Study of plastics additives industry
aggregation of antioxidant in plastics, granulation, storage, processing, application has been employed at various stages, is an essential additive in plastics processing. Commonly used plastics antioxidant molecules and mechanisms are divided into 4 categories: hindered phenols and phosphite esters, s-type and composite type for polymerization of polymeric hindered amine 622, 944 light stabilizer combination of anti-aging function and Thermo-oxidative stability and can be classified as 5th category of antioxidants.
about 40,000 t in 2006 China's total consumption plastics antioxidants, antioxidant species each year, exporting mainly. With the massive expansion of domestic petrochemical enterprises and the rapid development of the plastics processing industry, the "Eleven-Five" during the consumption of plastics additives in China will greatly enhance, is expected in 2010 will exceed 80,000 t.
hindered phenolic antioxidant
hindered phenolic antioxidant including alkyl phenols, alkyl phenols, phenol-thio-and so, its role is to prevent oxidative free radicals produced by the plastic continues to react with plastic molecules, has the characteristic of no discoloration, no pollution, so much for the plastics industry.
Bisphenol a and other species, due to low molecular weight, volatile and migration of large, plastic products can be easily colored in plastic consumption was significantly reduced in recent years.
polyphenol antioxidant 1010 and 1076 is a leading product, 1010 because of its high molecular weight, and good compatibility, excellent oxidation resistance of plastic materials, becoming one of the larger consumption plastics antioxidants products. 1010 and 1076 consumption in proportion to total antioxidant consumption 40%, nearly 30 domestic enterprises, production reached more than 5000t, large-scale production enterprises in Ningbo jinhai Albemarle, Shanghai jinhai Albemarle, Yixing Hankuang, linyi Mitutoyo, Ciba Takahashi 5.
n-heterocyclic highest antioxidant polyphenol antioxidant 3114 is melting point, melting point of 220 degrees, due to molecules containing triazine structure, so it has some light effect. Main production enterprise Ningbo jinhai Albemarle Corporation and chemical factory in Zhenjiang, and export-oriented products. With the improvement of domestic technology and plastics processing, consumption of antioxidant 3114 will significantly increase.
phosphite antioxidant, with decomposition of hydrogen peroxide and terminate the dual function of free radical chain reaction. 30% per cent of the total consumption of such antioxidants consumption mainly includes the following products:
(1) three antioxidant 168--(2,4-di-tert-butylphenyl) phosphite 1010 and 1076, most manufacturers also produce antioxidant 168. Although 168 production process is relatively simple, but quality varies, most of the domestic production of 168 products storage period exceeds 1 year, 168 products manufactured by a certain shelf life is only about 6 months.
pentaerythritol diphosphite antioxidant 618--, and double (18 alkyl) pentaerythritol diphosphite 626 and 618 mainly used about 300 ℃ high temperature processing of plastic materials or products, high temperature oxidation resistance of plastic materials can increase the capacity, while maintaining the appearance of plastics. 626 with other primary and secondary and 618 main antioxidant compound for sale. 626 in Ningbo jinhai Albemarle Corporation and other companies formed a certain scale of production and sales, 618 produced by the Research Institute of Jilin Chemical Group company.
(3) antioxidant TNP--TRIS (nonyl phenyl) phosphite antioxidant TNP is the largest producing energy dissipation capacity of liquid antioxidant. In 2006, Shandong laiwu, Maoming, Guangdong and other areas of production total production has reached more than 1000 tons, about 3 times the imports that year.
sulfur-containing antioxidant can break down hydrogen peroxide, resist oxidation and synergies with the phenolic antioxidants, and low toxicity, odor small. Domestic production of sulfur-containing additives classified according to the molecular structure of thio-ester, antioxidant, thio-phenol antioxidant phenolic antioxidants and sulfide-3 varieties.
thio-dipropionate dual 12-ester (DLTP, and DLTDP), thio-b dual 18 propionate ester (DSTP and the DSTDP) main production enterprises Tianjin lisheng chemical addition Assistant Research Institute and Beijing. Lisheng chemical company by using the s-acid esterification process directly with the higher alcohol; Beijing Institute of addition of auxiliaries by thio propanoic acid dimethyl esters and higher alcohols ester exchange of technology of production of such antioxidants.
thio-containing hindered phenol in phenol antioxidant molecule structures exhibit antioxidant properties in plastics material high, good heat resistance and other characteristics of main varieties of antioxidant 300--4,4'-thio-(6-tert-butyl-p-cresol), mainly used for xlpe cable, heat pipe, heat-shrink tubing. 300 to colored protective properties of plastic materials are not very ideal, required after mixing with DLTP or DSTP. Guangzhou Research Institute of synthetic materials are the main suppliers of this product.
sulfur ether type phenol class antioxidant main varieties has 1035--2,2'-sulfur generation double [3-(3,5-II tert-butyl -4-hydroxy phenyl) c acid b ester], production 1035 of raw materials one of is 3,5-methyl ester, another a raw materials is is production chemical weapons of key material sulfur II glycol, but sulfur II glycol belongs to second class monitoring chemicals, source limited and price high, 1035 of production by raw materials and cost of double restricted.
complex antioxidant by two (or more) different types or varieties of the same type of antioxidant compound, and 1010 with 168 different quality than composite antioxidant 215, 225, 561,1076 and 168 compound antioxidant 900, of which 215, consumption of 2,252 varieties account for complex antioxidant 80% per cent of total consumption. Ningbo jinhai Albemarle Corporation 1010 and 626 PW series produced by antioxidants sold high; Beijing Institute of addition of auxiliaries 1010 and secondary production of JC series of complex antioxidant antioxidants has stable sales. Development of composite antioxidant for new varieties, is one of the main directions of research and development.
thermal-oxidative stability of hindered amine light stabilizer function of
hindered amine light stabilizers (HALS) are a group of four methyl-piperidyl 2,2'6'6'-as ring has a steric effect of amine compounds.
HALS the stabilization mechanism of polymer materials is as follows: ① tetramethyl piperidine secondary amine-based polymer materials of light, generated by thermal oxidative aging of hydrogen peroxide, converted into nitrogen and oxygen free radicals NO •; ② NO • capture of free radicals produced by polymer material damaging active groups, for example r •, RO •, ROO • free radicals, transforming it into a relatively stable compound, R-R,R-O-R,R-OO-R, ③ nitrogen and oxygen free radical in this process NO • be regenerated, continue to other free radical reactions and material. In addition, HALS also have the function of quenching of Singlet oxygen, so its from the excited state to the ground state, the photooxidation aging before the chain initiation of intervention. Therefore, HALS in decomposition of hydrogen peroxide, quenching of the excited state oxygen, capture free radicals, itself recycled 4 functions, is not only the highly effective optical stabilizer, is also highly effective antioxidants.
polymerization of polymeric hindered amine 622, 944, anti aging is better than low molecular weight blocked-770, and Thermo-oxidative stability when used in conjunction with antioxidant effect is much better, more experimental data are shown in table 2 and table 3.
made in antioxidant product quality and stability, different batches of products often look and index difference using antioxidants instead of the same brands of imported products, the anti-aging properties of plastics are not stable; engineering plastics and modified plastic special-variety or special antioxidants, low yield, cannot meet the needs of engineering and modified plastics industry development. China antioxidant industry must speed up development pace, recommends following:
(1) strengthening on existing products of improved, production dedicated antioxidant China antioxidant varieties less, should research development new, and efficient antioxidant; for existing products of defects for chemical structure Shang of improved, for example phosphite ester class antioxidant processing stability good, but easy hydrolysis, available amine class to reduced hydrolysis sensitivity, also can improve Asia phosphate ester of molecular volume to reduced volatile sex, and improve resistance precipitation sex and durability. Ciba fine chemical, Sumitomo Chemical, Asahi, electro-chemical companies, Toray has hundreds of exclusive brands, we should focus on research and development of special engineering plastics antioxidants.
(2) increase the development of new antioxidant ① hindered phenolic antioxidant liquid should be developed, such as Irganox1135, 1141 volatile small, high migration of hindered phenolic antioxidant liquid second half of hindered phenolic antioxidant: the asymmetry hindered phenolic antioxidant such antioxidant and the Vulcanized and other auxiliary antioxidant synergy, such as Irganox245, Cyanox1790, ADkStabAO-80, and so on; ③ Amine class antioxidant: Fong amine class antioxidant main for rubber products, for example Irganox5070 of replaced II aniline class antioxidant, and blocked phenol, and Asia phosphate ester, antioxidant Association effect sex good; II phosphite ester antioxidant: is near 10 years to development most fast of field, especially to quarter e four alcohol double phosphite ester spiral structure and double phenol phosphite ester structure of mostly; ⑤ metal ion passivation agent: to double salicylidene II amine mainly, but should development multifunctional metal ion passivation agent, For example, Ciba-IrganoXMD1024 and youniluoyier NouguardXL-1.
(3) the complex technology we have made a lot of successful experience should be extended may research development of hindered phenol-thiol antioxidant complex technology.
(4) dust-, polymer quantization using concentrated masterbatch to improve antioxidant volatility and resistance extraction, the extension of its validity, can also help to improve operating environment.
(5) the ternary ternary antioxidant system and antioxidant system in high temperature oxidation resistance is better than binary antioxidant system, which is the development trend of high temperature antioxidant.
(6) the hindered phenol in phenol-free trend after capturing the oxygen free radicals into Quinones and yellowing of the products, should be used by hydroxylamine, benzene and furan phenol, hindered amine, UV absorbers and phosphite compound system composed of, to the non-phenolic antioxidant technology development. Can development of varieties has: ① carbon free base capture agent, as steam BA fine of of IrganoxHP-136; II Hydroxyl Amine class free base capture agent, as steam BA of FiberatabFSO42; ③ tert-amine nitride real free agent capture agent, as GE company of FiberstabEP; II double phenol single acrylic ester class carbon free base capture agent, as live friends chemical company of SamilizerGM and GS, Shanxi province Chemical Institute of KY-394.
(7) green, antioxidant vitamin e, vitamin e and egg lecithin compound environment-friendly antioxidants and vitamins e and phosphite esters, glycerin, polyethylene glycol, high porosity resin compound into the complex is focused on developing green antioxidant.