1. Forbidden range
Rules of the European Union 2003/53/EC stipulate that the use of APEO shall be strictly limited (except for specific circumstances) from 17 January 2005, the range not only refers to APEO itself, but also includes alkylphenol polyoxyethylene phosphate and alkylphenol polyoxyethylene sulfonates. They are both supplied and marketed at home and abroad. Such as nonylphenol polyoxyethylene phosphate and octyl polyoxyethylene sulfonates, etc. The properties of the latter two have better alkali resistance than APEO, Alkylphenol polyoxyethylene sulfonates have better mobility, they are mainly used to prepare pretreatment agents and rolling dyes, and toxicity is basically similar to APEO (table 1). The degradation metabolites also have low oxygen vinyl chain metabolites and alkyl phenols, it is also more toxic than alkylphenol polyoxyethylene ether phosphate and alkylphenol polyoxyethylene sulfonated.
In addition, the specific conditions referred to in EU rules refer to specific conditions for the use of alkylphenol polyoxyethylene. Such as the adhesive system. That's because there was no better or similar emulsifier that could replace the alkyl polyoxyethylene used in emulsion polymerization for the preparation of adhesives, but recently there have been reports that some European companies have addressed the issue. China's Zhejiang silk science research institute has also developed the self-crosslinking adhesives of non-alkylphenol polyoxyethylene from uncrosslinked adhesives UN-400, UN-800, UN-408, etc.
2. The range of alkyl phenols
Starting from the requirements of the hydrophilic equilibrium value (i.e., the HLB value) and the critical micelle concentration (CMC value) of the auxiliary agent, the study proves that the nonylphenol polyoxyethylene(in which the epoxy ethane polymerization degree is 6~10, the optimum polymerization degree is 9~10) is the most valuable. Emulsification, wetting, dispersion, infiltration, solubilization and washing of various alkylphenol polyoxyethylene ether are the best. But since nonylphenol and octylphenol are both low - carbon alkylphenols, they are difficult to separate in preparation. Therefore, the nonylphenol polyoxyethylene (NPEO) produced in the domestic and foreign markets contains a small amount of octylphenol polyoxyethylene ether (OPEO). There's also a small amount of NPEO in the OPEO.
At present, the production proportion of NPEO is 80%~85% in foreign countries and 85%~90% in China. OPEO accounts for more than 15% of foreign countries and 10% to 15% at home. In addition to the production and supply of NPEO and OPEO in foreign markets, the production and supply of a small amount of dodecylphenol polyoxyethylene (DPEO) to meet specific washing and solubilization requirements is approximately 1%. The most important of the APEO consumed in the world is NPEO, which is close to 90%. Therefore, many foreign countries and enterprises use NPEO to represent APEO.
3. The allowable limits of APEO on textiles
There is a lot of talk about the allowable limit of APEO on textiles, in accordance with EU law 2003/53/EC, the nonylphenol polyoxyethylene (i.e., 1, 000 mg/kg) is prohibited in the production of textiles and leather products. Obviously the law is for chemicals and auxiliaries that contain APEO, they involve the production of all textiles and leather (except for the production process of effluent waste), However, the allowable limit of APEO on textiles is not clear.
In fact, the allowable limits on APEO in many commercial standards are clearer than the EU rules. Some requirements are no more than 500 mg/kg, and there are no more than 100 mg/kg, and there are some standards that do not include APEO. In the absence of an explicit request to comply with the requirements of a commercial contract under the EU rules, the two points are to be clarified:
(1) limitation of APEO requirements, different business standards have different requirements for APEO in textile clothing. Some only ask to limit the total amount of APEO, and others not only ask to limit the amount of APEO, but also limit the amount of NPEO and/or OPEO in APEO, and there are more and more companies making this claim;
(2) restrictions on alkyl phenol, currently, most commercial standards specify the allowable limits of APEO, there are also some criteria for limiting the allowable limits of APEO to the limits of alkyl phenol. Since alkylphenol is an environmental hormone, it is much more toxic than APEO, so it is more demanding, and it allows a much lower limit. For example, the chemicals limitation clause of Swedish H&M company stipulates that the allowable limits of NPEO(9) and OPEO(9) are 500 mg/kg. The allowable limit of NP and OP is 30 mg/kg, which is the same as the allowable limit of 24 carcinogenic aromatic amines. In addition, the detection methods are different. APEO test uses extraction fluid for LC/MS analysis method, while AP test adopts extraction fluid for GC/MS analysis method.
4. The effect of APEO prohibition on textile auxiliaries in China
Because APEO has good surface activity, low surface tension, excellent emulsification, wetting, dispersion, infiltration, solubilization, decontamination, homogenization, etc., it is widely used. It is the most commonly used surfactant in China's textile auxiliary industry. It has developed rapidly since the late 1980s, at that time, many countries in the world, especially in Europe, had included APEO in the list of hazardous chemicals in the environment, and proposed an informal agreement to stop or restrict the use of APEO. China is not very clear about this situation. Instead, Shanghai, Shenyang, Nanjing and Beijing have not only introduced the preparation technology and equipment of non-ionic surfactants from Italy PI and Japan. The preparation technology and equipment of alkyl phenol were introduced, and APEO series products were soon formed.
4.1 The polymerization degree of ethylene oxide is below 10 surface active agent, epoxy ethane polymerization is under 10 surfactants, such as the surfactant NP- 3, 7, 9, 10,OP- 8, 10,TX- 4, 7, 8, 9, 10, etc., they form the main body part of many auxiliaries.
4.2 Epoxy ethane polymerization of surfactant of more than 10
epoxy ethane polymerization is more than 10 surfactants, such as the surfactant np-18, 30, 40,TX- 18, 30, 50, 100, etc., they constitute an important component of some auxiliaries. The textile AIDS prepared from them are estimated to have more than 30 categories, over 500 varieties:
(1) spinning auxiliaries, (a) the prespun POY oil and FDY oil containing surfactant np-10; (b) the DTY oil for post-spinning DTY is mainly containing the surfactant np-3, 7, 10.
(2) pretreatment agent; (a) the cleaning agent is usually made from the compound of surfactant np-10; (b) deoilers and desizing agents are made with a variety of APEO; (c) wetting agents, osmotic agents, scouring agents and other commonly used surfactant np-9, 10 or tx-9, 10, etc. APEO phosphates or APEO sulfonates are used for high alkalinity requirements. If 20% surfactant TX-10 plus 5% APEO sulfonate preparation of osmotic agent, the APEO phosphatates prepared with the reaction of the surface active agent tx-10 and the APEO and P2O5 reaction were mixed with a certain amount of solvent and water to form a scouring agent; (d) biological enzymes such as boiling and pectin are also added to a certain amount of APEO to improve the permeability of the fibers.
4.3 Dyeing assistant. The dyeing auxiliaries (high temperature levelling agent, dispersant, remover repair agent, carrier, defoamer, etc.) contain APEO and its derivatives, if the surfactant OP-9 and 10 are used in the levelling agent to improve its emulsification and dispersion, APEO sulfonates were used to improve the transfection.
4.4 Printing auxiliaries. Printing adhesive, etc. containing surfactant OP 9, 10 or np-9, 10, etc.
4.5 Finishing agent. After finishing agent [organic silicon softener, film, water repellent, coating system (paste, adhesive, coating glue), etc.] the amount of APEO is quite large. Such as amino silicon oil, hydroxy silicone oil, methyl silicone oil and so on, using APEO as emulsifier, the amount of APEO in the microemulsion is 30%~50% of the amino silicone oil. The slurry, adhesives and coating gums in the coating system are composed of different oxygen ethylene chain NPEO to form compound emulsifier or using surfactant op-10, K12 (that is, sodium dodecyl sulfate), plain plus O series or adding surfactant tx-30, 40, etc. to form a compound emulsifier and each constitute the emulsification system; In the film, the surfactant opt-10 is used as emulsifier, etc. The APEO in them will remain on the fabric after finishing the processing (impregnating or leaching). The chemical structure will not change.
4.6 Detergent. Detergent (cleaning agent and soap) is an auxiliary agent for printing and dyeing industry. The amount of APEO in this kind of auxiliaries is larger. Such as general aid agent works are using surfactant TX - 10 or NP - 10 and LAS (linear alkyl benzene sulfonate), 6501 (including 12 carbon amide type nonionic detergent) for distribution of high and low foam detergent or liquid detergent.
4.7 Other auxiliaries. Other auxiliaries are very broad, APEO is included in leather auxiliaries such as leather degreasing agent, leather fat agent and leather finishing agent. The surfactant OP- 9, 10 or np-9 and 10 are also found in silk degumming agents and down degreasing agents. Wool auxiliaries such as and hair oil L52 contain APEO; Metal cleaning agents in metallurgical industry use surfactant np-9 and 10 as emulsifying dispersants. The textile aid dose made up of APEO will not be lower than 50%~60% of China's textile auxiliaries. Therefore, the influence of APEO's disuse on our textile auxiliaries is considerable.
5. The APEO substituting
There is a lot of APEO in the market, however, in terms of performance, source of raw materials, convenience and economy, there are not many varieties that can be fully replaced, and basically the alternatives that can be used are:
(1) fatty alcohol polyoxyethylene, in recent years, as the catalyst for the polymerization reaction in the preparation of potassium hydroxide with alkaline earth metal hydroxide, the distribution of molecular weight of this kind of products is narrow, and the quality is improved, which can be used to replace APEO. They include AEO series (mainly C12~C16 fatty alcohol polyoxyethylene), flat plus O series (mainly C18 fatty alcohol polyoxyethylene);
(2) secondary alcohol polyoxyethylene ether, they has good biodegradability, excellent defoaming, super wetting emulsification properties, good low foam detergent and solubilization, dispersion and wettability, almost no gel phenomenon (low viscosity, low freezing point). Replaced by this kind of product including JFC series (mainly C8 secondary alcohol polyoxyethylene), XL series (mainly C10 secondary alcohol polyoxyethylene), Softanol series (mainly C12 ~ C14 secondary alcohol polyoxyethylene), TO series (mainly C13 secondary alcohol polyoxyethylene);
(3) water loss sorbitol esters and polyoxyethylene, such replacement products include Span series (S - 20, 40, 60, 65, 80, etc.), Tween series (with t-20, 40, 60, 80, 85, etc.);
(4) Alkyl or alkyl polyoxyethylene sulfate, sulfonate, with AES (lauryl polyoxyethylene ether sodium sulfate), K12 (sodium dodecyl sulfate), AOS (alpha olefin sulfonate), SAS (secondary alkyl sulfonate), etc.;
(5) Alkyl Polyglycoside (APG), they belong to multiple carboxyl structure, has the very good biodegradability, non-toxic, emulsifying performance is better than that of surfactant TX - 10, peregal O and Span of 60 and Tween - 20, is a kind of better replace of the product, but the price is a bit expensive.
The above five kinds of basic products, the performance is close to APEO, but the price is a bit high, we can use them to replace the APEO in the circumstances in our country, and can't say that, of course, they have been able to fully replace. In fact, there are many developing products, the better performance of the new replace product, such as N - alkyl amide (AGA) of glucose, fatty acid polyoxyethylene methyl ether (FMEE), alcohol ether carboxylate (AEC), etc., some haven't industrialization, the price also is higher, remains to be further improved.