of the right to take its heavy, the two evils of the right to take its light, to provide guidance for users, with practice and facts to prove to consumers that the reasonable use of plasticizer will be safe.

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