Patent Publication Number: US-2010130654-A1

Title: Use of low triphenylphosphate, high phosphorous content isopropyl phenyl phosphates as flame retardants in resins

Description:
FIELD OF THE INVENTION 
     The present invention relates to the use of low triphenyl phosphate, high phosphorous content, aryl phosphates, with high ortho alkylation as flame retardant compositions in styrenic resins. 
     BACKGROUND OF THE INVENTION 
     Styrenic resins are used in many applications today. Because of their widespread use, much research has been done on providing flame retardancy to styrenic resins. To this end, halogenated flame retardants and phosphorus flame retardants have been used to provide these flame retardant properties. For example, alkylated aryl phosphates are known in the art to be useful as flame-retardants in such applications. However, the processes typically used to form alkylated aryl phosphates produce triphenyl phosphate (“TPP”) as a by-product of the alkylated phenyl phosphate formation reaction and is unwanted in the final product because of environmental concerns For example, TPP has been classified as a marine pollutant in some jurisdictions. Thus, it would be desirable to provide for alkylated aryl phosphates flame retardants suitable for use in styrenic resins having reduced amounts of TPP, when compared to currently available products, and also flame retarded styrenic resins also containing reduced amounts of TPP. 
     SUMMARY OF THE INVENTION 
     In one embodiment, the present invention relates to the use of an alkylated triaryl phosphate ester comprising less than about 1 wt % triphenyl phosphate, based on the total weight of the alkylated triaryl phosphate ester, and an organic phosphorous content in the range of from about 5 to about 10 wt %, based on the total weight of the alkylated triaryl phosphate ester as a flame retardant in polyvinyl chloride resins. 
     In another embodiment, the present invention relates to the use of an alkylated triaryl phosphate ester comprising one or more of the following alkylated phenyl phosphates: a) monoalkylphenyl diphenyl phosphates; b) di-(alkylphenyl)phenyl phosphates; c) dialkylphenyl diphenyl phosphates; d) trialkylphenyl phosphates; e) alkylphenyl dialkylphenyl phenyl phosphates; and f) less than about 1 wt. % triphenyl phosphate, based on the total weight of the alkylated triaryl phosphate ester, wherein the alkyl moieties of the alkylated phenyl phosphates are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary-butyl, amyl, isoamyl, tertiary-amyl, and cyclohexyl groups and the total phosphorous content of the alkylated triaryl phosphate ester ranges from about 5 to about 10 wt %, based on the total weight of the alkylated triaryl phosphate ester, as a flame retardant in polyvinyl chloride resins. 
     In another embodiment, the present invention relates to a flame retarded resin formulation comprising at least one, sometimes only one, polyvinyl chloride resin and a flame retarding amount of an alkylated triaryl phosphate ester as described herein. 
     In another embodiment, the present invention relates to a flame retarded resin formulation or a flame retarded styrenic resin derivable from at least one, sometimes only one, polyvinyl chloride resin and a flame retarding amount of an alkylated triaryl phosphate ester as described herein. 
     In some embodiments, the present invention also relates to articles made from flame retarded resin formulations or a flame retarded styrenic resins according to the present invention. 
     The alkylated triaryl phosphate esters used as flame retardants in the present invention can be made by a process comprising:
         a) reacting an alkylated phenol comprising less than about 1 mole % phenol and up to about 75 mole % dialkyl phenol, both based on the total moles of reactive alkylated phenolics in the alkylated phenol, with POCl 3  in the presence of a first catalyst under first reaction conditions including temperatures ranging from about 80° C. to about 210° C. thereby producing a first reaction product comprising greater than about 75 mole % monoalkylated phenyl-dichloro phosphates, based on the total moles of the first reaction product; and   b) reacting the first reaction product with an alcohol selected from aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst under second reaction conditions including temperatures ranging from about 90° C. to about 260° C. thereby producing an alkylated triaryl phosphate ester;
 
or
   a) reacting an alkylated phenol comprising less than about 1% phenol and up to about 75% dialkyl phenol, both based on the total weight of the alkylated phenol, with a molar excess of POCl 3  in the presence of a first catalyst under first reaction conditions including temperatures ranging from about 80° C. to about 210° C. thereby producing a first reaction product comprising greater than about 50 mole %, based on the total moles of the first reaction product, monoalkylated phenyl-dichloro phosphates and excess POCl 3 ;   b) removing at least a portion of the excess POCl 3  from the first reaction product to produce an intermediate product, wherein said intermediate reaction product contains less than 15 mole % phosphorus, based on the total moles of the intermediate reaction product, in the form of POCl 3  remains; and   c) reacting the first reaction product with an alcohol selected from aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst under second reaction conditions including temperatures ranging from about 90° C. to about 260° C. thereby producing an alkylated triaryl phosphate ester.       

    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     As used herein, “IP&#39;s” is meant to refer to isopropylatedphenols; “OIP” is meant to refer to ortho-isopropylphenol; “MIP” is meant to refer to meta-isopropylphenol; “PIP” is meant to refer to para-isopropylphenol; “TPP” is meant to refer to triphenyl phosphate; “2,6-DIP” is meant to refer to 2,6-diisopropylphenol; “2,4-DIP” is meant to refer to 2,4-diisopropylphenol; “2,4,6-TIP” is meant to refer to 2,4,6-triisoproplylphenol; “2-IPP” is meant to refer to 2-isopropylphenyl diphenyl phosphate; “3-IPP” is meant to refer to 3-isopropylphenyl diphenyl phosphate; “4-IPP” is meant to refer to 4-isopropylphenyl diphenyl phosphate; “2,4-DDP” is meant to refer to 2,4-diisopropylphenyl diphenyl phosphate; “IPP&#39;s” is meant to refer to isopropylated triphenyl phosphates; “DTPP” is meant to refer to diisopropylated triphenyl phosphate; and “TTPP” is meant to refer to triisopropylated triphenyl phosphate. 
     Alkylated Triaryl Phosphate Esters 
     In one embodiment, the present invention relates to alkylated triaryl phosphate esters. The alkylated triaryl phosphate esters of the present invention are characterized as containing less than about 1 wt % TPP, based on the total weight of the alkylated triaryl phosphate ester, in some embodiments less than about 0.75 wt % TPP, on the same basis, and in other embodiments, less than about 0.5 wt % TPP, on the same basis. 
     Despite the low concentrations of TPP, the alkylated triaryl phosphate esters of the present invention still contain a high amount of phosphorus. Typically the alkylated triaryl phosphate esters of the present invention contain from about 5 to about 10 wt % organic phosphorous, based on the total weight of the alkylated triaryl phosphate ester. Preferably the organic phosphorus content ranges from about 7 to about 9 wt %, on the same basis, and in more preferred embodiments the organic phosphorous content ranges from about 7.5 to about 8.5 wt %, most preferably in the range of from about 8.0 to about 8.4%, on the same basis. 
     The alkylated alkylated triaryl phosphate esters of the present invention can also be described as containing monalkylphenyl diphenyl phosphates, di-(alkylphenyl)phenyl phosphates, dialkylphenyl diphenyl phosphates, dialkylphenyl diphenyl phosphates, trialkylphenyl phosphates, and mixtures thereof. 
     In some embodiment, the alkylated triaryl phosphate esters of the present invention are further characterized as containing greater than about 20 wt % monalkylphenyl diphenyl phosphates, based on the total weight of the alkylated triaryl phosphate ester. Preferably, the alkylated triaryl phosphate esters contain greater than about 75 wt %, on the same basis, monalkylphenyl diphenyl phosphates, more preferably greater than about 90 wt %, on the same basis. 
     The alkylated triaryl phosphate esters of the present invention can further be characterized as containing less than about 80 wt % di-(alkylphenyl)phenyl phosphates, based on the total weight of the alkylated triaryl phosphate ester. Preferably the alkylated triaryl phosphate esters of the present invention contain less than about 25 wt %, more preferably less than about 10 wt %, di-(alkylphenyl)phenyl phosphates, on the same basis. 
     The alkylated triaryl phosphate esters of the present invention can also be further characterized as containing less than about 50 wt %, based on the total weight of the alkylated triaryl phosphate ester, dialkylphenyl diphenyl phosphates. However, in preferred embodiments, the alkylated triaryl phosphate esters of the present invention contain less than about 25 wt %, more preferably less than about 10 wt %, dialkylphenyl diphenyl phosphates, on the same basis. In a most preferred embodiment, the alkylated triaryl phosphate esters of the present invention contain less than about 1 wt %, based on the total weight of the alkylated triaryl phosphate ester, dialkylphenyl diphenyl phosphates. The inventors hereof have unexpectedly discovered that, in some embodiments, the removal of unreacted alkylated phenols during the production of the alkylated triaryl phosphate esters of the present invention is more efficient for alkylated triaryl phosphate esters having these concentrations of dialkylphenyl diphenyl phosphates. 
     The amount of trialkylphenyl phosphates present in the alkylated triaryl phosphate esters of the present invention is generally less than about 20 wt %, based on the total weight of the alkylated triaryl phosphate ester. However, in preferred embodiments, the alkylated phenyl phosphates of the present invention can contain less than about 2 wt %, on the same basis, of trialkylphenyl phosphates. In some most preferred embodiments the level of trialkylphenyl phosphates is less than 0.5 wt %, on the same basis. The alkylated phenyl phosphates according to the present invention also comprise less than about 20 wt %, based on the total weight of the alkylated triaryl phosphate ester, alkylphenyl dialkylphenyl phenyl phosphates. In most preferred embodiments the alkylated triaryl phosphate esters of the present invention contain less than 0.05 wt %, based on the total weight of the alkylated triaryl phosphate ester, of the alkylphenyl dialkylphenyl phenyl phosphates. 
     Exemplary alkylated triaryl phosphate esters of the present invention are those a) those that comprise: in the range of from about 90 to about 92 wt. % IPP, in the range of from about 0.5 to about 0.75 wt. % TPP, in the range of from about 1 to about 3 wt. % DTPP, in the range of from about 0.05 to about 0.15 wt. % TTPP, and in the range of from about 0.5 to about 0.75 wt. % 2,4-DDP; b) in the range of from about 94 to about 96 wt. % IPP, in the range of from about 3.5 to about 5.5 wt. % DTPP, and in the range of from about 0.1 to about 0.3 wt. % TTPP; and c) in the range of from about 71 to about 73 wt. % IPP, in the range of from about 0.05 to about 0.15 wt. % TPP, in the range of from about 26 to about 28 wt. % DTPP, and in the range of from about 0.5 to about 0.7 wt. % TTPP. 
     Monoalkylphenyl diphenyl phosphates, di-(alkylphenyl)phenyl phosphates, dialkylphenyl diphenyl phosphates, trialkylphenyl phosphates, and alkylphenyl dialkylphenyl phenyl phosphates, present in the alkylated triaryl phosphate esters of the present invention are those wherein the alkyl moieties are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary-butyl, amyl, isoamyl, tertiary-amyl groups, and cyclohexyl alkyl moieties. Preferably, the alkyl moieties of at least one of, preferably at least two of, more preferably all of, the monoalkylphenyl diphenyl phosphates, di-(alkylphenyl)phenyl phosphates, dialkylphenyl diphenyl phosphates, trialkylphenyl phosphates, and alkylphenyl dialkylphenyl phenyl phosphates, present in the alkylated triaryl phosphate esters are isopropyl moieties. Thus, for example, in a most preferred embodiment, the alkylated triaryl phosphate esters according to the present invention are isopropylphenyl diphenyl phosphate esters. Of the total isopropylphenyl diphenyl phosphate esters weight, 0.1 to 99.9 wt % is 2-isopropylphenyl phosphate (2-IPP), 0.1 to 99.9 wt % is 3-isopropylphenyl phosphate (3-IPP), 0.1 to 99.9 wt % is 4-isopropylphenyl phosphate (4-IPP), all based on the total weight of the alkylated triaryl phosphate ester. In the most preferred embodiments 66 to 100 wt % of the isopropylphenyl phenyl phosphate present in the alkylated triaryl phosphate esters according to the present invention is 2-isopropylphenyl phosphate (2-IPP), 0.1 to 4 wt % is 3-isopropylphenyl phosphate (3-IPP), 0.1 to 40 wt % is 4-isopropylphenyl phosphate (4-IPP). It should be noted that although specific ranges of isopropylphenyl phenyl phosphate have been discussed above, it is within the scope of the present invention to produce an alkylated triaryl phosphate ester having any possible relative ratio of 2-IPP, 3-IPP and 4-IPP. However, in a most preferred embodiment, the alkylated triaryl phosphate esters according to the present invention are isopropylphenyl diphenyl phosphate esters wherein in the range of about 63 to about 68 wt. % of the isopropylphenyl diphenyl phosphate ester is 2-IPP, in the range of from about 0.5 to about 2.5 wt. % is 3-IPP and in the range of from about 30.5 to about 36.5 wt. % is 4-IPP, all based on the total weight of the isopropylphenyl diphenyl phosphate ester. In an exemplary embodiment of the present invention, the alkylated triaryl phosphate esters according to the present invention are isopropylphenyl diphenyl phosphate esters wherein about 66 wt. % of the isopropylphenyl diphenyl phosphate ester is 2-IPP, about 1 wt. % is 3-IPP and about 33 wt. % is 4-IPP, on the same basis. The alkylated triaryl phosphate esters of the present invention can suitably be formed by a process comprising reacting an alkylated phenol with POCl 3  in the presence of a first catalyst, thus forming a first reaction product. The first reaction product is then reacted with an alcohol selected from aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst under second reaction conditions including temperatures ranging from about 90° C. to about 260° C. thereby producing an alkylated triaryl phosphate ester according to the present invention. It should be noted that the reaction that produces the first reaction product is sometimes referred to as the first reaction herein, and the reaction of the first reaction product with the alcohol is sometimes referred to herein as the second reaction. 
     First Reaction—Alkylated Phenol 
     Alkylated phenols suitable for use in the first reaction include those wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, isobutyl, tertiary-butyl, amyl, isoamyl, tertiary-amyl alkyl moieties, and cyclohexyl, preferably isopropyl moieties. 
     Preferably, the alkylated phenol that is reacted with the POCl 3  in the presence of the first catalyst contains less than 1 mole % phenol and less than 25 mole % dialkyl phenol, both based on the total moles of reactive alkylated phenols (as described below) in the alkylated phenol. In a more preferred embodiment, the alkylated phenol contains less than 0.5 mole % phenol and less than 15 mole % dialkyl phenol, both based on the total moles of reactive alkylated phenols in the alkylated phenol. In a most preferred embodiment, the alkylated phenol contains less than 0.5 mole % phenol and less than 5 mole % 2,4-diisopropylphenol, both based on the total moles of reactive alkylated phenolics in the alkylated phenol. In preferred embodiments, the dialkyl phenol of the alkylated phenol is 2,4-disiopropylphenol. 
     In an even more preferred embodiment, the alkylated phenol stream comprises essentially OIP, MIP, and PIP constituents. In this embodiment, it is preferred that the alkylated phenol stream comprise in the range of from about 64 to about 68 wt. % OIP, in the range of from about 0.5 to about 2.5 wt. % MIP, and in the range of from about 31 to about 35 wt. % PIP, all based on the total weight of the alkylated phenol. 
     “Total moles of reactive alkylated phenols” and “Reactive alkylated phenol” as used herein is meant to refer to the total moles of alkylated phenols that are part of the reaction between the alkylated phenol and the POCl 3 . This unit of measure is used herein because unreactive alkylated phenols are also present in the alkylated phenol. For example, 2,6-DIP and 2,4,6-TIP are common impurities in an IP&#39;s stream but are for all intents and purposes unreactive. For example, see Table 1 below, which describes one example of an alkylated phenol suitable for use herein: 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Isopropylated Phenol Stream 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 GC 
                   
                 Reactive 
               
               
                 Component 
                 FW 
                 wt % 
                 Mole/100 g 
                 moles/100 g 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Phenol 
                 94.11 
                 0.35 
                 0.0037 
                 0.0037 
               
               
                 OIP 
                 136.19 
                 59.48 
                 0.4367 
                 0.4367 
               
               
                 PIP 
                 136.19 
                 29.76 
                 0.2185 
                 0.2185 
               
               
                 2,6-DIP 
                 178.27 
                 4.25 
                 0.0238 
                 Inert 
               
               
                 2,4-DIP 
                 178.27 
                 5.83 
                 0.0327 
                 0.0327 
               
               
                 2,4,6-TIP 
                 220.35 
                 0.32 
                 0.0015 
                 Inert 
               
            
           
           
               
               
               
               
            
               
                 Average FW 
                   
                 139.76 
                 *134.83 
               
               
                   
               
            
           
         
       
     
     In Table 1, the amounts described herein as based on the total moles of reactive alkylated phenols would thus be based on 134.83 moles. 
     First Reaction—POCl 3    
     The amount of POCl 3  used herein can be a molar equivalency, in some embodiments a molar excess, and in other embodiments, less than a molar equivalency. By a molar equivalency of POCl 3 , it is meant that a molar ratio of about 1 moles of POCl 3  to about 1 mole of reactive alkylated phenol. By a molar excess of POCl 3 , it is meant that a molar ratio of greater than 1 moles of POCl 3  to 1 mole of reactive alkylated phenol. Preferably a molar excess is in the range of from about 1.0 to about 5.0 moles of POCl 3  to about 1 mole of reactive alkylated phenol, and more preferably in the range of from about 1.15 to about 2.5 moles of POCl 3  to about 1 mole of reactive alkylated phenol are used in the practice of this embodiment of the present invention. 
     By less than a molar equivalency of POCl 3 , it is meant a molar ratio of less than 1 mole of POCl 3  to 1 mole of reactive alkylated phenol. For example, in one embodiment, which would produce a first reaction product having significantly higher DTTP and TTPP, a molar excess of alkylated phenol can be used, i.e. less than a molar equivalency of POCl 3 . In this embodiment, it is preferred to use greater than in the range of from about 1 to about 2, preferably in the range of from 1.1 to about 1.2, moles of reactive alkylated phenol per mole of POCl 3 . 
     Reactive alkylated phenol is defined above. 
     First Catalyst 
     Catalysts suitable for use as the first catalyst herein can be selected from tertiary amines such as trialkyl amines, dialkylaryl amines, and heterocyclic tertiary amines such as 1,4 Diazabicyclo[2,2,2]octane (DABCO); aromatic amines such as pyridine and substituted pyridines with N,N-dimethylaminopyridine being preferred from this group; pyrimidines and its derivatives; pyrazine and its derivatives; pyroles and its derivatives; imidizoles, its derivatives and their corresponding mineral and organic acid salts with N-methylimidazole, imidiazole and its derivatives being preferred from this group; quaternary ammonium salts; quaternary phosphonium salts; tetrakis dialkylamino phosphonium salts having the general formula P(NRR′) 4   + X −  especially tetrakis diethylamino phosphonium Bromide having the formula P(NEt 2 ) 4   + Br − ; alkali metal halide catalysts; and alkali earth metal halides, oxides, sulfates, sulfonates, hydroxides, and phosphates. It should be noted that any alkali metal halide and salts, e.g. ammonium, phosphonium, etc., as described above, can be used as long as the salt/halide has appreciable solubility to initiate the reaction with POCl 3  such that co-produced hydrogen chloride ultimately converts the metal catalyst salt to the metal chloride salt. Non-limiting examples of alkali metal and alkali earth metal catalysts include AlCl 3 , MgCl 2 , CaCl 2 , NaCl, KCl, FeCl 3 , LiCl, TiCl 4 , SbCl 4 , AgCl and BaCl 2 . Non-limiting examples of suitable quaternary ammonium salts include tetrabutylammonium halide, tetra alkyl or mixed alkyl ammonium mineral or organic acid salt. Non-limiting examples of suitable quaternary phosphonium salts include any tetra-alkyl or tetra-aryl phosphonium salt. Preferably the first catalyst is selected from quaternary ammonium salts, quaternary phosphonium salts, tetrabutylammonium chloride, MgCl 2 , and pyridine. In one preferred embodiment the first catalyst is tetrabutylammonium chloride. In yet another preferred embodiment the first catalyst is MgCl 2 . In a particularly preferred embodiment, the first catalyst is pyridine. 
     First Reaction Conditions 
     The POCl 3  and alkylated phenol are reacted under first reaction conditions that include temperatures ranging from about 75° C. to about 210° C. Preferably, first reaction conditions include temperatures ranging from about 80° C. to about 150° C., more preferably temperatures ranging from about 90° C. to about 140° C. The reactants and first catalyst can be combined, contacted, etc. in any order. However, it is preferred that the alkylated phenol reactant be added to the POCl 3  reactant. It has been found that an alkylated phenol phosphate with superior viscosity, i.e. less viscous, can be produced by combining the reactants and catalyst in this order. In a more preferred embodiment, the alkylated phenol is added to a reaction vessel containing both the POCl 3  reactant and first catalyst. 
     It should be noted that the reaction between the alkylated phenol and POCl 3  produces HCl gas, which can cause undesirable cleavage and/or transesterification reactions. Thus, in preferred embodiments, first reaction conditions also include venting of HCl gas. This venting can be conducted by any means known to be effective at venting HCl gas from a reaction vessel. However, in preferred embodiments, the venting is accomplished by conducting the reaction under first reaction conditions that include sub-atmospheric pressures, i.e. under a vacuum. The amount of vacuum used is readily selected by one having ordinary skill in the art taking into consideration that too much vacuum would cause the reaction temperature to fall outside of the ranges described above, thus slowing the reaction rate. Further, while vacuum pressures are preferred, the reaction can be conducted at atmospheric pressures up to about 5 psig and still produce a desirable product, albeit at a reduced rate. A pressure significantly above 5 psig would slow the reaction rate somewhat more and potentially lead to the undesirable cleavage and/or transesterification reactions. 
     In preferred embodiments, first reaction conditions further include the substantial absence of oxygen. 
     First Reaction—Optional Diluent 
     In some embodiments, a diluent can be added along with the POCl 3 , first catalyst, and alkylated phenol. Diluents suitable for use herein are those that i) do not react substantially with the reagents, products and co-products, including HCl, utilized or generated during the first and/or second reactions; and ii) do not substantially reduce the catalytic activity of the first and/or second catalyst. In preferred embodiments, diluents suitable for use herein can be further characterized as those that iii) do not lower the reaction temperature such that the reaction rate slows significantly to the point of not being commercially feasible, i.e. below the ranges disclosed herein. It should be noted that the diluent can be added as a complex with the first catalyst. Non-limiting examples of suitable diluents include a) hydrocarbon solvents, such as heptane, petroleum ethers, methylcyclohexane and boiling point heptane; b) aromatic hydrocarbons such as toluene, xylene(s) and ethyl benzene; c) halo hydrocarbons and halo aromatic hydrocarbons such as chlorobenzene, dibromomethane, dibromoethane, and all isomers of trichloroethylene; d) ether solvents such as, tetrahydrofuran or 1,4-dioxane. Preferably, if an ether diluent is used, the diluent is 1,4-dioxane. In a most preferred embodiment, the diluent is toluene. 
     First Reaction Product 
     The reaction of the POCl 3  and alkylated phenol produces a first reaction product comprising greater than about 50 mole % monoalkylatedphenyl dichloro phosphates, based on the total moles of the first reaction product excluding unreacted POCl 3  and any added diluent. 
     In some embodiments, the first reaction product can comprise in the range of from about 70 to about 99.9 mole % monoalkylatedphenyl dichloro phosphates, on the same basis, and in the range of from about 0.1 mole % to about 30 mole % bis-(monoalkylated)phenyl-chloro phosphates, on the same basis. 
     By excess POCl 3  it is meant any POCl 3  that did not react with the alkylated phenol, i.e. unreacted POCl 3 . Typically, the first reaction product comprises in the range of from about 5 to about 80 mole % unreacted POCl 3 , based on the total phosphorus in the first reaction product, as determined by some suitable method, preferably quantitative P-31 NMR. The amount of unreacted POCl 3  in the first reaction product is obviously dependent on the amount of POCl 3  used in the first reaction stage. For example, if less than a molar equivalency of POCl 3  is used, then the first reaction product can contain substantially no excess POCl 3 , depending on the efficiency of the reaction between the alkylated phenol and POCl 3 ; however, if a molar excess of POCl 3  is used, then the amount of excess POCl 3  will depend on the efficiency of the reaction and on the amount of POCl 3  used. In the practice of the present invention, if less than a molar equivalency, or up to about a 15% molar excess of POCl 3 , is used to produce the first reaction product, then the first reaction product can be, and in some embodiments is, directly reacted with an alcohol without removal of unreacted POCl 3 . 
     Optional POCl 3  Removal 
     If excess POCl 3  is used in producing the first reaction product, then it is preferred that at least a portion of the excess POCl 3  be removed from the first reaction product, thereby producing an intermediate reaction product. In preferred embodiments, the amount of excess POCl 3  removed from the first reaction product is that amount necessary to produce an intermediate product containing less than about 15 mole %, preferably less than about 10 mole %, more preferably less than about 5 mole %, most preferably less than about 1 mole %, POCl 3 , all based on the total phosphorus in the first reaction product. In a particularly preferred embodiment, substantially all unreacted POCl 3  is removed from the first reaction product, which in some embodiments can produce an intermediate reaction product that contains substantially no unreacted alkylated phenol. However, it should be noted that if the intermediate reaction product is reacted with phenol, the amount of unreacted POCl 3  removed from the first reaction product must be that amount necessary to produce an intermediate product containing less than about 1.2 mole %, preferably less than about 1 mole % of total organic phosphorus. 
     The method by which the POCl 3  is removed from the first reaction product to produce the intermediate product is not critical to the present invention, and non-limiting examples of suitable removal techniques include vacuum distillation, flashing, stripping, vacuum stripping, and the like. In preferred embodiments, POCl 3  is removed by vacuum stripping. Vacuum stripping can suitably be carried out by heating the first reaction product to within the range of about 115° C. to about 170° C., under constant agitation and vacuum in the range of from about 700 mmHg to about 0.001 mmHg. It is within the scope of the present invention that a nitrogen purge accompany the vacuum stripping. It is also within the scope of the present invention to add an inert “chaser” solvent at the end of the vacuum stripping to reduce the POCl 3  in the intermediate reaction product to less than 1 mole %, based on the intermediate reaction product. If a chaser solvent is used, it is preferred to use toluene, methylcyclohexane, boiling-point heptanes or n-heptane. 
     It should be noted that, while not necessary, in some embodiments, the optional POCl 3  removal is accompanied by the removal of a portion of any diluent added during the first reaction. In this embodiment, conditions can be adjusted to within the above ranges and means selected from those described above to provide for more efficient removal of both the POCl 3  and diluent. 
     Second Reaction 
     In the practice of the present invention, the first reaction product or intermediate reaction product is reacted with an alcohol selected from aryl alcohols including phenol, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst or processed to remove at least a portion of excess POCl 3 . 
     In an alternative embodiment, the first reaction product or intermediate product can be reacted sequentially with more than one alcohol selected from aryl alcohols including phenol, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof. In this embodiment, it is preferred that the first reaction product or intermediate product be reacted with a first alcohol, and when the first alcohol has been consumed, as determined by a suitable method such as P 31  NMR, a second alcohol, preferably different from the first alcohol, be added. 
     More preferably, in this embodiment, the first alcohol is divided into a first and second portion. The first reaction product or intermediate reaction product is reacted with the first portion of the first alcohol until substantially all of the first portion of the first alcohol is consumed, as determined by a suitable method such as P 31  NMR. After substantially all of the first portion of the first alcohol has been consumed, the second portion of the first alcohol is added, and the reaction allowed to continue until substantially all of the second portion of the first alcohol has been consumed, as determined by a suitable method such as P 31  NMR, thus producing a first intermediate reaction product comprising at least aryl dichlorophosphate and chloro diarylphosphate. 
     The first intermediate reaction product, which is richer, in chloro diarylphosphates then the first reaction product, is then reacted with an effective amount of the second alcohol. By an effective amount of the second alcohol, it is meant that amount of the second alcohol that is effective at converting substantially all of the aryl dichlorophosphate and chloro diarylphosphate to alkylated triaryl phosphate esters according to the present invention. 
     In this embodiment, the first and second alcohol can be independently selected from aryl alcohols including phenol, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof. 
     Non-limiting examples of suitable alkylated aryl alcohols are those wherein the alkyl group contains from about 1 to about 5 carbon atoms such as methyl. Non-limiting examples of suitable alkyl alcohols are those wherein the alkyl group contains from about 1 to about 20 carbon atoms such as n-decanol. Preferably the alcohol is selected from phenol, decanol, dodecanol or mixtures thereof and in a most preferred embodiment, the alcohol is phenol. 
     Second Catalyst 
     Catalysts suitable for use as the second catalyst herein can be selected from quaternary ammonium salts, quaternary phosphonium salts, MgCl 2 , CaCl 2 , AlCl 3 , KCl, FeCl 3 , LiCl, and BaCl 2 . Non-limiting examples of suitable quaternary ammonium salts and quaternary phosphonium salts include are those listed above in relation to the first catalyst. Preferably the second catalyst is selected from MgCl 2 , CaCl 2 , AlCl 3 , KCl, FeCl 3 , LiCl, and BaCl 2 . More preferably the second catalyst is MgCl 2 . 
     Second Reaction Conditions 
     The first reaction product or intermediate reaction product and alcohol are reacted in the presence of the second catalyst under second reaction conditions including temperatures ranging from about 75° C. to about 260° C. Preferably, second reaction conditions include temperatures ranging from about 100° C. to about 180° C., most preferred from about 140° C. to about 150° C. The first reaction product or intermediate reaction product, alcohol, and second catalyst can be combined, contacted, etc., in any order. For example, the first reaction product or intermediate reaction product, alcohol, and second catalyst can be co-fed to a reaction vessel, the first reaction product or intermediate reaction product can be added to a reaction vessel containing the alcohol and second catalyst, etc. However, it is preferred that the alcohol, preferably in the molten or liquid state, be added to the first reaction product reactant or intermediate reaction product to which the second catalyst has already been introduced. The inventors have unexpectedly discovered that combining, contacting, etc. the first reaction product or intermediate reaction product, second catalyst and alcohol in this manner provides for an alkylated phenol phosphate having TPP concentrations lower than those formed when the reactants are not added in this manner. In this embodiment, the catalyst is preferably present with the alcohol, but it can be co-fed or fed after the intermediate product. 
     In preferred embodiments, second reaction conditions further include the substantial absence of oxygen. 
     The reaction of the first reaction product or intermediate reaction product and alcohol produces an alkylated triaryl phosphate ester according to the present invention, as described above. 
     Optional Processing of Alkylated Triaryl Phosphate Ester 
     In some embodiments, it may be desirable to further refine the alkylated triaryl phosphate ester produced from the present process, for example to remove any excess alcohol that may be present in the alkylated triaryl phosphate ester. Further processing can also include adding an additional amount of alcohol such as monoisopropylated phenols, diisopropylated phenols, phenol, and mixtures thereof and/or second catalyst to the alkylated triaryl phosphate ester. The alcohol-rich alkylated triaryl phosphate ester product comprising excess alcohol can then be recovered, and at least a portion, preferably substantially all, of the excess alcohol removed by, for example, phase separation and/or stripping and/or distillation. In preferred embodiments, steam stripping is used. 
     The alkylated triaryl phosphate ester may also be washed one or more times with an acid, a base, or water. In this embodiment, the alkylated triaryl phosphate ester can first be washed with an acid and/or base, preferably a base, and then washed with water. In this embodiment, it is preferred to wash the alkylated triaryl phosphate ester with a base such as NaOH, preferably a diluted base comprising in the range of about 1 to about 5 wt. %, based on the diluted base, NaOH, in the range of about 1 to about 4 times, followed by washing with water until the pH of the water recovered from the washing is in the range of from about 7 to about 9. 
     In another embodiment, the alkylated triaryl phosphate ester can also be processed in a wipe film evaporator, a distillation column, or other similar separation device, in conjunction with the above further refinement processes or as a stand-alone refinement. 
     Use of Alkylated Triaryl Phosphate Esters as Flame Retardant 
     The alkylated triaryl phosphate esters of the present invention are suitable for use as a flame retardant in a variety of resins. In this embodiment, the present invention relates to a flame retardant polyvinyl chloride resin formulation comprising at least one, in some embodiments only one, polyvinyl chloride resin and a flame retarding amount of at least one, in some embodiments only one, alkylated triaryl phosphate ester, as described herein. By a flame retarding amount of alkylated triaryl phosphate ester, it is meant in the range of from about 2 to about 150 parts per hundred resin (“phr”) of the at least one alkylated triaryl phosphate ester, based on the total weight of the flame retardant polyvinyl chloride resin formulation. In preferred embodiments, a flame retarding amount of alkylated triaryl phosphate ester is to be considered in the range of from about 5 to about 70 phr, more preferably in the range of from about 12 to about 45 phr, of the at least one alkylated triaryl phosphate ester, on the same basis. 
     Resins suitable for use in this embodiment of the present invention include those comprising a polymer comprised of one or more polymerized monomers having a polymerizable olefinic double bond in the molecule. There are three groups of such polymers, namely (i) one or more vinylaromatic homopolymers or copolymers, preferably high-impact polystyrene, (ii) one or more acyclic olefinic hydrocarbon homopolymers or copolymers, such as polyethylene, polypropylene, and copolymers of ethylene or propylene with at least one higher olefin and with or without a diene monomer, and (iii) one or more copolymers of at least one vinylaromatic monomer and at least one non-vinylaromatic monomer containing a functional group, such as acrylonitrile, an acrylate monomer, or a methacrylate monomer with or without a diene monomer. Examples of group (ii) include ABS, MBS, SAN, and ASA. Of the above three groups of polymers, preferred are vinylaromatic polymers. 
     Vinylaromatic polymers that can be flame retarded in the practice of this invention can be homopolymers, copolymers or block polymers and such polymers can be formed from such vinylaromatic monomers as styrene, ring-substituted styrenes in which the substituents are one or more C 1-6  alkyl groups, alpha-methylstyrene, ring-substituted alpha-methylstyrenes in which the substituents are one or more C 1-6  alkyl groups, vinylnaphthalene, and similar polymerizable styrenic monomers, i.e., styrenic compounds capable of being polymerized, e.g., by means of peroxide or like catalysts, into thermoplastic resins. Homopolymers and copolymers of simple styrenic monomers (e.g., styrene, p-methyl-styrene, 2,4-dimethylstyrene, alpha-methyl-styrene, p-chloro-styrene, etc.) are preferred from the standpoints of cost and availability. The vinylaromatic polymers that are flame retarded pursuant to this invention can be homopolymers or copolymers can be produced by free-radical polymerization, cationically-initiated polymerization, or anionically-initiated polymerization. In addition, the vinylaromatic polymers that are flame retarded in the practice of this invention can be foamable, expanded, or foamed vinylaromatic polymer compositions. The vinylaromatic polymers can have various structural configurations. For example they can be isotactic polymers, syndiotactic polymers, or mixtures of isotactic and syndiotactic polymers. In addition the vinylaromatic polymers can be in the form of blends or alloys with other thermoplastic polymers, such as polyphenylene ether-styrenic polymer blends and polycarbonate-styrenic polymer blends. The vinylaromatic polymers can be impact-modified or rubber-modified polymers. In some embodiments, the resin is a polyvinyl chloride resin. 
     The flame retarded resins and flame retardant resin formulations of the present invention can also include conventional additives such as, for example, process aids, acid scavengers, dyes, pigments, fillers, stabilizers, antioxidants, antistatic agents, reinforcing agents, blowing agents, nucleating agents, plasticizers, and the like. The amount of these additives used herein is conventional, and one having ordinary skill in the art can readily select the amount and specific additive depending on the desired characteristics of the flame retardant polyvinyl chloride resin formulation. 
     The above description is directed to several embodiments of the present invention. Those skilled in the art will recognize that other means, which are equally effective, could be devised for carrying out the spirit of this invention. It should also be noted that preferred embodiments of the present invention contemplate that all ranges discussed herein include ranges from any lower amount to any higher amount. For example, when discussing the second reaction conditions, these ranges can include temperatures in the range of from about 75° C. to about 100° C., 90° C. to about 180° C., 100° C. to about 260° C., 150° C. to about 180° C., etc. 
     The following examples will illustrate the present invention, but are not meant to be limiting in any manner. 
     EXAMPLES 
     In the following Examples, the notation “Wt % in Crude” indicates the amount of each component in the ester product recovered from the reactor, and is thus based on the total weight of the product recovered from the reactor. “Normalized wt %” indicates the amount of each component calculated by dividing the “Wt % in Crude” values by the “Normalization Factor”, thus indicating the amount of each component in relation to the alkylated triaryl phosphate ester. 
     Example 1 
     Comparative 
     A reaction flask was purged with nitrogen. 15.3 g (0.1 mole) of phosphorous oxychloride (“POCl 3 ”) followed by 13.6 g (0.1 mole) of ortho-isopropylphenol (“OIP”). The mixture was heated to about 110° C. for 10 hours under agitation. The content of the flask were analyzed via  1 H-NMR and it was discovered that greater than 50 mol. % of the OIP was unreacted. The content of the flask were also analyzed via  31 P-NMR, and the molar ratio of 2-isopropylphenyl dichlorophosphate to bis-(2-isopropylphenyl) chlorophosphate bis to tris-(2-isopropylphenyl) phosphate was found to be 40.8:22.6:5.0. 
     Example 2 
     Comparative 
     A reaction flask was purged with nitrogen. 15.3 g (0.1 mole) of phosphorous oxychloride (“POCl 3 ”) followed by 13.6 g (0.1 mole) of ortho-isopropylphenol (“OIP”) was then added to the flask over a 30 minute period. The mixture was heated to 195° C. for 5 hours under agitation. The content of the flask were analyzed via Proton NMR, and the presence of unreacted OIP in the flask detected by this analysis indicated that the reaction was incomplete. The content of the flask were then heated to 250° C. for 3 hours under agitation until no OIP was detected. The content of the flask were analyzed via  31 P-NMR, and the molar ratio of 2-isopropylphenyl dichlorophosphate to bis-(2-isopropylphenyl) chlorophosphate bis to tris-(2-isopropylphenyl) phosphate was found to be 56.2:28.7:2.8. 
     Example 3 
     Example 1 Extracted from U.S. Pat. No. 4,139,487—Comparative 
     Phenol (65.2 parts) and a mixture of meta- and para-isopropyl phenols (47.9 parts) were mixed with phosphorus oxychloride (51 parts; that is a 5% excess of phenolic reactants). Powdered anhydrous magnesium chloride (0.5 part) was added to catalyze the reaction. The reaction mixture was rapidly heated to 130° C. and then slowly to 230° C. over a period of about 2 hours, after which there was no further appreciable evolution of hydrogen chloride. Completion of the reaction was checked by titration tests on the crude product which was then distilled under vacuum to give a fraction of recovered phenols, a small intermediate fraction and a main ester fraction (88% of crude product) boiling at 205° C.-225° C. at 1 mm. of mercury. 
     The composition of the recovered phenolic fraction was shown by analysis to be substantially the same as that of the phenolic feedstock mixture, indicating that there had been no appreciable separation of the components due to preferential esterification, which was verified by hydrolyzing a portion of the main ester fraction and analyzing the recovered phenols. The distilled phosphate ester had a satisfactory color, content of oxidizable impurities and acidity and was not therefore further purified. The viscosity of the distilled phosphate ester was 30 cs at 25° C. and the specific gravity (25° C./25° C.) was 1.169. The constitution of the distilled phosphate ester is indicated in Table 2, below. The wt. % is based on the total weight of the distilled phosphate ester. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Component 
                 wt. % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Triphenylphosphate 
                 30 
               
               
                   
                 Mono-(isopropylphenyl) diphenyl phosphate 
                 44 
               
               
                   
                 Bis-(isopropylphenyl) phenyl phosphate 
                 22 
               
               
                   
                 Tris-(isopropylphenyl) phosphate 
                 4 
               
               
                   
                 Total 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     The distilled phosphate esters had a calculated carbon number of 21 and containing 33 mole-percent of the isopropylphenyl group. 
     Example 4 
     Example 2 Extracted from U.S. Pat. No. 4,139,487—Comparative) 
     Phenol (32.6 parts) and a mixture of meta- and para-isopropyl phenols (95.8 parts) were mixed with phosphorus oxychloride (51 parts) and anhydrous magnesium chloride (0.6 part) as catalyst. Reaction and purification were carried out as in Example 1 (Example 3 herein) and the main ester fraction (89% by weight of the crude product) distilled at 207-230° C. at 1 mm of mercury. As in Example 1 (Example 3 herein) the product required no further purification and had a viscosity of 58 cs at 25° C. and a specific gravity (25° C./25° C.) of 1.123 
     Analysis of the mixed ester indicated it to possess the following constitution (Table 3) (wt %). The wt. % is based on the total weight of the distilled phosphate ester. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 Component 
                 wt. % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Triphenylphosphate 
                 4 
               
               
                   
                 Mono-(isopropylphenyl) diphenyl phosphate 
                 19 
               
               
                   
                 Bis-(isopropylphenyl) phenyl phosphate 
                 52 
               
               
                   
                 Tris-(isopropylphenyl) phosphate 
                 25 
               
               
                   
                 Total 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     The mixed phosphate esters had a carbon number of 24 and contained 66 mole-percent of the isopropylphenyl group. 
     Example 5 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated phenyl phosphate began. A 150 g charge of the mixture (1.1 mole of reactive isopropylated phenols prepared via ortho alkylation of phenol with propylene and AlCl 3 ), described in Table 4 below was combined with 640 g (4.17 mole) of POCl 3  and 1.5 grams of tetrabutyl ammonium bromide in a reactor. The mixture was heated under constant agitation to about 114° C. and refluxed at that temperature until evolution of HCl ceased, thus indicating the formation of the intermediate product. Excess POCl 3  was recovered from the intermediate product (95% of theoretical amount) by first heating it at atmospheric pressure to about 130° C. and then heating it to about 135° C. at 1 mmHg. Heating of the reactor&#39;s content was discontinued, the reactor&#39;s content allowed to cool, and the reactor charged with 0.3 g of MgCl 2  and 188 g of phenol (2.0 mole, 99.6%). 
     After the addition of the MgCl 2  and phenol, the temperature of the reactor&#39;s content was increased to about 110° C., and the reaction mixture in the reactor was then heated from about 110 to about 130° C. over a period of about 3 hours under agitation.  31 P-NMR indicated complete conversion of the mono aryl dichlorophosphate and about a 55/45 mixture of the diaryl to triaryl intermediate and the alkylated triaryl phosphate ester product. 
     An additional 0.9 g of MgCl 2  was then added to the reactor and the reaction was conducted for an additional 4 hours, during which moderate HCl evolution was observed, until HCl evolution ceased. After HCl evolution ceased, 12.00 g of fresh phenol (0.13 mole, 99.6%) was charged to the reactor and the reaction was run with a nitrogen sparge at 130° C. until complete (about 2 hrs). Pressure was reduced to 10 mmHg and unreacted phenol removed overhead at 130° C. The alkylated triaryl phosphate ester thus produced was analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 5, below. Normalized, or relative weight percents, are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 AlCl 3  o-Alkylation IPS Mixture 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 wt % in 
                 Normalized 
               
               
                   
                 Component 
                 Crude 
                 wt % 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                   
                 phenol 
                 0.53 
                 0.55 
               
               
                   
                 OIP 
                 82.50 
                 85.05 
               
               
                   
                 PIP 
                 8.03 
                 8.28 
               
               
                   
                 2,6-DIP 
                 4.87 
                 5.02 
               
               
                   
                 2,4-DIP 
                 1.03 
                 1.06 
               
               
                   
                 TIP 
                 0.04 
                 0.04 
               
               
                   
                 Normalization 
                 97.00 
                 100.00 
               
               
                   
                 Factor (%) 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 5 
               
               
                   
                   
               
               
                   
                   
                 Formula 
                 Wt % in 
                 Normalized 
               
               
                   
                 Component 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.18 
                 0.20 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 84.49 
                 94.39 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 0.82 
                 0.92 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 3.91 
                 4.37 
               
               
                   
                 TTPP 
                 452.52 
                 0.11 
                 0.12 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 89.51 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 6 
     Unless otherwise indicated, the reactants were added to the autoclave under constant agitation and the autoclave content remained under this agitation until recovery of the isopropylated phenols began. 
     A 2.0-liter Parr autoclave was charged with 50 grams of dry Amberlyst® 15 and 1200 g (12.75 mole) of molten Phenol (Mallinckrodt, 99.6% loose crystals). The autoclave was sealed, purged with N 2  and heated to 110° C. The headspace of the autoclave was vented to atmospheric pressure and then purged with a 10-gram charge of propylene. Propylene, 190 g (4.5 mole), was then fed to the autoclave over a 90-minute period. The feed was such that the autoclave pressure varied from 80-30 psig during the addition. The reaction temperature was maintained from 110 to 118° C. for an additional hour, and the autoclave content then cooled to 70° C. The autoclave content was then allowed to settle for 30 minutes prior to transferring (positive N 2  pressure through dip leg) to a nitrogen purged storage bottle. 
     A second 1000 g (10.6 mole) charge of molten phenol was made to the autoclave containing the IP&#39;s/Amberlyst® 15 heel. The propylation reaction was repeated with 156 g (3.7 mole) of propylene. The combined decanted reaction mixture from the first and second molten phenol additions was then fractionally distilled (1 atmosphere). The light cut (typically 93% phenol, 7% OIP) was returned to the autoclave with make-up phenol and again propylated. This decantation and distillation process was continued through 8 runs. 
     The concentrated crude IP&#39;s was distilled at 1 atmosphere to produce 3300 g of material. The analysis of which is reported in Table 5, below. The material was separated via distillation into a light cut (2200 g, 93% phenol and 7% OIP), which was combined with (2200 g) fresh phenol and subsequently used as the alcohol of the second step to make IPP crude in Examples 7, 8 and 10-13 below. After recovery of unreacted phenol, through the eight runs a total of 2500 g of phenol had been reacted with 1200 g of propylene to yield 3300 g of IPs suitable for use in making low TPP IPP. This material is described in Table 6 and was used as the alkylated phenol of the first step in Examples 7-13 below. 
     
       
         
           
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
               
                   
                 Molecular 
                 IPPP Crude 
               
               
                 Component 
                 Weight 
                 (wt %) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Phenol 
                 94.11 
                 0.35 
               
               
                 2-isopropylphenol (OIP) 
                 136.19 
                 59.48 
               
               
                 4-isopropylphenol (PIP) 
                 136.19 
                 29.76 
               
               
                 2,6-diisopropylphenol (2,6-DIP) 
                 178.27 
                 4.25 
               
               
                 2,4-diisopropylphenol (2,4-DIP) 
                 178.27 
                 5.83 
               
               
                 2,4,6-triisopropylphenol (2,4,6-TIP) 
                 220.35 
                 0.32 
               
               
                   
               
            
           
         
       
     
     Example 7 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated phenyl phosphate began. 
     A 475 g (3.34 mole of reactive isopropylated phenols) sample of the material described in Table 5, above, was combined with 795 g (5.19 mole) of POCl 3  and 356 grams (0.33 mole %) of tetrabutyl ammonium bromide. The mixture was heated to 114° C. and refluxed at that temperature until evolution of HCl slowed. The temperature was gradually increased to 135° C. and left at that temperature until HCl evolution ceased. The excess POCl 3  was recovered in vacuo, stripping to an end point of 135° C. and &lt;1.0 mmHg. 
     After the removal of excess POCl 3  was complete, the reactor was allowed to cool. The reactor was then charged with 3.26 g of MgCl 2  (1.0 mole %) and heated to 110° C. To the reactor was fed 629.1 g (6.69 moles) of a mixture comprising phenol (96.3 wt %) and 2-isopropylphenol (3.7 wt %), recycled from the final light cut of IP&#39;s preparation described above (Example 6) with concomitant heating of the reactor&#39;s content from 110° C. to 135° C. over a 3 hour period. Within one hour after the completion of the feed,  31 P-NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to triaryl phosphates. The pressure was reduced to 10 mmHg and unreacted phenol partially removed overhead at 140° C. 
     The alkylated triaryl phosphate ester thus produced was analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 7, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 7 
               
               
                   
                   
               
               
                   
                   
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.86 
                 0.98 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 77.90 
                 88.37 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 6.50 
                 7.37 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 2.53 
                 2.87 
               
               
                   
                 TTPP 
                 452.52 
                 0.36 
                 0.41 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 88.15 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 8 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated triaryl phosphate ester began. 
     A 470 g sample of the material described in Table 5, above, was combined with 571 g (3.73 mole) of POCl 3  recycled from previous Examples and 6.15 grams (0.58 mole %) of tetrabutyl ammonium bromide in a reactor. The mixture was heated to 118° C. and refluxed at that temperature until evolution of HCl slowed. The temperature was gradually increased to 135° C. and left at that temperature until HCl evolution ceased. The excess POCl 3  was recovered in vacuo, stripping to an end point of 135° C. and &lt;1.0 mmHg. The reactor was allowed to cool, and then charged with 5.5 g of MgCl 2  (1.75 mole %) and heated to 110° C. To the reactor was fed 622.5 g (6.61 moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol, with concomitant gradual increased heating from 110° to 135° C. over a 3-hour period. 
     Within one hour after the completion of the phenol/2-isopropylphenol mixture feed,  31 P-NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to triaryl phosphates. The pressure of the reactor was reduced to 10 mmHg and unreacted phenol partially removed overhead at 140° C. The alkylated triaryl phosphate ester was recovered from the reactor and analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 8, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 8 
               
               
                   
                   
               
               
                   
                   
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.58 
                 0.66 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 76.49 
                 86.72 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 7.04 
                 7.98 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 3.35 
                 3.80 
               
               
                   
                 TTPP 
                 452.52 
                 0.74 
                 0.84 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 88.20 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 9 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated triaryl phosphate ester began. 
     A 246 g sample of the material described in Table 5, above, was combined with 800 g (5.22 mole) of POCl 3  and 2.56 grams (0.46 mole %) of tetrabutyl ammonium bromide. The mixture was heated to 114° C. and refluxed at that temperature until evolution of HCl slowed. The temperature was gradually increased to 135° C. and held at that temperature until HCl evolution ceased. The excess POCl 3  was recovered in vacuo stripping to an end point of 135° C. and &lt;1.0 mmHg. 
     The reactor was allowed to cool and then charged with 2.96 g of MgCl 2  (1.8 mole %) and heated to 110° C. 622.5 g (6.61 moles) of Phenol (99.6%) was fed to the reactor while gradually and simultaneously increasing the temperature of the reactor&#39;s content from 110° to 135° C. over a 3-hour period. Within one hour after the completion of the feed, P-31 NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to triaryl phosphates. The pressure was reduced to 10 mmHg and unreacted phenol partially removed overhead at 140° C. 
     The alkylated triaryl phosphate ester was recovered from the reactor and analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 9, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 9 
               
               
                   
                   
               
               
                   
                   
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.54 
                 0.61 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 80.41 
                 91.23 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 5.27 
                 5.98 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 1.80 
                 2.04 
               
               
                   
                 TTPP 
                 452.52 
                 0.12 
                 0.14 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 88.14 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 10 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated triaryl phosphate ester began. 
     A 462 g charge of the material described in Table 5, above, was combined with 1000 g (6.52 mole) of a 1:2 mix of fresh and recycled POCl 3  and 3.8 grams (1.23 mole %) of MgCl 2 . The mixture was heated initially to 85° C., and at that temperature, evolution of HCl was apparent. The temperature of the mixture was gradually increased to 135° C. and held at that temperature until HCl evolution ceased. The excess POCl 3  was recovered in vacuo, stripping to an end point of 135° C. and 50 mmHg. Toluene (2×100 g) was charged (subsurface) to the hot reactor, and the toluene was then stripped to the ending conditions of 140° C. and 50 mmHg. 
     The reactor was allowed to cool, and after cooling to 110° C., 612 g (6.5 moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol, was fed to the reactor while gradually increasing the temperature of the reactor&#39;s content from 110° to 135° C. over a 3-hour period. Within one hour after the end of the phenol/2-isopropylphenol mixture feed,  31 P-NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to triaryl phosphates. The pressure of the reactor was reduced to 10 mmHg and unreacted phenol removed overhead at 140° C. 
     The alkylated triaryl phosphate ester was recovered from the reactor and analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 10, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated phenyl phosphate as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 10 
               
               
                   
                   
               
               
                   
                   
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.73 
                 0.80 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 78.69 
                 85.82 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 7.64 
                 8.33 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 3.97 
                 4.33 
               
               
                   
                 TTPP 
                 452.52 
                 0.66 
                 0.72 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 91.69 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 11 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated triaryl phosphate ester began. 
     A 231.5 g (1.63 mole of reactive isopropylated phenols) sample of the material described in Table 5, above, was combined with 750 g (3.01 mole) of a mix 1:2 mix of fresh and recycled POCl 3  and 2.6 grams (1.20 mole %) of AlCl 3 . The mixture was heated initially to 80° C., and at that temperature, evolution of HCl was apparent. The temperature of the reactor&#39;s content was gradually increased to 135° C. and held at that temperature until HCl evolution ceased. 
     Excess POCl 3  was recovered in vacuo stripping to an end point of 135° C. and 50 mmHg. Toluene (2×100 g) was then charged (subsurface) to the hot reactor, and the toluene was then stripped to the ending conditions of 140° C. and 50 mmHg. The reactor&#39;s content was allowed to cool to 110° C., and 305 g (3.25 moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol, was fed to the reactor while gradually increasing the temperature of the reactor&#39;s content from 110° C. to 135° C. over a 3-hour period. Foaming was very problematic throughout the phenol feed. Within one hour after the end of the feed,  31 P-NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to triaryl phosphates. The pressure was reduced to 50 mmHg and unreacted phenol partially removed overhead at 140° C. 
     The alkylated triaryl phosphate ester phosphate was recovered from the reactor and analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 11, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 11 
               
               
                   
                   
               
               
                   
                   
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.65 
                 0.72 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 75.00 
                 82.53 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 8.13 
                 8.95 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 5.96 
                 6.56 
               
               
                   
                 TTPP 
                 452.52 
                 1.14 
                 1.25 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 90.88 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 12 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated triaryl phosphate ester began. 
     A 197.2 g (1.39 mole of reactive isopropylated phenols) sample of the material described in Table 5, above, was combined with 640 g (4.17 mole) of POCl 3  and 4.0 grams (3.64 mole %) of pyridine (dried over molecular sieves) in a reactor. The mixture was heated to 114° C. and refluxed at that temperature until evolution of HCl slowed. The temperature was then gradually increased to 135° C. with distillation of POCl 3  and held at that temperature until HCl evolution ceased. The remaining excess POCl 3  was recovered in vacuo stripping to an end point of 135° C. and 50 mmHg. During the POCl 3  strip, some pyridine-HCl was observed in the overhead and in the recycle POCl 3  Toluene (2×100 g) was charged (subsurface) to the hot reactor. Toluene was stripped to the ending conditions of 140° C. and 50 mmHg. The reactor&#39;s content was allowed to cool to 110° C., and 278 g (2.78 moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol, was fed to the reactor while gradually increasing the temperature of the reactor&#39;s content from 110° to 135° C. over a 3-hour period. Within one hour after the end of the feed,  31 P-NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to triaryl phosphates. The pressure was reduced to 10 mmHg and unreacted phenol removed overhead at 140° C. 
     The alkylated triaryl phosphate ester was recovered from the reactor and analyzed, and the alkylated phenyl phosphate was found to have the characteristics outlined in Table 12, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 12 
               
               
                   
                   
               
               
                   
                   
                   
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 FW 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.52 
                 0.61 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 76.90 
                 89.53 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 6.21 
                 7.23 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 2.15 
                 2.50 
               
               
                   
                 TTPP 
                 452.52 
                 0.11 
                 0.13 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 85.89 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 13 
     Unless otherwise indicated, the reactants were added to the reactor under constant agitation and the reactor&#39;s content remained under this agitation until recovery of the alkylated triaryl phosphate ester began. 
     A fully jacketed 2000 ml dry round bottom flask was used as a reactor in this example. It was equipped with an overhead stirrer, thermometer, oil jacketed addition funnel and an efficient condenser/takeoff head. The reactor was vented through a Drierite® column to a caustic scrubber. 1100 g (7.17 mole) of POCl 3  (comprised of 2:1 mix of recycle and fresh POCl 3 ), 530 g (3.74 mole of reactive IPPs) of a mixture of isopropylated phenols comprised of 59.48 wt % OIP, 29.76 wt % PIP, 5.83 wt % 2,4-DIP and 6.0 g (2 mole % relative to reactive IPP&#39;s charged) of pyridine were charged to the reactor. The reactor&#39;s content was heated to 113° C. (oil jacket temperature 124° C.). HCl evolution initiated at 80° C. and became much more apparent at 105° C. After 90 minutes at 113° C. HCl evolution slowed. The jacket temperature was increased to 135° C., within an additional 60 minutes the pot temperature had reached 127° C., HCl Evolution was essentially complete, and pyridine•HCl separated as an oil suspended in the reaction mixture (the resulting turbidity seems to be a good visual indictor of the reaction endpoint). 
     The reactor jacket temperature was increased to 145° C. and the valve on the take off head was opened to the receiver, and POCl 3  was collected for recycle. Distillation of POCl 3  was facilitated with a slow nitrogen purge through the reactor headspace. Once the pot temperature reached 135° C. and POCl 3  distillation had slowed, the reactor pressure was gradually reduced (max vacuum 50 mmHg) until the theoretical amount of POCl 3  was collected (495 g, [95% of Theory] of POCl 3  was thus recovered). During the distillation pyridine•HCl formed in the overheads, but caused no operational problems. The last trace of POCl 3  was removed via the addition and stripping with 300 ml of toluene (ending conditions 135° C. 50 mmHg). An aliquot was removed for analysis;  31 P-NMR analysis indicated a 97.4:2.6 relative ratio of ArOCl 2 PO:(ArO) 2 ClPO as well as verified complete removal of POCl 3 . 
     3.5 g (0.98 mole % relative to IPPs) of MgCl 2  were then charged to the reactor and left to stir at 140° C. under a stream of nitrogen for 1 hr. A second aliquot was removed for analysis, and  31 P-NMR indicated this second aliquot had a 97.2:2.8 relative ratio of ArOCl 2 PO:(ArO) 2 ClPO. Phenol (706 g, 96.3 wt % Phenol, 3.7 wt % 2-isopropylphenol, 7.4 mole total phenols) was then charged to the oil jacketed addition funnel, from which it was gradually fed over a 75-minute period to the reactor. During this addition, HCl evolution was extremely vigorous. The reaction appeared to be complete after 170 minutes total reaction time. Conversion as measured by  31 P-NMR was 99.3%. An additional 23 g charge of the phenol mixture described above was made. After an additional 30 minutes the nearly water white mixture (density=1.09, 1370 g total reaction mass, 1378 g Theory) was transferred to a wash kettle. 
     After the nearly water white mixture was charged to the wash kettle, 350 g of a Na 2 CO 3 /HNa 2 PO 4  solution (pH=9 density=1.15) was charged to the wash kettle. The content of the wash kettle were then stirred at 88° C. for 5 minutes and then allowed to settle for a period of 20 minutes. The bottom milky (suspended MgCO 3 ) aqueous layer was removed (226 g, pH=7.5-8.0) from the wash kettle, and the resulting crude IPPP was washed for an additional 5 minutes with a second aliquot (90° C., 200 g) of the Na 2 CO 3 /HNa 2 PO 4  solution. A second phase was removed from the bottom of the reactor to yield a 195 g less turbid yet still milky aqueous solution having a pH of 10. 530 g of a dilute H 3 PO 4  solution, 0.56 wt %, H 3 PO 4 , based on the solution, was then charged to the reactor, and the bottom turbid product layer was collected (1357 g). The aqueous phase was removed (pH=3.5, 610 g), and the product layer was placed in a reactor and sparged with nitrogen at 95° C. to remove water, thus yielding an 1335 g of an alkylated phenyl phosphate. The alkylated triaryl phosphate ester was recovered from the reactor and analyzed, and the alkylated triaryl phosphate ester was found to have the characteristics outlined in Table 13, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated phenyl phosphate as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 13 
               
               
                   
                   
               
               
                   
                   
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Major Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 TPP 
                 326.28 
                 0.47 
                 0.53 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 77.51 
                 87.79 
               
               
                   
                 2,4 DDP + DTPP (1) 
                 410.44 
                 7.10 
                 8.04 
               
               
                   
                 DTPP (2,3) 
                 410.44 
                 3.05 
                 3.45 
               
               
                   
                 TTPP 
                 452.52 
                 0.16 
                 0.18 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 88.29 
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Example 14 
     The crude alkylated triaryl phosphate ester recovered from Examples 7-12 were combined and washed with a Na 2 CO 3 /HNa 2 PO 4  having the concentrations and in the same manner described in Example 13, above. That material was then combined with the crude product from Example 13. The total mixture was then distilled under a reduced pressure (&lt;2 mmHg) nitrogen atmosphere. During the distillation, the “forerun” (6 wt % of the total mixture, based on the mixture) was collected between 180-218° C. The “product cut” (92 wt % of the total of the total mixture, based on the mixture) was collected between 118.5-235° C. The undistilled bottoms represented the last 2 wt %, based on the mixture, of the total mass of the mixture. The forerun was analyzed by HPLC, which found 13.2 wt % phenol, 0.7 wt % 4-isopropylphenol, 13.0 wt % 2-isopropylphenol, 7.0 wt % 2,6-diisopropylphenol, 0.0 wt % TPP, 2.3 wt % monoisopropylphenyl diphenyl phosphates, 0.2 wt % diisopropylated triaryl phosphates, and 0.02 wt % triisopropylated triaryl phosphate. The product cut was also analyzed for purity and physical properties; the results are presented in the Table 14, below. All weight percents are absolute and are based on the total mass of that which is being analyzed. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 14 
               
               
                   
                   
               
               
                   
                 Analysis 
                 Flashed Product 
               
               
                   
                 HPLC 
                 Wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Triphenyl Phosphate 
                 0.71 
                   
               
               
                   
                 Isopropylphenyl diphenyl phosphates 
                 87.21 
               
               
                   
                 Diisopropylated triaryl phosphates 
                 11.44 
               
               
                   
                 Triisopropylated triaryl phosphates 
                 0.64 
               
               
                   
                 Acid Number 
                 0.11 
                 mg KOH/g 
               
               
                   
                 APHA Color 
                 28.00 
               
               
                   
                 Density (20° C.) 
                 1.1689 
                 g/ml 
               
               
                   
                 Flash Point (Cleveland Open Cup) 
                 222° 
                 C. 
               
               
                   
                 Moisture 
                 19.2 
                 ppm 
               
               
                   
                 Wt % Phosphorus (NMR) 
                 8.34 
               
               
                   
                 [Al] 
                 &lt;0.11 
                 ppm 
               
               
                   
                 [Mg] 
                 &lt;0.0018 
                 ppm 
               
               
                   
                 [Na] 
                 &lt;0.6 
                 ppm 
               
               
                   
                 Kinetic Viscosity (25° C.) 
                 52.91 
                 cSt 
               
               
                   
                   
               
            
           
         
       
     
     Thus, as illustrated in Table 14, our product, on average, is 10% higher in Phosphorous than those produced in the comparatives examples above, and is also 10% less viscous than the products of the comparative examples. 
     Example 15 
     A 5-liter reactor was equipped with an addition funnel, thermal well and distillation apparatus. The distillation apparatus was vented to a caustic scrubber through a Drierite® column. The reactor was purged with N 2  and charged with 3886 g (25.34 mole) of recycled POCl 3  and 6.37 g (0.53 mole %) of MgCl 2 . The content of the reactor was heated to 85° C. A redistilled 67:1:32 blend (1725 g, 12.67 mole) of OIP (Aldrich)) MIP (Aldrich) and PIP (Aldrich) was fed to the reactor over a 3-hour period. During the feed the reaction temperature was gradually increased to 130° C. After 4 hours total reaction time distillation of POCl 3  was initiated. The reactor pressure was decreased gradually as the rate of POCl 3  distillation decreased. Distillation was continued to an ending condition of 140° C. and 50 mmHg. Toluene was then charged (2×250 ml) and stripped at 140° C. (50 mmHg). Phosphorus NMR of the stripped reaction mixture verified the complete removal of POCl 3  and indicted a 100:4.2 relative ratio of ArOPOCl 2 :(ArO) 2 POCl. 
     The content of the reactor was cooled to 130° C. Molten phenol (99.6%), 2362 g (25.1 mole) was feed to the reactor over a 5-hour period. Towards the end of the feed the reaction temperature was increased to 150° C. Phosphorus NMR analysis of the reactor&#39;s content confirmed complete reaction within 1-hour of the end of the feed. The content of the reactor was transferred under N 2  to a 5-liter storage bottle, 4547 g. HPLC analysis is Tabulated below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in Table 15, below. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 15 
               
               
                   
                   
               
               
                   
                 Major 
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Phenol 
                 94.11 
                 4.10 
                 4.35 
               
               
                   
                 TPP 
                 326.28 
                 0.10 
                 0.11 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 85.90 
                 91.09 
               
               
                   
                 DTPP 
                 410.44 
                 4.20 
                 4.45 
               
               
                   
                 TTPP 
                 452.52 
                 0.00 
                 0.00 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 94.30 
               
               
                   
                   
               
            
           
         
       
     
     A 5-liter glycol jacketed baffled reactor was charged with 500 g of 11% aqueous Na 2 CO 3  and 2065 g of the alkylated triaryl phosphate ester of Table 13. The mixture was briefly stirred at 85-92° C. and then left to phase separate. The bottom aqueous layer was removed along with a clear rag layer of intermediate density. The wash procedure was repeated through 4 washes. In order to completely remove the suspended rag layer, comprised primarily of sodium and magnesium phenoxide, 2000 ml of Toluene was added. The IPP/toluene mixture was then washed with tap water (2×500 ml). 
     To the same 5-liter glycol jacketed baffled reactor was charged with 540 g of 4% aqueous NaOH, 2478 g of the crude product mixture and 1750 g of Toluene. The mixture was briefly stirred at 45-50° C. and then warmed to 65° C. without stirring. The resulting bottom aqueous layer was removed along with the suspended Mg(OH) 2  suspended within it. A second wash was conducted at 65° C. with 608 g of 1% NaOH. The product mixture was then washed at 85° C. with 532 g of tap water (resulting aqueous cut pH=10). The IPP/toluene mixture was contaminated with a fine suspension of trace Mg(OH) 2 . This was removed by washing at 90° C. with 514 g of 0.7% H 3 PO 4  (resulting aqueous cut pH=3.5). A final 212 g tap water wash (90° C.) resulted in an aqueous phase with pH=4.5. 
     The washed and stripped IPP-crude from the two separate work-up procedures above was combined. The mixture was heated to 180° C. and sparged with nitrogen to remove trace toluene, moisture and phenol. An analytical sample (500 g) was removed for the analyses reported in Table 16, below. The balance of the material was combined with the product from Example 16 and later flash distilled at 1 mmHg and 220-240° C. (see example 17 for final product analyses). All weight percents are absolute and are based on the total mass of that which is being analyzed (indicated in the table). 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 16 
               
               
                   
                   
               
               
                   
                 Analysis 
                 Stripped Crude Product 
               
               
                   
                 HPLC 
                 Wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Phenol 
                 0.81 
                   
               
               
                   
                 Triphenyl Phosphate 
                 0.15 
               
               
                   
                 Isopropylphenyl diphenyl phosphates 
                 94.1 
               
               
                   
                 Diisopropylated triaryl phosphates 
                 4.58 
               
               
                   
                 Triisopropylated triaryl phosphates 
                 0.45 
               
               
                   
                 Acid Number 
                 0.45 
                 mg KOH/g 
               
               
                   
                 APHA Color 
                 149.00 
               
               
                   
                 Density (20° C.) 
                 1.1725 
                 g/ml 
               
               
                   
                 Flash Point (Cleveland Open Cup) 
                 229° 
                 C. 
               
               
                   
                 Moisture 
                 46 
                 ppm 
               
               
                   
                 Wt % Phosphorus (NMR) 
                 8.40 
               
               
                   
                 [Al] 
                 &lt;2.0 
                 ppm 
               
               
                   
                 [Mg] 
                 &lt;0.90 
                 ppm 
               
               
                   
                 [Na] 
                 1.2 
                 ppm 
               
               
                   
                 Kinetic Viscosity (25° C.) 
                 47.81 
                 cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 16 
     A 5-liter reactor was equipped with an addition funnel, thermal well and distillation apparatus. The distillation apparatus was vented to a caustic scrubber through a Drierite® column. The reactor was purged with N 2  and charged with 3385 g (22.08 mole) of recycled POCl 3  and 8.90 g (0.85 mole %) of MgCl 2 . The content of the reactor was heated to 85° C. A redistilled 67:32:1 blend (1503.3 g, 11.04 mole) of OIP (Aldrich), PIP (Aldrich) and MIP (Aldrich) was fed to the reactor over a 3-hour period. During the feed the reaction temperature was gradually increased to 130° C. After 4 hours total reaction time distillation of POCl 3  was initiated. The reactor pressure was decreased gradually as the rate of POCl 3  distillation decreased. Distillation was continued to an ending condition of 150° C. and 50 mmHg. Toluene was then charged (2×250 ml) and stripped at 150° C. (50 mmHg). Phosphorus NMR of the stripped reaction mixture verified the complete removal of POCl 3  and indicted a 100:4 relative ratio of ArOPOCl 2 :(ArO) 2 POCl. 
     The content of the reactor was cooled to 130° C. Molten phenol (99.6%), 1984.97 g (20.75 mole) was fed to the reactor over a 5-hour period. Toward the end of the feed the reaction temperature was increased to 150° C. Phosphorus NMR analysis of the reactor&#39;s content confirmed the completion of the reaction within 1-hour of the end of the feed. The content of the reactor was transferred under N 2  to a 5-liter storage bottle, 3847 g. HPLC analysis of the content is in Table 175, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated triaryl phosphate ester as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 17 
               
               
                   
                   
               
               
                   
                 Major 
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Phenol 
                 94.11 
                 2.29 
                 2.30 
               
               
                   
                 TPP 
                 326.28 
                 0.15 
                 0.15 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 92.4 
                 92.98 
               
               
                   
                 DTPP 
                 410.44 
                 4.50 
                 4.53 
               
               
                   
                 TTPP 
                 452.52 
                 0.04 
                 0.04 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 99.38 
               
               
                   
                   
               
            
           
         
       
     
     A 5-liter glycol jacketed baffled reactor was charged with 650 g of tap water, 1750 ml of toluene and 1915 g of the crude product mixture of Table 15. The mixture was briefly stirred at from 85 to 92° C. and then left to phase separate. The bottom aqueous layer was removed along with a turbid rag layer of intermediate density. The organic layer was washed (2×1000 g) with 2% aqueous NaOH at 85° C. and then washed (4×800 g) with tap water until a neutral pH of the wash water was achieved. The above process was repeated with the balance of the crude material (1897 g). The washed crude product mixtures were combined and transferred to a third reactor where toluene, and moisture were removed in vacuo, ending conditions 180° C. and 1 mmHg. An analytical sample was found to have the characteristics listed in Table 18, below. All weight percents are absolute and are based on the total mass of that which is being analyzed. The balance of the material left after analysis was combined with the product from Example 15 and later flash distilled at 1 mmHg and 220-240° C. (see Example 17 for final product analyses). 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 18 
               
               
                   
                   
               
               
                   
                 Analysis 
                 Stripped Crude Product 
               
               
                   
                 HPLC 
                 Wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Phenol 
                 407 
                 ppm 
               
               
                   
                 Triphenyl Phosphate 
                 0.16 
                 wt % 
               
               
                   
                 Isopropylphenyl diphenyl phosphates 
                 94.6 
                 wt % 
               
               
                   
                 Diisopropylated triaryl phosphates 
                 4.6 
                 wt % 
               
               
                   
                 Triisopropylated triaryl phosphates 
                 0.01 
                 wt % 
               
               
                   
                 Acid Number 
                 0.05 
                 mg KOH/g 
               
               
                   
                 APHA Color 
                 221 
               
               
                   
                 Wt % Phosphorus (NMR) 
                 8.32 
               
               
                   
                 [Al] 
                 &lt;3.6 
                 ppm 
               
               
                   
                 [Mg] 
                 1.41 
                 ppm 
               
               
                   
                 [Na] 
                 1.68 
                 ppm 
               
               
                   
                   
               
            
           
         
       
     
     Example 17 
     The stripped crude product mixtures from Examples 15 and 16 were combined and flash distilled at from 220 to 240° C. and vacuum of &lt;1 mmHg. The product thus obtained had the characteristics presented in the Table 19, below. All weight percents are absolute and are based on the total mass of that which is being analyzed in the Table. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 19 
               
               
                   
                   
               
               
                   
                 Analysis 
                 Flashed Product 
               
               
                   
                 HPLC 
                 Wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Phenol 
                 200 
                 ppm 
               
               
                   
                 Triphenyl Phosphate 
                 0.17 
               
               
                   
                 Isopropylphenyl diphenyl phosphates 
                 94.93 
               
               
                   
                 Diisopropylated triaryl phosphates 
                 4.87 
               
               
                   
                 Triisopropylated triaryl phosphates 
                 0.02 
               
               
                   
                 Acid Number 
                 0.03 
                 mg KOH/g 
               
               
                   
                 APHA Color 
                 27.00 
               
               
                   
                 Density (20° C.) 
                 1.1729 
                 g/ml 
               
               
                   
                 Flash Point (Cleveland Open Cup) 
                 236° 
                 C. 
               
               
                   
                 Moisture 
                 24 
                 ppm 
               
               
                   
                 Wt % Phosphorus (NMR) 
                 8.36 
               
               
                   
                 [Al] 
                 &lt;0.1 
                 ppm 
               
               
                   
                 [Mg] 
                 &lt;0.06 
                 ppm 
               
               
                   
                 [Na] 
                 &lt;0.56 
                 ppm 
               
               
                   
                 Kinetic Viscosity (25° C.) 
                 48.74 
                 cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 18 
     A 5-liter reactor was equipped with an addition funnel, thermal well and distillation apparatus. The distillation apparatus was vented to a caustic scrubber through a Drierite® column. The reactor was purged with N 2  and charged with 900.00 g (5.88 mole) of recycled POCl 3  21.0 g (3.94 mole %) of dry pyridine and 916.1 g (6.73 mole) of the redistilled 67:32:1 blend of OIP (Aldrich), PIP (Aldrich) and MIP (Aldrich). The stirred content of the reactor was heated to 114° C., the temperature at which HCl evolution began in earnest. During the course of 7 hours the reaction temperature was gradually increased to 130° C. After 8 hours of total reaction time a sample was removed and analyzed by Phosphorus NMR, which indicted a 93.6:18.5 relative ratio of ArOPOCl 2 :(ArO) 2 POCl. 
     The content of the reactor was left to stand overnight and then again heated to 130° C. with stirring. Molten phenol (99.6%), 996.46 g (10.59 mole) was fed to the reactor over a 5-hour period. Toward the end of the feed the reaction temperature was increased to 170° C. Phosphorus NMR analysis of the reactor&#39;s content confirmed complete reaction within 3-hours after the end of the feed. The content of the reactor was transferred under N 2  to a 5-liter storage bottle, 2055 g. HPLC analysis indicated it had the properties set out in Table 20, below. Normalized or relative weight percents are based on the total weight of phenol and the alkylated phenyl phosphate as is indicated in the table. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 20 
               
               
                   
                   
               
               
                   
                 Major 
                 Molecular 
                 Wt % in 
                 Normalized 
               
               
                   
                 Components 
                 Weight 
                 Crude 
                 wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Phenol 
                 94.11 
                 2.08 
                 2.09 
               
               
                   
                 TPP 
                 326.28 
                 0.13 
                 0.13 
               
               
                   
                 2-IPP + 3-IPP + 4-IPP 
                 368.36 
                 70.33 
                 70.83 
               
               
                   
                 DTPP 
                 410.44 
                 26.16 
                 26.35 
               
               
                   
                 TTPP 
                 452.52 
                 0.59 
                 0.59 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Normalization Factor 
                   
                 99.29 
               
               
                   
                   
               
            
           
         
       
     
     A 5-liter glycol jacketed baffled reactor was charged with 650 g of tap water, 1750 ml of toluene and 2055 g of the crude product mixture. The mixture was briefly stirred at from 85 to 92° C. and then left to phase separate. The bottom aqueous layer was removed along with a turbid rag layer of intermediate density. The organic layer was washed (2×1000 g) with 2% aqueous NaOH at 85° C. and then washed (4×800 g) with tap water until a neutral pH of the wash water was achieved. The washed crude product mixtures were then transferred to a third reactor where toluene, moisture and phenols were removed in vacuo, ending conditions 180° C. and 1 mmHg. An analytical sample was removed and characterized. The results are reported in the Table 21, below. All weight percents are absolute and are based on the total mass of that which is being analyzed in the Table. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 21 
               
               
                   
                   
               
               
                   
                 Analysis 
                 Flashed Product 
               
               
                   
                 HPLC 
                 Wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Phenol 
                 0.07 
                   
               
               
                   
                 Triphenyl Phosphate 
                 0.14 
               
               
                   
                 Isopropylphenyl diphenyl phosphates 
                 72.2 
               
               
                   
                 Diisopropylated triaryl phosphates 
                 27.0 
               
               
                   
                 Triisopropylated triaryl phosphates 
                 0.61 
               
               
                   
                 Acid Number 
                 0.01 
                 mg KOH/g 
               
               
                   
                 APHA Color 
                 92 
               
            
           
           
               
               
               
            
               
                   
                 Wt % Phosphorus (NMR) 
                 8.1% 
               
               
                   
                   
               
            
           
         
       
     
     The balance of the material in the reactor was flash distilled at 1 mmHg and 220-240° C. The product thus obtained was analyzed and found to exhibit the characteristics presented in Table 22, below. All weight percents are absolute and are based on the total mass of that which is being analyzed in the Table. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 22 
               
               
                   
                   
               
               
                   
                 Analysis 
                 Flashed Product 
               
               
                   
                 HPLC 
                 Wt % 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Phenol 
                 &lt;100 
                 ppm 
               
               
                   
                 Triphenyl Phosphate 
                 0.14 
               
               
                   
                 Isopropylphenyl diphenyl phosphates 
                 72.16 
               
               
                   
                 Diisopropylated triaryl phosphates 
                 27.10 
               
               
                   
                 Triisopropylated triaryl phosphates 
                 0.61 
               
               
                   
                 Acid Number 
                 &lt;0.01 
                 mg KOH/g 
               
               
                   
                 APHA Color 
                 35 
               
               
                   
                 Density (20° C.) 
                 1.1631 
               
            
           
           
               
               
               
            
               
                   
                 Wt % Phosphorus (NMR) 
                 8.22% 
               
            
           
           
               
               
               
               
            
               
                   
                 Kinetic Viscosity (25° C.) 
                 55.80 
                 cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 18 
     Several test formulations were prepared by combining the materials outlined below in the amounts described below. Each formulation was prepared by mixing the components in a #5 Brabender bowl at 160-165° C. and compression molded at 165° C. into the appropriate thickness test specimens. ASTM type IV tensile bars were die cut from compression-molded plaques at 1/16″ thickness. All formulations are based on a 75 Shore A hardness, 60° C. flexible PVC formulation. Resin molecular weight is suitable for thick wall injection molding or thin wall profile or wire extrusion or film. Each test formulations contained the following: 
     Component Amounts in Formulation: 
       
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 Oxy 226 PVC Resin 
                 100 
               
               
                   
                 Flame Retardant 
                 55 
               
               
                   
                 Drapex 6.8 Epoxidized Soybean Oil 
                 6 
               
               
                   
                 Mark 4782A Ba/Zn Heat Stabilizer 
                 2.5 
               
               
                   
                 Stearic Acid 
                 0.25 
               
               
                   
                 Total 
                 163.75 
               
               
                   
                   
               
            
           
         
       
     
     Flame Retardants Evaluated: 
     TS-06-9A—Antiblaze® 519 
     TS-06-9B—Chemtura Reofos 50® 
     TS-06-9C—Supresta™ Phosflex 31L 
     TS-06-9D—Flame Retardant According to the Present Invention 
     TS-06-9E—Flame Retardant According to the Present Invention 
     TS-06-9F—Flame Retardant According to the Present Invention 
       
     
       
         
           
               
             
               
                 TABLE 23 
               
             
            
               
                   
               
               
                 MECHANICAL, ELECTRICAL AND COMPATIBILITY RESULTS IN 75 SHORE A 
               
               
                 FLEXIBLE PVC 
               
            
           
           
               
               
            
               
                   
                 TS-06- 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test 
                 9A 
                 9B 
                 9C 
                 9D 
                 9E 
                 9F 
               
               
                   
               
               
                 Hardness Shore A Inst/15 sec. 
                 85/76 
                 82/74 
                 84/78 
                 83/76 
                 84/77 
                 84/77 
               
               
                 ¼″ Thick 
               
               
                 Specific Gravity 
                 1.30 
                 1.29 
                 1.29 
                 1.29 
                 1.28 
                 1.28 
               
               
                 Tensile Strength 1/16″ Thick, 
                 3100 
                 3050 
                 3020 
                 2980 
                 3020 
                 3000 
               
               
                 psi 
               
               
                 100% Modulus, psi 
                 2010 
                 1920 
                 1920 
                 1810 
                 1850 
                 1930 
               
               
                 200% Modulus, psi 
                 2860 
                 2810 
                 2710 
                 2600 
                 2670 
                 2710 
               
               
                 Elongation @ Break 1/16″ 
                 240 
                 250 
                 260 
                 270 
                 260 
                 260 
               
               
                 Thick, % 
               
               
                 Aged 7 days @ 100° C. 
               
               
                 Tensile Retention % 
                 103 
                 107 
                 108 
                 109 
                 106 
                 100 
               
               
                 Elongation Retention % 
                 54 
                 46 
                 55 
                 67 
                 75 
                 60 
               
               
                 Limiting Oxygen Index, % O 2   
                 32.2 
                 32.3 
                 32.0 
                 31.6 
                 31.8 
                 32.2 
               
               
                 Volume Resistivity @ 23° C., 
                 3.6E12 
                 2.5E12 
                 2.9E12 
                 3.2E12 
                 3.5E12 
                 3.5E11 
               
               
                 Ω · cm 
               
               
                 Loop Spew, 1/16″ thick, 1″ 
                 None 
                 None 
                 None 
                 None 
                 None 
                 None 
               
               
                 loop 
               
               
                 Clarity, ¼″ thick 
                 Good 
                 Good 
                 Good 
                 Good 
                 Good 
                 Good 
               
               
                 Yellowness Index, ¼″ thick 
                 16.6 
                 20.0 
                 17.8 
                 15.8 
                 16.1 
                 22.6 
               
               
                 Haze, ¼″ thick 
                 None 
                 None 
                 None 
                 None 
                 None 
                 None 
               
               
                 High Humidity Exudation, 72 
               
               
                 hours @ 80° C. 
               
               
                 Tack 
                 Slight 
                 Slight 
                 Slight 
                 V. Slight 
                 Slight 
                 V. 
               
               
                   
                   
                   
                   
                   
                   
                 Slight 
               
               
                 Haze 
                 High 
                 High 
                 High 
                 High 
                 High 
                 High 
               
               
                 Color Development 
                 None 
                 Slight 
                 None 
                 None 
                 None 
                 None 
               
               
                   
                   
                 Yellow