Phosphite antioxidants

Another method for slowing oxidation of rubber adhesives is to add a compound which destroys the hydroperoxides formed in step 3, before they can decompose into radicals and start the degradation of new polymer chains. These materials are called hydroperoxide decomposers, preventive antioxidants or secondary antioxidants. Phosphites (phosphite esters, organophosphite chelators, dibasic lead phosphite) and sulphides (i.e. thiopropionate esters, metal dithiolates) are typical secondary antioxidants. Phosphite esters decompose hydroperoxides to yield phosphates and alcohols. Sulphur compounds, however, decompose hydroperoxides catalytically. 

While the primary antioxidant serves a critical role, it cannot stop all polymer peroxy radicals from propagating. This is where a second class of antioxidants, called peroxide decomposers, comes in. These molecules catalyze the decomposition of the peroxides to nonradical species, thus breaking the repetitive cycle of radical formation. Phosphites and thioesters commonly serve as secondary antioxidants. Phosphites are commonly used in HIPS resins, but care must be taken to use hydrolysis-resistant molecules to avoid the degradation of these species into black specks that render the final product unacceptable. Phosphites are usually found at levels between 500 and 2000 ppm. 

Metal deactivator that acts as a hindered phenolic antioxidant. Used in conjunction with phenolic antioxidants, phosphites/ phosphonites, thio-synergists and other co-additives. Most suited for PA PE, Rubbers and PP applications. 

Naugard PS-30 is a liquid amine antioxidant typically used with phenolic antioxidants, phosphites, and synergists in poly-ether polyols to inhibit physical/color scorch associated with the production of flexible urethane foam. 

Stabilisers/Antioxidants Phosphite/phosphonites are generally regarded as the most effective stabilisers during processing, protecting both the polymer and the primary antioxidant. The most expensive stabilisers are organotin stabilisers, while lead compounds are the cheapest. 

U626 is a rather complex molecule. Very interestingly the phosphite moieties in U626 can have also an important role in the stabilization. Phosphites are well-known stabilizers and they are called secondary antioxidants, while hindered phenol-based stabilizers are known as primary antioxidants. Phosphites have the ability to react with hydroperoxides to yield phosphates according to scheme 5.[20,38] U626 combines primary and secondary stabilizers in the same molecule. 

Polymer is degraded by heat, energy, UV or residues of catalyst and generates alkyl radicals. This alkyl radical reacts with oxygen and form peroxy radicals. These peroxy radicals abstract hydrogen from other polymer and forms alkyl radicals and hydroperoxide. The decomposition of hydroperoxide to alkoxy and hydroxyl radicals induces additional decomposition of the polymer chain. In order to stop the radical chain reaction of degradation, stabilisers such as phenolic antioxidant, phosphites, thioether and hindered amine light stabilisers (HALS) are added. 

Reacts with secondary antioxidants (phosphites, hydroxyi amines) to yieid inactive products... 

Costabilizers enhancing light stability phenolic antioxidants, phosphites and... 

Introduction of additives is a well-known method for the mechanism of the chemical reaction investigation. The experience has shown effectiveness of triple stabilizing formulations (Cu-containing compound + phenolic antioxidant + phosphite) for aryl-aliphatic polyamides, polyphthtalamides and other thermally stable polymers. The conception of such formulation is based on the mechanisms of the stabilizing action of the components ... 

OIT/Tox measurements provide rapid and reliable results. Many materials contain a system of antioxidants, often a combination of a primary antioxidant (hindered phenol or amine) and a secondary antioxidant (phosphite, thioester, etc.). Thermal analysis provides no information about the concentration of the different antioxidants separately but rather an overall assessment of the stability. Extraction followed by chromatography (HPLC) is one of the main techniques for the determination of antioxidant concentration, but it is no doubt much more time-consuming than DSC/DTA. 

Here we have to distinguish between transparent and non-transparent polyamides. In the former, the known phenolic antioxidants soluble in polyamides may be used, and perhaps compatible UV-stabilizers based on benzotriazole. For the latter, all stabilizers or stabilizer systems suitable for polyamides can be used, such as phenolic antioxidants, phosphites, and inorganic systems [502]. 

HAS light/UV stabilizers, phenolic antioxidants, benzophenone stabilizers, antioxidants, phosphite antioxidants, bis(tribomophenoxy)ethane... 

Peroxide-decomposing antioxidants destroy hydroperoxides, the sources of free radicals in polymers. Phosphites and thioesters such as tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, and dialkyl thiodipropionates are examples of peroxide-decomposing antioxidants. 

Cost bilizers. In most cases the alkyl tin stabilizets ate particularly efficient heat stabilizers for PVC without the addition of costabilizers. Many of the traditional coadditives, such as antioxidants, epoxy compounds, and phosphites, used with the mixed metal stabilizer systems, afford only minimal benefits when used with the alkyl tin mercaptides. Mercaptans are quite effective costabilizets for some of the alkyl tin mercaptides, particularly those based on mercaptoethyl ester technology (23). Combinations of mercaptan and alkyl tin mercaptide ate currendy the most efficient stabilizers for PVC extmsion processes. The level of tin metal in the stabilizer composition can be reduced by up to 50% while maintaining equivalent performance. Figure 2 shows the two-roU mill performance of some methyl tin stabilizers in a PVC pipe formulation as a function of the tin content and the mercaptide groups at 200°C. 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Phosphites. Tertiary phosphites are also commonly used and are particularly effective ia most mixed metal stabilizers at a use level of 0.25—1.0 phr. They can take part ia a number of different reactions duting PVC processing they can react with HCl, displace activated chlorine atoms on the polymer, provide antioxidant functionaHty, and coordinate with the metals to alter the Lewis acidity of the chloride salts. Typical examples of phosphites are triphenyl phosphite [101 -02-0], diphenyl decyl phosphite [3287-06-7], tridecyl phosphite [2929-86-4], and polyphosphites made by reaction of PCl with polyols and capping alcohols. The phosphites are often included in commercial stabilizer packages. 

The basic metal salts and soaps tend to be less cosdy than the alkyl tin stabilizers for example, in the United States, the market price in 1993 for calcium stearate was about 1.30— 1.60, zinc stearate was 1.70— 2.00, and barium stearate was 2.40— 2.80/kg. Not all of the coadditives are necessary in every PVC compound. Typically, commercial mixed metal stabilizers contain most of the necessary coadditives and usually an epoxy compound and a phosphite are the only additional products that may be added by the processor. The requited costabilizers, however, significantly add to the stabilization costs. Typical phosphites, used in most flexible PVC formulations, are sold for 4.00— 7.50/kg. Typical antioxidants are bisphenol A, selling at 2.00/kg Nnonylphenol at 1.25/kg and BHT at 3.50/kg, respectively. Pricing for ESO is about 2.00— 2.50/kg. Polyols, such as pentaerythritol, used with the barium—cadmium systems, sells at 2.00, whereas the derivative dipentaerythritol costs over three times as much. The P-diketones and specialized dihydropyridines, which are powerful costabilizers for calcium—zinc and barium—zinc systems, are very cosdy. These additives are 10.00 and 20.00/kg, respectively, contributing significantly to the overall stabilizer costs. Hydrotalcites are sold for about 5.00— 7.00/kg. 

Oxidation of LLDPE starts at temperatures above 150°C. This reaction produces hydroxyl and carboxyl groups in polymer molecules as well as low molecular weight compounds such as water, aldehydes, ketones, and alcohols. Oxidation reactions can occur during LLDPE pelletization and processing to protect molten resins from oxygen attack during these operations, antioxidants (radical inhibitors) must be used. These antioxidants (qv) are added to LLDPE resins in concentrations of 0.1—0.5 wt %, and maybe naphthyl amines or phenylenediamines, substituted phenols, quinones, and alkyl phosphites (4), although inhibitors based on hindered phenols are preferred. 

Both thermooxidation and photooxidation of polyolefins can be prevented by using the same antioxidants as those employed for the stabilization of polypropylene, ie, alkylated phenols, polyphenols, thioesters, and organic phosphites in the amount of 0.2—0.5% (22,25). 

Organophosphoms compounds, primarily phosphonic acids, are used as sequestrants, scale inhibitors, deflocculants, or ion-control agents in oil wells, cooling-tower waters, and boiler-feed waters. Organophosphates are also used as plasticizers and flame retardants in plastics and elastomers, which accounted for 22% of PCl consumed. Phosphites, in conjunction with Hquid mixed metals, such as calcium—zinc and barium—cadmium heat stabilizers, function as antioxidants and stabilizer adjutants. In 1992, such phosphoms-based chemicals amounted to slightly more than 6% of all such plastic additives and represented 8500 t of phosphoms. Because PVC production is expected to increase, the use of phosphoms additive should increase 3% aimually through 1999. 

The tendency of aliphatic ethers toward oxidation requires the use of antioxidants such as hindered phenoHcs (eg, BHT), secondary aromatic amines, and phosphites. This is especially tme in polyether polyols used in making polyurethanes (PUR) because they may become discolored and the increase in acid number affects PUR production. The antioxidants also reduce oxidation during PUR production where the temperature could reach 230°C. A number of new antioxidant products and combinations have become available (115,120,124—139) (see Antioxidants). 

Solubility. Another desirable property of a degradant is its high solubihty in mbber but poor solubihty in water and solvents that come in contact with mbber. Poor solubihty in the mbber means that only small quantities of antioxidants can be dissolved without producing a bloom. As an example, N,lSf-diphenyl- phenylenediamine (DPPD) has limited use because of its poor solubihty in mbber. On the other hand, phenohc and phosphite antioxidants have high solubihty and bloom is not a problem. 

Antioxidant Types. Commercially available antioxidants may be divided into three general classes secondary amines, phenolics, and phosphites. 

In general, the amines are more active than the phenoHcs which are in turn more active than the phosphites. Amine antioxidants, however, often cause staining problems and are therefore used mainly in black stocks. The phenoHcs and phosphites are relatively nonstaining and are normally used ia light-colored mbbers. 

These polymers are subjected to high temperatures, ca 300°C, duting extmsion and iajection molding. Processing stabilizers are used to decrease both the change ia viscosity of the polymer melt and the development of color. A phosphite, such as tris(2,4-di-/ f2 -butyiphenyi)phosphite (25) or bis(2,4-di-/ f2 butyiphenyi)pentaerythritol diphosphite [26741-53-7] ia combination with a phenoHc antioxidant such as octadecyl... 

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