CN101426801B - Low triphenylphosphate, high phosphorous content isopropyl phenyl phosphates with high ortho alkylation - Google Patents

Abstract

This invention relates to low-phosphorus triphenyl phosphates, highly ortho-alkylated aryl phosphates with high phosphorus content suitable for use in flame retardant compositions, methods for preparing them, and their use as flame retardants.

Description

Triphenylphosphate-low, high-phosphorus, highly ortho-alkylated cumyl phosphate

technical field

The present invention relates to flame retardant compositions and methods of making them. In more detail, the present invention relates to highly ortho-alkylated low triphenyl phosphate content, high phosphorus content aryl phosphate esters suitable for use as flame retardant compositions and processes for their preparation. the

Background of the invention

Alkylated aryl phosphates are known in the art for use as flame retardants. These compounds can be formed by a number of methods commonly used in the art. For example, it is known to prepare mixed synthetic triaryl phosphates by alkylating phenol with an olefin such as propylene or isobutylene to obtain a mixture of phenol and substituted phenols. According to US Patent No. 4,093,680, the alkylate mixture is then reacted with phosphorus oxychloride ( _POCl3 ) to form mixed triaryl phosphates. The product mixture is a statistical mixture based on the initial alkylate composition and always includes some fraction of triphenylphosphate ("TPP"), usually from 5 to 50%. The physical properties of the product are determined by the degree of alkylation of phenol. Highly alkylated phenol mixtures will result in more viscous phosphate ester products than less substituted phenol mixtures.

Triphenyl phosphate is a by-product of the alkylated phenyl phosphate formation reaction and is not desired in the final product because of environmental impact. For example, TPP is already classified as a marine pollutant in some jurisdictions. Thus, there has been much focus in the art on the removal of TPP from alkylated phenyl phosphates. For example, US Patent No. 5,206,404 discloses that wiped film purification can be used to produce mixed alkylated triphenyl phosphates with a TPP concentration of less than 2 wt%. The '404 patent also discloses that an undesirable method of reducing the TPP concentration of alkylated phenyl phosphates is through fractional distillation. the

U.S. Patent No. 6,232,485 discloses a process for producing liquid triaryl phosphates with low triphenyl phosphate concentration and low viscosity, comprising (a) an alkylation stage in which phenol is mixed with 2 reaction of alkenes to 12 carbon atoms to produce reaction products including a mixture of meta- and para-alkylated phenols; (b) a transalkylation stage in which the alkanes from the alkylation stage are heated in the presence of a strong acid catalyst; sylating a phenol mixture to increase the meta-isomer content of the mixture to at least 20% while keeping the phenol content below 22%; and (c) a phosphorylation stage. In the '485 process, the alkylated phenol mixture from the transalkylation stage is reacted with a phosphorylating reagent, and the strong acid catalyst used in stages (a) and (b) is a Bronsted acid with an acid strength less than zero. the

However, there are drawbacks in the prior art methods. For example, the '404 patent teaches that repeated passes through a wiped film evaporator may be required to reduce the TPP concentration to the desired level. Fractional distillation is also taught as a method of reducing the concentration of TPP in the final triaryl phosphate product, which also has drawbacks. As shown in the '404 patent, fractional distillation of the final triaryl phosphate product produces a product with undesirable color and acidity. Likewise, the '485 patent, as well as others such as US Pat. Nos. 4,069,279, 4,139,487, and 6,232,485, disclose methods for producing mixtures of products comprising alkylated phenyl phosphates having alkyl groups distributed over more than one phenyl group. These product distributions have undesirable properties such as high viscosity, inconsistent viscosity characteristics, and high triphenyl phosphate concentrations. the

Thus, there is a need in the art for low triphenyl phosphate, high phosphorus, alkylated phenyl phosphates with a high degree of ortho-alkylation and methods for forming them. the

Summary of the invention

In one embodiment, the present invention relates to alkylated triaryl phosphates comprising less than about 1 wt% triphenyl phosphate, based on the total weight of the alkylated triaryl phosphates, and The organophosphorus content ranges from about 5 to about 10 wt%, based on the total weight of the ester. the

In another embodiment, the invention relates to alkylated triaryl phosphates comprising one or more of the following alkylated phenyl phosphates: a) monoalkylphenyldiphenyl phosphates ); b) di-(alkylphenyl)phenylphosphates; c) dialkylphenyl diphenylphosphates; d) trialkylphenylphosphates Ester (trialkylphenyl phosphates); e) alkylphenyl dialkylphenyl phenyl phosphates (alkylphenyl dialkylphenyl phenyl phosphates); and f) less than about 1 wt. Phenyl esters wherein the alkyl portion of the alkylated phenyl phosphate is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-amyl and cyclohexyl groups, and the total phosphorus content of the alkylated triaryl phosphate varies from about 5 to about 10 wt%, based on the total weight of the alkylated triaryl phosphate. the

The present invention also relates to a process for the manufacture of alkylated triaryl phosphates comprising:

a) in the presence of the first catalyst, according to the first reaction conditions comprising a temperature change from about 80°C to about 210°C, based on the total moles of active alkylated phenols in the alkylated phenol, comprising less than about Alkylated phenols of 1 mole percent phenol and up to about 75 mole percent dialkylphenols are reacted with _POCl to thereby produce a first reaction product comprising, based on the total moles of the first reaction product, greater than about 75 mole percent monoalkylated phenyl dichlorophosphate; and

b) in the presence of a second catalyst according to second reaction conditions comprising a temperature varying from about 90°C to about 260°C, the first reaction product is reacted with an alcohol selected from the group consisting of aryl alcohols, alkyl alcohols, alkylated aryl alcohols Alcohol reactions of alcohols and mixtures thereof, thereby producing alkylated triaryl phosphates. the

The present invention also relates to a process for the manufacture of alkylated triaryl phosphates comprising:

a) In the presence of the first catalyst, according to the first reaction conditions comprising a temperature ranging from about 80°C to about 210°C, based on the total weight of the alkylated phenol, comprising less than about 1% phenol and up to about Alkylated phenol of 75% dialkylphenol is reacted with _a molar excess of POCl, thereby producing a first reaction product comprising greater than about 50 mole percent mono Alkylated phenyl dichlorophosphate and excess POCl ₃ ;

b) removing at least part of the excess _POCl3 from the first reaction product to produce an intermediate product, wherein the intermediate reaction product comprises less than 15 mole % residual phosphorus in the form of _POCl3 based on the total moles of the intermediate reaction product; and

c) in the presence of a second catalyst according to second reaction conditions comprising a temperature varying from about 90°C to about 260°C, the first reaction product is reacted with an alcohol selected from the group consisting of aryl alcohols, alkyl alcohols, alkylated aryl alcohols Alcohol reactions of alcohols and mixtures thereof, thereby producing alkylated triaryl phosphates. the

Detailed description of the invention

As used herein, "IP's" means reference to isopropylated phenol; "OIP" means reference to ortho-isopropylphenol; "MIP" means reference to meta-isopropylphenol; "PIP" means a reference to p-isopropylphenol; "TPP" means a reference to triphenylphosphate; "2,6-DIP" means a reference to 2,6-diisopropylphenol; "2,4-DIP " means mention of 2,4-diisopropylphenol; "2,4,6-TIP" means mention of 2,4,6-triisopropylphenol; "2-IPP" means mention of 2 - Isopropylphenyl diphenyl phosphate; "3-IPP" means reference to 3-isopropylphenyl diphenyl phosphate; "4-IPP" means reference to 4-isopropylphenyl Diphenyl phosphate; "2,4-DDP" means reference to 2,4-diisopropylphenyl diphenyl phosphate; "IPP's" means reference to isopropylated triphenyl phosphate ; "DTPP" means reference to diisopropylated triphenyl phosphate; and "TTPP" means reference to triisopropylated triphenyl phosphate. the

Alkylated triaryl phosphate

In one embodiment, the present invention relates to alkylating triaryl phosphates. The alkylated triaryl phosphates of the present invention are characterized as comprising less than about 1 wt % TPP based on the total weight of the alkylated triaryl phosphate, and in some embodiments less than about 0.75 wt % TPP on the same basis, and at Other embodiments are less than about 0.5 wt% TPP on the same basis. the

Although the concentration of TPP is low, the alkylated triaryl phosphates of the present invention still contain a high amount of phosphorus. Typically, the alkylated triaryl phosphates of the present invention contain from about 5 to about 10 weight percent organophosphorus, based on the total weight of the alkylated triaryl phosphate. Preferably the organophosphorus content varies from about 7 to about 9 wt % on the same basis, and in more preferred embodiments the organophosphorus content varies from about 7.5 to about 8.5 wt %, most preferably from about 8.0 to about 8.0 wt % on the same basis. in the range of about 8.4%. the

In some embodiments, the alkylated triaryl phosphates of the present invention can be further characterized as comprising greater than about 20 weight percent monoalkylphenyl diphenyl phosphate, based on the total weight of the alkylated triaryl phosphate. Preferably, the alkylated triaryl phosphate comprises greater than about 75 weight percent monoalkylphenyl diphenyl phosphate on the same basis, more preferably the amount is greater than about 90 weight percent on the same basis. the

The alkylated triaryl phosphates of the present invention can be further characterized as comprising less than about 80 weight percent bis(alkylphenyl)phenyl phosphates, based on the total weight of the alkylated triaryl phosphates. Preferably, on the same basis, the alkylated triaryl phosphates of the present invention comprise less than about 25 wt%, more preferably less than about 10 wt% bis(alkylphenyl)phenyl phosphate. the

The alkylated triaryl phosphates of the present invention can be further characterized as comprising less than about 50 weight percent dialkylphenyl diphenyl phosphate, based on the total weight of the alkylated triaryl phosphate. However, in preferred embodiments, on the same basis, the alkylated triaryl phosphates of the present invention comprise less than about 25 wt%, more preferably less than about 10 wt% dialkylphenyl diphenyl phosphate. In the most preferred embodiment, the alkylated triaryl phosphates of the present invention comprise less than about 1 ?? wt % dialkylphenyl diphenyl phosphate, based on the total weight of the alkylated triaryl phosphate ester. The present inventors have surprisingly found that, in some embodiments, removal of unreacted alkylated phenol during production of the alkylated triaryl phosphates of the present invention, for dialkylphenylbiphenyl at these concentrations Alkylation of triaryl phosphates with base phosphates is more efficient. the

The amount of trialkylphenyl phosphate present in the alkylated triaryl phosphates of the present invention is generally less than about 20 weight percent, based on the total weight of the alkylated triaryl phosphate. However, in preferred embodiments, on the same basis, the alkylated phenyl phosphates of the present invention may contain less than about 2 weight percent trialkylphenyl phosphates. In some most preferred embodiments the trialkylphenyl phosphate content is less than 0.5 wt% on the same basis. The alkylated phenyl phosphates according to the present invention also include less than about 20 weight percent of alkylphenyl dialkylphenyl phenyl phosphates, based on the total weight of the alkylated triaryl phosphates. In a most preferred embodiment, the alkylated triaryl phosphates of the present invention comprise less than 0.05% by weight of alkylphenyl dialkylphenylphenyl phosphates, based on the total weight of the alkylated triaryl phosphates . the

Exemplary alkylated triaryl phosphates of the invention are those a) comprising: IPP in the range of from about 90 to about 92 wt%, TPP in the range of from about 0.5 to about 0.75 wt%, TPP in the range of from about 1 to DTPP in the range of about 3 wt %, TTPP in the range of from about 0.05 to about 0.15 wt %, and 2,4-DDP in the range of from about 0.5 to about 0.75 wt %; b) in the range of from about 94 to about 96 wt % in the range of IPP, DTPP in the range from about 3.5 to about 5.5 wt%, and TTPP in the range from about 0.1 to about 0.3 wt%; and c) IPP in the range from about 71 to about 73 wt% , TPP in the range from about 0.05 to about 0.15 wt%, DTPP in the range from about 26 to about 28 wt%, and TTPP in the range from about 0.5 to about 0.7 wt%. the

Monoalkylphenyl diphenyl phosphate, di(alkylphenyl)phenyl phosphate, dialkylphenyl diphenyl phosphate, trialkyl Phenyl phosphate and alkylphenyl dialkylphenyl phenyl phosphate are wherein the alkyl moiety is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, Those of the pentyl, isopentyl, tert-pentyl and cyclohexyl alkyl moieties. Preferably, monoalkylphenyldiphenylphosphate, di(alkylphenyl)phenylphosphate, dialkylphenyldiphenylphosphate, trialkylphenylphosphate present in the alkylated triarylphosphate At least one, preferably at least two, and more preferably all of the alkyl moieties of the alkylphenyl phosphate and the alkylphenyl dialkylphenyl phenyl phosphate are isopropyl moieties. Thus, for example, in the most preferred embodiment, the alkylated triaryl phosphate according to the invention is cumylphenyl diphenyl phosphate. 0.1 to 99.9 wt% of the total isopropylphenyl diphenyl phosphate is 2-isopropylphenyl phosphate (2-IPP), and 0.1 to 99.9 wt% is 3-isopropylphenyl phosphate (3 -IPP), 0.1 to 99.9% by weight is 4-isopropylphenyl phosphate (4-IPP), all based on the total weight of the alkylated triaryl phosphate. In the most preferred embodiment, 66 to 100% by weight of the isopropylphenyl diphenyl phosphate present in the alkylated triaryl phosphates according to the 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 cumylphenyl phosphates have been discussed above, generating alkylated triaryl phosphates with any possible relative ratio of 2-IPP, 3-IPP, and 4-IPP is not an issue in the present invention. In the range. However, in the most preferred embodiment, the alkylated triaryl phosphate according to the present invention is cumyl phenyl diphenyl phosphate, wherein the cumyl phenyl in the range of about 63 to about 68% Diphenyl phosphate is 2-IPP, 3-IPP in the range of from about 0.5 to about 2.5%, and 4-IPP in the range of from about 30.5 to about 36.5%. In an exemplary embodiment of the invention, the alkylated triaryl phosphate according to the invention is cumyl phenyl diphenyl phosphate, wherein about 66% of the cumyl phenyl diphenyl phosphate is 2- Of the IPP, about 1% is 3-IPP and about 33% is 4-IPP. A method of suitably forming an alkylated triaryl phosphate of the invention comprising reacting an alkylated phenol with POCl in the presence of _a first catalyst to form a first reaction product; and then in the presence of a second catalyst Under second reaction conditions comprising a temperature varying from about 90°C to about 260°C, the first reaction product is reacted with an alcohol selected from the group consisting of aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof, whereby Alkylated triaryl phosphates according to the invention are produced. It should be noted that the reaction that produces the first reaction product is sometimes referred to herein as the first reaction, and the reaction of the first reaction product with the alcohol is sometimes referred to herein as the second reaction.

First Reaction - Alkylation of Phenol

Alkylated phenols suitable for the first reaction include those in which the alkyl moiety is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-amyl base moieties and cyclohexyl, preferably isopropyl. the

Preferably, the alkylated phenol reacted with _POCl in the presence of the first catalyst comprises less than 1 mole % phenol and Less than 25 mole % dialkylphenols. In a more preferred embodiment, the alkylated phenol comprises less than 0.5 mole percent phenol and less than 15 mole percent dialkylphenol based on the total moles of active alkylated phenol in the alkylated phenol. In the most preferred embodiment, the alkylated phenol contains less than 0.5 mole percent phenol and less than 5 mole percent 2,4-diisopropyl, based on the total moles of active alkylated phenols in the alkylated phenolic novolac. phenol. In a preferred embodiment, the dialkylphenol of the alkylated phenol is 2,4-diisopropylphenol.

In a more preferred embodiment, the alkylated phenol stream consists essentially of OIP, MIP and PIP components. In this embodiment, it is preferred that the alkylated phenol stream comprises OIP in the range of from about 64 to about 68 wt%, MIP in the range of from about 0.5 to about 2.5 wt%, and in the range of from about 31 to about 35 wt% All PIPs in are based on the total weight of alkylated phenol. the

"Total moles of active alkylated phenol" and "active alkylated phenol" as used herein are meant to refer to the total moles of alkylated phenol participating in the reaction between alkylated phenol and _POCl . This unit of measure is used herein because unreacted alkylated phenol is also present in the alkylated phenol. For example, 2,6-DIP and 2,4,6-TIP are common impurities in streams of IP's, but are unreacted in any sense. See, for example, Table 1 below, which describes an example of an alkylated phenol suitable for use herein:

In Table 1, this is based on the total moles of active alkylated phenol, the amounts stated would thus be based on 134.83 moles. the

First Reaction - POCl ₃

The amount of _POCl3 used herein may be a molar equivalent, in some embodiments a molar excess, and in other embodiments less than a molar equivalent. By molar equivalents of _POCl3 is meant a molar ratio of about 1 mole of _POCl3 to about 1 mole of active alkylated phenol. By molar excess of _POCl3 is meant a molar ratio of greater than 1 mole of _POCl3 to 1 mole of active alkylated phenol. Preferably the molar excess is in the range of from about 1.0 to about 5.0 moles of POCl _to about 1 mole of active alkylated phenol, and more preferably in the range of from about 1.15 to about _2.5 moles of POCl to about 1 mole of active alkylated phenol within, for use in the practice of this embodiment of the invention.

By less than a molar equivalent of _POCl3 is meant a molar ratio of less than 1 mole of _POCl3 to 1 mole of active alkylated phenol. For example, in one embodiment that produces a first reaction product having significantly higher DTTP and TTPP, a molar excess of alkylated phenol, ie, less than a molar equivalent of _POCl3 , may be employed. In this embodiment, it is preferred to employ greater than a range of from about 1 to about 2 moles, preferably a range of from 1.1 to about 1.2 moles, of active alkylated phenol per mole of _POCl3 .

Active alkylated phenols are defined above.

first catalyst

Catalysts suitable for use as the first catalyst herein may be selected from tertiary amines such as trialkylamines, dialkylarylamines, and heterocyclic tertiary amines such as 1,4-diazobicyclo-[2,2,2]- Octane (DABCO); Aromatic amines such as pyridine and substituted pyridines, N,N-dimethylaminopyridine being preferred; Pyrimidine and its derivatives; Pyrazine and its derivatives; Pyroles and their derivatives; Imidazole , its derivatives and their corresponding mineral salts and organic acid salts with N-methylimidazole, imidazole and derivatives derived from this group are preferred; quaternary ammonium salts; quaternary phosphonium salts; having the general formula P(NRR ') Tetrakisdialkylamino phosphonium salts (tetrakisdialkylamino) phosphonium salts of ₄ ⁺ X ^- , especially tetrakis (diethylamino) phosphonium bromide salts of formula P(NEt ₂ ) ₄ ⁺ Br ^- ; base metal halide catalysts; and alkaline earth metal halides, oxides, sulfates, sulfonates, hydroxides, and phosphates. It should be noted that any of the alkali metal halides and salts mentioned above can be used, such as ammonium, phosphonium, etc., as long as the salt/halide has suitable solubility to initiate the reaction with _POCl so that the by-product hydrogen chloride eventually converts the metal catalyst salt to metal chlorides. Non-limiting examples of alkali metal and alkaline 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 halides, tetraalkyl or mixed alkylammonium mineral salts, or organic acid salts. Non-limiting examples of suitable quaternary phosphonium salts include any tetraalkyl or tetraaryl phosphonium salts. Preferably the first catalyst is selected from quaternary ammonium salts, quaternary phosphonium salts, tetrabutylammonium chloride, _MgCl2 and pyridine. In a preferred embodiment the first catalyst is tetrabutylammonium chloride. In yet another preferred embodiment the first catalyst is _MgCl2 . In a particularly preferred embodiment, the first catalyst is pyridine.

first reaction condition

The _POCl3 and the alkylated phenol are reacted according to first reaction conditions comprising a temperature ranging from about 75°C to about 210°C. Preferably, the first reaction conditions comprise a temperature ranging from about 80°C to about 150°C, more preferably a temperature ranging from about 90°C to about 140°C. The reactants and first catalyst may be mixed, contacted, etc. in any order. However, it is preferred to add an alkylated phenol reactant to the _POCl3 reactant. It has been found that mixing the reactants and catalyst in this order produces an alkylated phenol phosphate of superior viscosity, ie less viscous. In a more preferred embodiment, the alkylated phenol is added to the reaction vessel containing the _POCl3 reactant and the first catalyst.

It should be noted that the reaction between the alkylated phenol and _POCl generates HCl gas that may cause undesired cleavage and/or transesterification reactions. Thus, in a preferred embodiment, the first reaction conditions also include venting HCl gas. This venting can be carried out by any method known to be effective for venting HCl gas from the reaction vessel. However, in a preferred embodiment, venting is accomplished by carrying out the reaction according to the first reaction conditions comprising reduced pressure, ie under vacuum. A person of ordinary skill in the art can easily select the degree of vacuum to be used, taking into account that too high a vacuum will cause the reaction temperature to fall outside the above-mentioned range, thereby reducing the reaction rate. Furthermore, while negative pressure is preferred, the reaction can be carried out at atmospheric pressure up to about 5 psig and still yield the desired product, albeit at a somewhat reduced rate. Pressures significantly above 5 psig will reduce the reaction rate somewhat and may result in undesired cleavage and/or transesterification reactions.

In preferred embodiments, the first reaction conditions further comprise the substantial absence of oxygen. the

First Reaction - Optional Diluent

In some embodiments, a diluent may be added with _POCl3 , the first catalyst, and the alkylated phenol. Diluents suitable for use herein are i) substantially non-reactive with the reactants, products, and by-products comprising HCl used or produced during the first and/or second reactions; and ii) substantially do not degrade the first and/or second or those of the catalytic activity of the second catalyst. In preferred embodiments, diluents suitable for use herein can be further characterized as iii) not lowering the reaction temperature so that the reaction rate is significantly reduced to a commercially unviable level, ie below the range disclosed herein. It should be noted that the diluent may be added as a mixture with the first catalyst. Non-limiting examples of suitable diluents include a) hydrocarbon solvents such as heptane, petroleum ether, methylcyclohexane and boiling point heptane; b) aromatic hydrocarbons such as toluene, xylene and ethylbenzene; c) halogenated hydrocarbons and halogenated 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 the most preferred embodiment, the diluent is toluene.

first reaction product

The reaction of _POCl3 and alkylated phenol produces a first reaction product comprising greater than about 50 mole percent monoalkyl based on the total moles of the first reaction product excluding unreacted _POCl3 and any added diluent Phenyl dichlorophosphate.

In some embodiments, the first reaction product may include monoalkylated phenyl dichlorophosphate in the range of about 70 to about 99.9 mole percent, and in the range from about 0.1 mole percent, based on the same basis, to % to about 30 mole % bis-(monoalkylated) phenyl-chlorophosphates. the

By excess POCl ₃ is meant POCl ₃ that has not reacted with the alkylated phenol, ie unreacted POCl ₃ . Typically, the first reaction product comprises unreacted POCl in the range _of from about 5 to about 80 mole percent based on the total phosphorus in the first reaction product, as determined by some suitable method, preferably quantitative P ^NMR . The amount of unreacted _POCl3 in the first reaction product obviously depends on the amount of _POCl3 used in the first reaction stage. For example, if less than a molar equivalent of _POCl3 is used, then depending on the efficiency of the reaction between the alkylated phenol and _POCl3 , the first reaction product may be substantially free of excess _POCl3 ; however, if a molar excess of POCl3 is used ₃ , then the excess amount of _POCl3 will depend on the reaction efficiency and the amount of _POCl3 used. In the practice of the present invention, if less than a molar equivalent or up to about a 15% molar excess of _POCl3 is used to produce the first reaction product, the first reaction product may, and in some embodiments, react directly with the alcohol without removing untreated Reactive POCl ₃ .

Optional removal of _POCl3

If an excess of _POCl3 is employed in producing the first reaction product, then preferably at least a portion of the excess _POCl3 is removed from the first reaction product, thereby producing an intermediate reaction product. In a preferred embodiment, the amount of excess _POCl3 removed from the first reaction product is such that the amount of excess POCl3 is removed from the first reaction product to produce a concentration comprising less than about 15 mole percent, preferably less than about 10 mole percent, more preferably less than about 10 mole percent, based on the total phosphorus in the first reaction product. The amount necessary for the intermediate product is at about 5 mole % and most preferably less than about 1 mole % _POCl3 . In particularly preferred embodiments, substantially all of the unreacted _POCl3 is removed from the first reaction product, which in some embodiments may result in an intermediate reaction product substantially free of unreacted alkylated phenol. However, it should be noted that if the intermediate reaction product is reacted with phenol, the amount of unreacted _POCl3 removed from the first reaction product must be such that an intermediate product comprising less than about 1.2 mole %, preferably less than about 1 mole % total organophosphorus required amount.

The method by which _POCl3 is removed from the first reaction product to produce the intermediate product is not critical to the invention, and non-limiting examples of suitable removal techniques include vacuum distillation, flashing, steam stripping, vacuum stripping, and the like. In a preferred embodiment, _POCl3 is removed by vacuum stripping. Vacuum stripping may conveniently be performed by heating the first reaction product to a temperature in the range of from about 115°C to about 170°C under constant agitation under a vacuum in the range of from about 700 mmHg to about 0.001 mmHg. Compressed nitrogen purge with vacuum stripping is within the scope of this invention. It is also within the scope of this invention to add an inert "chaser" solvent at the end of the vacuum stripping to reduce the _POCl3 in the intermediate reaction product to less than 1 mole percent (based on the intermediate reaction product). If a squeeze liquid solvent is used, preferably toluene, methylcyclohexane, boiling point heptane or n-heptane are used.

It should be noted that, although not required, in some embodiments the optional removal of _POCl3 is accompanied by the removal of a portion of any diluent added during the first reaction. In this embodiment, the conditions can be adjusted to the above ranges, selecting methods as those described above for more efficient removal of _POCl and diluent.

second reaction

In the practice of the present invention, the first or intermediate reaction product is reacted with an alcohol selected from the group consisting of aryl alcohols (including phenol), alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in the presence of a second catalyst. reacted, or treated to remove at least a portion of the excess _POCl3 .

In another embodiment, the first reaction product or intermediate can be reacted continuously with more than one alcohol selected from the group consisting of aryl alcohols including phenol, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof . In this embodiment, preferably a first reaction product or intermediate is reacted with a first alcohol, and a second alcohol, preferably different from the first alcohol, is added when the first alcohol has been consumed as determined by a suitable method such as ^P31 NMR.

More preferably, in this embodiment, the first alcohol is divided into first and second fractions. 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 ^P31 NMR. After the first portion of the first alcohol has been substantially completely consumed, the second portion of the first alcohol is added and the reaction is allowed to continue until the second portion of the first alcohol has been substantially completely consumed as determined by a suitable method such as P ^NMR , thereby producing a first intermediate reaction product comprising at least an aryl dichlorophosphate and a chlorodiarylphosphate.

The first intermediate reaction product, which is richer, ie, has a higher concentration of chlorinated diaryl phosphate, than the first reaction product, is then reacted with an effective amount of a second alcohol. By an effective amount of the second alcohol it is meant that the amount of the second alcohol is such that substantially all of the aryl dichlorophosphates and chlorodiarylphosphates are converted to the alkylated triarylphosphates according to the invention It is effective. the

In this embodiment, the first reaction product and the second alcohol may be independently selected from aryl alcohols including phenol, alkyl alcohols, alkylated aryl alcohols, and mixtures thereof. the

Non-limiting examples of suitable alkylated aryl alcohols are those wherein the alkyl group contains from about 1 to about 5 carbon atoms, eg methyl. Non-limiting examples of suitable alkyl alcohols are those wherein the alkyl group contains from about 20 carbon atoms such as n-decanol. Preferably the alcohol is selected from phenol, decyl alcohol, dodecanol or mixtures thereof, and in a most preferred embodiment the alcohol is phenol. the

second catalyst

Catalysts suitable for use as the second catalyst herein may 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 and phosphonium salts include those listed above with respect 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 _MgCl2 .

Second reaction condition

The first or intermediate reaction product is reacted with an alcohol in the presence of a second catalyst according to second reaction conditions comprising a temperature ranging from about 75°C to about 260°C. Preferably, the second reaction conditions comprise a temperature ranging from about 100°C to 180°C, most preferably from about 140°C to about 150°C. The first or intermediate reaction product, the alcohol, and the second catalyst may be mixed, contacted, etc., in any order. For example, the first or intermediate reaction product, the alcohol, and the second catalyst may be fed together to a reaction vessel, the first or intermediate reaction product may be added to the reaction vessel containing the alcohol and the second catalyst, and the like. However, it is preferred to add the alcohol, preferably in molten or liquid state, to the first reaction product reactant or intermediate reaction product which has been introduced into the second catalyst. The inventors have unexpectedly discovered that mixing, contacting, etc. of the first reaction product or intermediate reaction product, second catalyst and alcohol in this manner provides alkylated phenol phosphates with lower TPP concentrations than in reactions not added in this manner. those that are formed when things are. In this embodiment, it is preferred that the catalyst is provided with the alcohol, but it may be co-fed or fed after the intermediate product. the

In preferred embodiments, the second reaction conditions further comprise the substantial absence of oxygen. the

As noted above, the reaction of the first or intermediate reaction product with an alcohol produces an alkylated triaryl phosphate according to the invention. the

Optional Alkylated Triaryl Phosphate Treatment

In some embodiments, it may be desirable to further purify the alkylated triaryl phosphate produced from the present process, eg, to remove any excess alcohol that may be present in the alkylated triaryl phosphate. Further processing may also include adding to the alkylated triaryl phosphate an additional amount of alcohol such as monoisopropanyl phenol, diisopropanyl phenol, phenol and mixtures thereof and/or a second catalyst. The alcohol-rich alkylated triarylphosphate product including excess alcohol may then be recovered and at least some, preferably substantially all, of the excess alcohol removed by, for example, phase separation and/or stripping and/or distillation. In a preferred embodiment, steam stripping is employed. the

It is also possible to wash the alkylated triaryl phosphate one or more times with acid, base or water. In this embodiment, the alkylated triaryl phosphate may be washed first with acid and/or base, preferably base, and then with water. In this embodiment, the alkylated triaryl phosphate is preferably washed about 1 to about 4 times with a base such as NaOH, preferably with a dilute base comprising NaOH in the range of about 1 to about 5 wt % (based on the dilute base). range, followed by washing with water until the pH of the water recovered from the washing is in the range from about 7 to about 9. the

In another embodiment, the alkylated triaryl phosphate can also be treated in a wiped film evaporator, distillation column or other similar separation device together with the above further purification method or as a separate purification. the

Use of alkylated triaryl phosphates as flame retardants

The alkylated triaryl phosphates of the present invention are suitable for use as flame retardants in many applications. In particular, the alkylated triaryl phosphates of the present invention are especially suitable for use in polyurethane foams, polymeric resins and polyester resins. the

In one embodiment, the present invention is directed to flame retardant polyvinyl chloride resin formulations comprising at least one (in some embodiments only one) polyvinyl chloride resin and a flame retardant amount of at least one (in some embodiments Only one) an alkylated triaryl phosphate as described herein. In terms of the flame retardant amount of the alkylated triaryl phosphate, it means that based on the total weight of the flame retardant polyvinyl chloride resin formulation, at least one alkylated triaryl phosphate is in the range of from about 2 to about In the range of 150 parts ("phr"). In preferred embodiments, the flame retardant amount of the alkylated triaryl phosphates is considered to be in the range of from about 5 to about 70 phr, more preferably from about In the range of 12 to about 45phr. the

Resins suitable for use in this embodiment of the invention include those comprising polymers composed of one or more polymerizable monomers having a polymerizable olefinic double bond in the molecule. There are three groups of such polymers, namely (i) one or more vinyl aromatic homopolymers or copolymers, preferably high impact polystyrene, (ii) one or more acyclic olefin homopolymers or Copolymers such as polyethylene, polypropylene, and copolymers of ethylene or propylene with at least one higher olefin with or without diene monomers, and (iii) at least one vinylaromatic monomer and at least one One or more copolymers of non-vinyl aromatic monomers, acrylate monomers or methacrylate monomers with or without diene monomers containing functional groups such as acrylonitrile. Examples of group (ii) include ABS, MBS, SAN and ASA. Preferred among the above three groups of polymers are vinyl aromatic polymers. the

Vinyl aromatic polymers that may be flame retardant in the practice of this invention may be homopolymers, copolymers, or block polymers, and such polymers may be ring-substituted from vinyl aromatic monomers such as styrene, Styrene (where the substituent is one or more C _1-6 alkyl groups), alpha-methylstyrene (where the substituent is one or more C _1-6 alkyl groups), vinyl naphthalene and similar polymerizable styrenic monomers (ie styrenic compounds capable of being polymerized into thermoplastic resins by means of, for example, peroxides or similar catalysts). Simple styrenic monomers (e.g., styrene, p-methylstyrene, 2,4-dimethylstyrene, α-methylstyrene, p-chlorostyrene, etc.) are preferred from the standpoint of cost and availability. ) homopolymers and copolymers. The flame-retardant vinylaromatic polymers according to the invention may be homopolymers or copolymers which can be produced by free-radical polymerization, cationically initiated polymerization or anionically initiated polymerization. Additionally, the flame retardant vinyl aromatic polymer in the practice of the present invention may be a foamable, expanded, or foamed vinyl aromatic polymer composition. Vinyl aromatic polymers can have various structural forms. For example they may be isotactic polymers, syndiotactic polymers or mixtures of isotactic and syndiotactic polymers. Additionally the vinyl aromatic polymers may be in the form of mixtures or alloys with other thermoplastic polymers, such as polyphenylene ether-styrenic polymer blends and polycarbonate-styrenic polymer blends. The vinyl aromatic polymers may be impact modified or rubber modified polymers. In some embodiments, the resin is polyvinyl chloride resin.

In these embodiments, the flame retardant resin formulation may also include conventional additives such as processing aids, acid scavengers, dyes, pigment fillers, stabilizers, antioxidants, antistatic agents, reinforcing agents, blowing agents, nucleating agents, agents and plasticizers etc. The amounts of these additives used in flame retardant polyvinyl chloride resin formulations are conventional, and those of ordinary skill in the art can easily select the amounts and specific additives according to the desired properties of flame retardant polyvinyl chloride resin formulations. the

The alkylated triaryl phosphates of the present invention are suitable for use as flame retardants in polyurethane/polyisocyanurate foams and polyurethane/polyisocyanurate foam formulations. Thus, in some embodiments, the present invention relates to polyurethane/polyisocyanurate foams, polyurethane/polyisocyanurate foam formulations, and methods for forming flame-retardant polyurethane/polyisocyanurate foam formulations, Both rigid and flexible, comprise a flame retardant amount of at least one (and in some embodiments only one) alkylated triaryl phosphate as described herein. In some embodiments, the present invention relates to polyurethane foams, polyurethane foam formulations, and methods for forming flame retardant polyurethane foam formulations, both rigid and flexible (in some embodiments flexible), comprising a flame retardant amount of at least One (in some embodiments only one) alkylated triaryl phosphate as described herein. In terms of flame retardant amounts of alkylated triaryl phosphates, it is meant from about 5 to about 75 wt. based on the total weight of the polyurethane/polyisocyanurate foam or polyurethane/polyisocyanurate foam formulation % of at least one alkylated triaryl phosphate in the range. In a preferred embodiment, the flame retardant amount of the alkylated triaryl phosphate is contemplated to be in the range of from about 5 to about 70 weight percent.

Polyurethanes and polyisocyanurates, their foams, and methods of making such polymers are well known in the art and reported in the literature.例如参见Encyclopedia of Polymer Science andTechnology，vol.11，pgs.506563(1969Wiley & Sons)和vol.15，pp.445479(1971Wiley & Sons)，美国专利号3,974,109；4,209,609；4,405,725；4,468,481；4,468,482；5,102,923；5,164,417 7,045,564 and 7,153,901; and US Patent Application No. 11/569,210, which are incorporated by reference in their entirety. For example, flexible polyurethane foam is typically prepared by a chemical reaction between two liquids, an isocyanate and a polyol. The polyols are polyether or polyester polyols. The reaction occurs readily at room temperature in the presence of blowing agents such as water, volatile hydrocarbons, halocarbons or halocarbons, or mixtures of two or more such materials. Catalysts used to effect this reaction include amine catalysts, tin-based catalysts, bismuth-based catalysts, or other organometallic catalysts, among others. In order to maintain the uniformity of the units in the polymerization system, surfactants such as substituted organosilicon compounds are often used. Hindered phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol and methylene bis(2,6-di-tert-butylphenol) can be used to further assist in stabilization against oxidative degradation. the

In some embodiments, the present invention also relates to polyurethane/polyisocyanurate foam formulations comprising a flame retardant amount of at least one (and in some embodiments only one) alkylated triaryl as described herein a phosphate ester; at least one, and in some embodiments only one, isocyanate or polyol; and at least one (in some embodiments only one) blowing agent, and polyurethane/polyisocyanurate foam formed therefrom, rigid and flexible. Blowing agents suitable for use herein include water, volatile hydrocarbons, halocarbons or halocarbons, or mixtures of two or more such materials. the

In addition to these ingredients, polyurethane/polyisocyanurate foams and foam formulations may contain any other ingredients known in the art and used to form flexible and rigid polyurethane/polyisocyanurate foams, and to form These other components of polyurethane polymerization formulations or formulations are well known to those of ordinary skill in the art. For example, polyurethane/polyisocyanurate foam formulations may contain surfactants, antioxidants, diluents such as low viscosity liquid C _1-4 halogenated hydrocarbons and/or halogenated hydrocarbon diluents (wherein the halogen component is 1 to 4 bromine and/or chlorine atoms). Non-limiting examples of such diluents include bromochloromethane, methylene chloride, dichloroethane, dibromoethane, isopropane chloride, n-butane bromide, sec-butane bromide, n-butane chloride , Chloro-sec-butane, Chloroform, Perchloroethylene, Methyl Chloroform and Carbon Tetrachloride.

It should be noted that these and other ingredients useful in the polyurethane/polyisocyanurate foam formulations of the present invention, as well as the proportions and manner of using them, are reported in the literature. See for example: Herrington and Hock, Flexible Polyurethane Foams, The Dow Chemical Company (The Dow Chemical Company), 1991, 9.259.27, or Roegler, M "Slabstock Foams"; Pofyurethane Handbook; Oertel, G., Ed.; Hanser Munich, 1985, 176177, or Woods, G. Flexible Pofyurethane Foams, Chemistry and Technology; Applied Science Publishers, London, 1982, 257260, all of which are incorporated by reference, and have been incorporated US Patent Application No. 11/569,210, incorporated herein by reference. the

The above description is directed to several embodiments of the invention. Those skilled in the art will recognize that other equally effective methods can be devised for carrying out the spirit of the invention. It should also be noted that the 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 ranging 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, and the like. The following examples illustrate the invention but are not meant to be limiting in any way. the

Example

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 product recovered from the reactor. "Normalized wt%" indicates the amount of each component calculated by dividing the value of "Wt% in Crude" by the "Normalization Factor", thus indicating the amount of each component related to the alkylated triaryl phosphate. the

Embodiment 1 (comparison)

The reaction flask was purged with nitrogen. 15.3 g (0.1 mole) of phosphorus oxychloride (" _POCl3 ") was followed by 13.6 g (0.1 mole) of o-isopropylphenol ("OIP"). The mixture was heated to about 110°C for 10 hours with stirring. The contents of the flask were analyzed by means ^of1H -NMR and it was found that more than 50 mol% of the OIP was unreacted. The contents of the flask were also analyzed by means of ³¹ P-NMR and it was found that 2-cumyl dichlorophosphate was more The molar ratio of esters is 40.8:22.6:5.0.

Embodiment 2 (comparison)

The reaction flask was purged with nitrogen. Then 15.3 g (0.1 moles) of phosphorus oxychloride (" _POCl3 ") followed by 13.6 g (0.1 moles) of o-isopropylphenol ("OIP") were added to the flask over 30 minutes. The mixture was heated to 195°C with stirring for 5 hours. The contents of the flask were analyzed by means of proton NMR, and the presence of unreacted OIP in the flask was detected by this analysis, indicating that the reaction was incomplete. The contents of the flask were then heated to 250°C with stirring for 3 hours until no OIP was detected. The contents of the flask were analyzed by means of ³¹ P-NMR, and it was found that 2-cumyl dichlorophosphate was more abundant than bis(2-cumyl)chlorophosphate than tris(2-cumyl)phosphate. The molar ratio is 56.2:28.7:2.8.

Example 3 (example 1-comparison drawn from US4,139,487)

Phenol (65.2 parts) and a mixture of m- and p-isopropylphenols (47.9 parts) were mixed with phosphorus oxychloride (51 parts; ie 5% excess of phenolic reactants). Addition of crushed anhydrous magnesium chloride (0.5 parts) catalyzed the reaction. The reaction mixture was heated rapidly to 130°C and then slowly to 230°C over a period of about 2 hours, after which no further significant evolution of hydrogen chloride occurred. Completion of the reaction was checked by a titration test on the crude, which was then vacuum distilled to yield a recovered phenol fraction, a small middle distillate and a major ester fraction (88% of the crude) boiling at 205°C to 225°C at 1 mm Hg. . the

The composition of the recovered phenol fraction was shown by analysis to be essentially the same as the phenol feed mixture, indicating that there had been no apparent component separation due to preferential esterification, as evidenced by hydrolysis of a portion of the major ester fraction and analysis of the recovered phenol. The distilled phosphate esters had a satisfactory color, oxidizable impurity content and acidity and were therefore not 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 composition of the distilled phosphate esters is shown in Table 2 below. The wt% is based on the total weight of distilled phosphate ester. the

Table 2

components wt% Triphenyl Phosphate 30 Mono-(isopropylphenyl)diphenyl phosphate 44 Bis-(isopropylphenyl)phenyl phosphate twenty two Tris-(isopropylphenyl)phosphate 4 total 100

The distilled phosphate had a calculated carbon number of 21 and contained 33 mole percent cumyl groups. the

Example 4 (example 2-comparison drawn from US4,139,487)

Phenol (32.6 parts) and a mixture of m- and p-isopropylphenol (95.8 parts) were mixed with phosphorus oxychloride (51 parts) and anhydrous magnesium chloride (0.6 parts) as a catalyst. The reaction and cleanup were carried out as in Example 1 (Example 3 herein), and the main ester fraction (89 wt% of the crude product) was distilled at 207-230° C. at 1 mm Hg. The product as in Example 1 (herein Example 3) required no further purification and had a viscosity of 58 cs at 25°C and a specific gravity of 1.123 (25°C/25°C).

Analysis of the mixed ester showed that it had the following composition (Table 3) (wt %). The wt% is based on the total weight of distilled phosphate ester. the

table 3

components wt% Triphenyl Phosphate 4 Mono-(isopropylphenyl)diphenyl phosphate 19 Bis-(isopropylphenyl)phenyl phosphate 52 Tris-(isopropylphenyl)phosphate 25 total 100

The mixed phosphate has a carbon number of 24 and contains 66 mol% cumyl groups. the

Example 5

Unless otherwise indicated, the reactants were added to the reactor under steady agitation, and the contents of the reactor were maintained under such agitation until recovery of the alkylated phenyl phosphate began. 150 g of the mixture described in Table 4 below (1.1 moles of active isopropylated phenol prepared by ortho-alkylation of phenol with propylene and _AlCl3 ) was fed into the reactor with 640 g (4.17 moles) _{of POCl3} and 1.5 g of tetrabutylammonium bromide were mixed. The mixture was heated to about 114°C with steady stirring and refluxed at this temperature until the evolution of HCl ceased, indicating the formation of an intermediate product. Excess POCl ₃ (95% of theory) was recovered from the intermediate product by first heating it to about 130° C. at atmospheric pressure and then heating it to 135° C. under 1 mmHg. Heating of the reactor contents was stopped, the reactor contents were allowed to cool, and 0.3 g MgCl ₂ and 188 g phenol (2.0 moles, 99.6%) were charged to the reactor.

After addition of _MgCl2 and phenol, the temperature of the reactor contents was raised to 110°C, and then the reaction mixture in the reactor was heated from about 110 to about 130°C under stirring over a period of about 3 hours. ³¹ P-NMR indicated complete conversion of the monoaryl dichlorophosphate, and an approximately 55/45 mixture of diaryl to triaryl intermediate and alkylated triaryl phosphate product.

An additional 0.9 g of _MgCl2 was then added to the reactor and the reaction proceeded for an additional 4 hours, during which time moderate HCl evolution was observed until HCl evolution ceased. After HCl evolution ceased, 12.00 g of neophenol (.13 mol, 99.6%) was charged to the reactor and the reaction was carried out at 130° C. with nitrogen sparging until completion (approximately 2 hours). The pressure was reduced to 10 mmHg and unreacted phenol was removed overhead at 130°C. The resulting alkylated triaryl phosphates were thus analyzed and found to have the characteristics summarized in Table 5 below. As indicated in this table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate.

Table 4

table 5

Example 6

Unless otherwise indicated, the reactants were added to the autoclave under steady agitation and the contents of the autoclave were maintained under such agitation until recovery of isopropylated phenol began. the

15和1200g(12.75摩尔)熔融的苯酚(Mallinckrodt，99.6％疏松结晶)装入2.0升Parr高压釜。封闭高压釜，用N₂吹扫并加热到110℃。使高压釜的顶部空间放空到大气压然后用10克丙烯进料冲洗。然后在90分钟的时期内将190g(4.5摩尔)丙烯送到高压釜中。如此进料以致在添加期间高压釜压力从80～30psig变化。反应温度从110到118℃保持额外的1小时，然后将高压釜内含物冷却到70℃。然后在(N₂正压力 通过浸入管)传输到压缩氮气吹洗过的储存瓶之前允许使高压釜内含物静置30分钟。  with 50 g dried

15 and 1200 g (12.75 moles) of molten phenol (Mallinckrodt, 99.6% loose crystalline) were charged to a 2.0 liter Parr autoclave. The autoclave was closed, purged with _N2 and heated to 110 °C. The headspace of the autoclave was vented to atmospheric pressure and flushed with 10 grams of propylene feed. Then 190 g (4.5 moles) of propylene were fed to the autoclave over a period of 90 minutes. 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, then the autoclave contents were cooled to 70°C. The autoclave contents were then allowed to sit for 30 minutes before being transferred ( _N2 positive pressure through a dip tube) to a compressed nitrogen-purged storage bottle.

A second 1000 g (10.6 moles) charge of molten phenol was charged to the IP's/Amberlyst 15 to the rear of the autoclave. The propylation reaction with 156 g (3.7 moles) of propylene was repeated. The reaction mixture was then decanted from the combined first and second molten phenol additions by partial distillation (1 atmosphere). The light ends (typically 93% phenol, 7% OIP) were returned to the autoclave with make-up phenol and repropylated. This decanting and distillation step was continued over 8 runs.

Distillation of the concentrated crude IP's at 1 atmosphere yielded 3300 g of material. Its analysis is reported in Table 5 below. The material was separated by distillation into a light fraction (2200 g, 93% phenol and 7% OIP), which was mixed with neophenol (2200 g) and subsequently used as the second step of alcohol production in Examples 7, 8 and 10-13 below Crude IPP. After recovery of unreacted phenol, a total of 2500 g of phenol had been reacted with 1200 g of propylene over 8 runs to produce 3300 g of IPs suitable for making low TPP IPP. This material is described in Table 6 and was used as the alkylated phenol in the first step in Examples 7-13 below. the

Table 6

components molecular weight Crude IPPP (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 steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated phenyl phosphate began. the

A sample of 475 g (3.34 moles of active isopropylated phenol) of the material described in Table 5 above was mixed with 795 g (5.19 moles) of _POCl3 and 3.56 grams (0.33 mole %) of tetrabutylammonium bromide. The mixture was heated to 114°C and refluxed at this temperature until HCl evolution slowed. The temperature was gradually increased to 135°C and held there until HCl evolution ceased. Excess _POCl3 was recovered in vacuo and stripped to an endpoint of 135°C and <1.0 mmHg.

After removal of excess _POCl3 was complete, the reactor was allowed to cool. The reactor was then charged with 3.26 g _MgCl2 (1.0 mole %) and heated to 110°C. From 110° C. to 135° C. with concomitant heating of the reactor contents over a period of 3 hours, 629.1 g (6.69 mol) of phenol (96.3 wt %) and 2-isopropanol were fed to the reactor. A mixture of base phenols (3.7 wt%) was reused to produce IP's final light ends as described above (Example 6). Within 1 hour after the end of the feed, ³¹ P-NMR analysis indicated complete conversion of monoaryl dichlorophosphates to triaryl phosphates. The pressure was reduced to 10 mmHg and unreacted phenol was partially removed overhead at 140°C.

The resulting alkylated triaryl phosphates were thus analyzed and found to have the characteristics summarized in Table 7 below. As indicated in the table, the normalized or relative weight percentages are based on the total weight of phenol and alkylated triaryl phosphate as indicated in the table. the

Table 7

Example 8

Unless otherwise indicated, the reactants were added to the reactor under steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated triaryl phosphate began. the

A 470 g sample of the material described in Table 5 was mixed in the reactor with 571 g (3.73 moles) of _POCl3 and 6.15 grams (0.58 mole %) of tetrabutylammonium bromide recycled from the previous example. The mixture was heated to 118°C and refluxed at this temperature until HCl evolution slowed. The temperature was gradually increased to 135°C and held at this temperature until the evolution of HCl ceased. Excess _POCl3 was recovered in vacuo and stripped to an endpoint of 135°C and <1.0 mmHg. The reactor was allowed to cool, then charged with 5.5 g _MgCl2 (1.75 mole %) and heated to 110 °C. Over a period of 3 hours, with concomitant gradual heating from 110°C to 135°C, the reactor was fed with 622.5 g (6.61 moles) of phenol/2-isopropylphenol comprising 96.3 wt% phenol and 3.7 wt% 2-isopropylphenol Propylphenol mixture.

Within 1 hour after the end of the phenol/2-isopropylphenol mixture feed, ³¹ P-NMR analysis indicated complete conversion of monoaryl dichlorophosphates to triaryl phosphates. The pressure of the reactor was reduced to 10 mmHg and unreacted phenol was partially removed overhead at 140°C. The alkylated triaryl phosphate was recovered from the reactor and analyzed and found to have the characteristics summarized in Table 8 below. As indicated in this table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate.

Table 8

Example 9

Unless otherwise indicated, the reactants were added to the reactor under steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated triaryl phosphate began. the

A 246 g sample of the material described in Table 5 above was mixed with 800 g (5.22 moles) of _POCl3 and 2.56 grams (0.46 mole %) of tetrabutylammonium bromide. The mixture was heated to 114°C and refluxed at this temperature until HCl evolution slowed. The temperature was gradually increased to 135°C and held at this temperature until the evolution of HCl ceased. Excess _POCl3 was recovered in vacuo and stripped to an endpoint of 135°C and <1.0 mmHg.

The reactor was allowed to cool then charged with 2.96 g _MgCl2 (1.8 mol%) and heated to 110°C. 622.5 g (6.61 moles) of phenol (99.6%) were fed to the reactor over a period of 3 hours while gradually and simultaneously increasing the temperature of the reactor contents from 110°C to 135°C. Within 1 hour after the end of the feed, P31 NMR analysis indicated complete conversion of the monoaryl dichlorophosphate to the triaryl phosphate. The pressure was lowered to 10 mmHg, and unreacted phenol was partially removed overhead at 140°C.

The alkylated triaryl phosphate was recovered from the reactor and analyzed and found to have the characteristics summarized in Table 9 below. As indicated in this table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate.

Table 9

Example 10

Unless otherwise indicated, the reactants were added to the reactor under steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated triaryl phosphate began. the

A sample of 462 g of the material described in Table 5 above was mixed with 1000 g (6.52 moles) of a 1:2 mixture of fresh and recycled POCl ₃ and 3.8 grams (1.23 mole %) of MgCl ₂ . The mixture was initially heated to 85°C, and evolution of HCl was evident at this temperature. The temperature of the mixture was gradually increased to 135°C and maintained at this temperature until the evolution of HCl ceased. Excess _POCl3 was recovered in vacuo and stripped to an endpoint of 135°C and 50 mmHg. Toluene (2 x 100 g) was charged (subsurface) to the heated reactor and the toluene was then stripped to final 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 were fed into the reactor, Simultaneously the temperature of the reactor contents was gradually increased from 110°C to 135°C over a period of 3 hours. Within 1 hour after the end of the phenol/2-isopropylphenol mixture feed, ³¹ P-NMR analysis indicated complete conversion of monoaryl dichlorophosphates to triaryl phosphates. The reactor pressure was reduced to 10 mmHg and unreacted phenol was removed overhead at 140°C.

The alkylated triaryl phosphate was recovered from the reactor and analyzed and found to have the characteristics summarized in Table 10 below. As indicated in the table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated phenyl phosphate.

Table 10

Example 11

Unless otherwise indicated, the reactants were added to the reactor under steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated triaryl phosphate began. the

A sample of 231.5 g (1.63 moles of active isopropylated phenol) of the material described in Table 5 above was mixed with a 1:2 mixture of fresh and recycled _POCl3 , 750 g (3.01 moles) and 2.6 grams (1.20 mole %) of AlCl ₃ mix. The mixture was initially heated to 80°C, and evolution of HCl was evident at this temperature. The temperature of the contents of the reactor was gradually increased to 135°C and maintained at this temperature until the evolution of HCl ceased.

Excess _POCl3 was recovered in vacuo and stripped to an endpoint of 135°C and 50 mmHg. Toluene (2 x 100 g) was then charged (subsurface) to the heated reactor and the toluene was then stripped to final conditions of 140°C and 50 mmHg. The contents of the reactor were cooled to 110° C., and then 305 g (3.25 moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol were fed into the reactor, Simultaneously the temperature of the reactor contents was gradually increased from 110°C to 135°C over a period of 3 hours. Foaming is a big problem during phenol feed. Within 1 hour after the end of the feed, ³¹ P-NMR analysis indicated complete conversion of monoaryl dichlorophosphates to triaryl phosphates. The pressure was reduced to 50 mmHg and unreacted phenol was partially removed overhead at 140°C.

The alkylated triaryl phosphate was recovered from the reactor and analyzed and found to have the characteristics summarized in Table 11 below. As indicated in this table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate.

Table 11

Example 12

Unless otherwise indicated, the reactants were added to the reactor under steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated triaryl phosphate began. the

A sample of 197.2 g (1.39 moles of active isopropylated phenol) of the material described in Table 5 above was mixed in a reactor with 640 g (4.17 moles) of _POCl3 and 4.0 grams (3.64 mole %) of pyridine (dried over molecular sieves). The mixture was heated to 114°C and refluxed at this temperature until HCl evolution slowed. The temperature was then gradually increased to 135°C as the POCl ₃ was distilled and held at this temperature until HCl evolution ceased. The remaining excess _POCl3 was recovered in vacuo and stripped to an endpoint of 135°C and 50 mmHg. During the stripping of POCl ₃ some pyridine-HCl was observed in the overhead and in the recycled POCl ₃ . Toluene (2 x 100 g) was charged (subsurface) to the heated reactor. The toluene was stripped to final conditions of 140°C and 50 mmHg. The contents of the reactor were cooled to 110° C., and then 278 g (2.78 moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol were fed into the reactor, Simultaneously the temperature of the reactor contents was gradually increased from 110°C to 135°C over a period of 3 hours. Within 1 hour after the end of the feed, ³¹ P-NMR analysis indicated complete conversion of monoaryl dichlorophosphates to triaryl phosphates. The pressure was reduced to 10 mmHg and unreacted phenol was removed overhead at 140°C.

The alkylated phenyl phosphate was recovered from the reactor and analyzed and found to have the characteristics summarized in Table 12 below. As indicated in this table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate.

Table 12

Example 13

Unless otherwise indicated, the reactants were added to the reactor under steady agitation and the contents of the reactor were maintained under such agitation until recovery of the alkylated triaryl phosphate began. the

A fully jacketed 2000 ml dry round bottom flask was used as the reactor in this example. It is fitted with overhead stirrer, thermometer, oil jacketed addition funnel and high efficiency condenser/takeoffhead. Reactor through Drierite The column is evacuated to a caustic scrubber. 1100 g (7.17 moles) of _POCl3 (consisting of a 2:1 mixture of recycled and fresh _POCl3 ), 530 g (3.74 moles of active IPPs) were composed of 59.48 wt% OIP, 29.76 wt% PIP, 5.83 wt% 2,4 - An isopropylated phenol mixture consisting of DIP and 6.0 g (2 mole % relative to the active IPP charged) of pyridine was charged to the reactor. The contents of the reactor were heated to 113°C (oil jacket temperature 124°C). HCl evolution was initiated at 80°C and became more pronounced at 105°C. HCl evolution slowed after 90 minutes at 113°C. The jacket temperature was raised to 135°C, and the kettle temperature reached 127°C within an additional 60 minutes, HCl evolution essentially ended, and the separated pyridine·HCl was suspended in the reaction mixture as an oil (the resulting turbidity appeared to be a reaction good visual indicator of the endpoint).

The reactor jacket temperature was raised to 145 °C and the valve on the production head was opened to the receiver, then _POCl3 was collected for recirculation. Distillation of _POCl3 was facilitated with a slow nitrogen purge through the reactor headspace. Once the kettle temperature reached 135°C and POCl ₃ distillation slowed down, the reactor pressure was gradually reduced (maximum vacuum 50 mmHg) until the theoretical amount of POCl ₃ was collected (thus recovering 495 g, [95% of theory] POCl ₃ ). Pyridine·HCl was formed overhead during the distillation, but did not cause operational problems. The last traces of _POCl3 were removed by addition and stripping with 300ml of toluene (final conditions 135°C 50mmHg). An aliquot was removed for analysis; ³¹ P-NMR analysis indicated a relative ratio of ArOCl ₂ PO:(ArO) ₂ ClPO of 97.4:2.6 and confirmed complete removal of POCl ₃ .

Then 3.5 g (0.98 mol% with respect to IPPs) _{of MgCl2} was charged into the reactor and kept under nitrogen flow at 140 °C for 1 hr. A second aliquot was removed for analysis, which was shown by ³¹ P-NMR to have a relative ratio of ArOCl ₂ PO:(ArO) ₂ ClPO of 97.2:2.8. Phenol (706 g, 96.3 wt% phenol, 3.7 wt% 2-isopropylphenol, 7.4 moles of phenol in total) was then charged to the oil-jacketed addition funnel and gradually fed into the reactor over a period of 75 minutes. During this addition, HCl evolution was very violent. The reaction appeared to be complete after a total reaction time of 170 minutes. The conversion measured by ³¹ P-NMR was 99.3%. An additional 23 g of the phenol mixture as described above was fed. After an additional 30 minutes, the almost colorless clear mixture (density = 1.09, 1370 g total reaction mass, theoretical 1378 g) was transferred to a wash tank.

After the almost colorless and transparent mixture was charged to the wash tank, 350 g of Na ₂ CO ₃ /HNa ₂ PO ₄ solution (pH=9 density=1.15) was charged to the wash tank. The contents of the wash tank were then stirred at 88°C for 5 minutes and then clarified for a period of 20 minutes. The bottom milky (suspended MgCO ₃ ) aqueous layer (226 g, pH=7.5-8.0) was removed from the wash kettle and washed with a second aliquot of Na ₂ CO ₃ /HNa ₂ PO ₄ solution (90° C., 200 g) Obtain crude IPPP for an additional 5 min. The secondary phase was removed from the bottom of the reactor yielding 195 g of a less turbid but still milky aqueous solution at pH 10. Then 530 g of diluted H ₃ PO ₄ solution (0.56 wt% H ₃ PO ₄ based on solution) was charged to the reactor, and the bottom cloudy product layer (1357 g) was collected. The aqueous phase (pH = 3.5, 610 g) was removed and the product layer was placed in a reactor and the water was removed by bubbling nitrogen at 95°C to yield 1335 g of the alkylated phenyl phosphate. The alkylated triaryl phosphate was recovered from the reactor and analyzed and found to have the characteristics summarized in Table 13 below. As indicated in the table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated phenyl phosphate.

Table 13

Example 14

The crude alkylated triaryl phosphates recovered from Examples 7-12 were mixed and washed in the same manner with Na ₂ CO ₃ /HNa ₂ PO ₄ having the concentration described in Example 13 above. This material was then mixed with the crude product from Example 13. The whole mixture was then distilled under reduced pressure (<2mmHg) nitrogen atmosphere. During the distillation, the "first run" (6% by weight of the total mixture, based on the mixture) was collected between 180-218°C. A "product fraction" (92 wt% of the total mixture based on the mixture) was collected between 118.5-235°C. The undistilled residue is the last 2% by weight of the total mass of the mixture, based on the mixture. The forerunt was analyzed by HPLC and 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 phosphate, 0.2 wt% diisopropylated triaryl phosphate and 0.02 wt% triisopropylated triaryl phosphate. The product fractions were also analyzed for purity and physical properties; the results appear in Table 14 below. All weight percentages are absolute and based on the total mass of analyte.

Table 14

analyze flash product HPLC Wt% Triphenyl Phosphate 0.71 Cumyl phenyl diphenyl phosphate 87.21 Diisopropylated Triaryl Phosphate 11.44 Triisopropylated Triaryl Phosphate 0.64 acid value 0.11mg KOH/g APHA Chromaticity 28.00 Density(20℃) 1.1689g/ml Flashpoint (Cleveland Open Cup) 222°C moisture 19.2ppm Wt% Phosphorus (NMR) 8.34 [Al] <0.11ppm [Mg] <0.0018ppm [Na] <0.6ppm Kinematic viscosity (25℃) 52.91 cSt

Thus, as described in Table 14, on average, our products were 10% higher in phosphorus than those prepared in the comparative examples above, and were also 10% less viscous than the products of the comparative examples. the

Example 15

The 5 liter reactor was equipped with addition funnel, hot wall and distillation equipment. Distillation equipment through Drierite The column is evacuated to a caustic scrubber. The reactor was purged with _N2 and charged with 3886 g (25.34 mol) of recycled _POCl3 and 6.37 g (0.53 mol%) of _MgCl2 . The contents of the reactor were heated to 85°C. A redistilled 67:1:32 mixture of OIP (Aldrich), MIP (Aldrich) and PIP (Aldrich) (1725 g, 12.67 moles) was fed to the reactor over a period of 3 hours. The reaction temperature was gradually increased to 130°C during the feed. After a total reaction time of 4 hours, distillation of _POCl3 was started. The reactor pressure was gradually reduced as the POCl ₃ distillation rate decreased. Distillation was continued to final conditions of 140 °C and 50 mmHg. Toluene (2 x 250ml) was then charged and stripped at 140°C (50mmHg). Phosphorus NMR of the stripped reaction mixture confirmed complete removal of POCl ₃ and indicated a relative ratio of ArOPOCl ₂ :(ArO) ₂ POCl of 100:4.2.

The contents of the reactor were cooled to 130°C. 2362 g (25.1 moles) of molten phenol (99.6%) were fed to the reactor over a period of 5 hours. The reaction temperature was raised to 150°C near the end of the feed. Phosphorus NMR analysis of the reactor contents confirmed completion of the reaction within 1 hour of the end of the feed. The contents of the reactor, 4547 g, were transferred to a 5 liter storage bottle by means of N2. The HPLC analysis is summarized below. As indicated in Table 15 below, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate. the

Table 15

A 5 _liter glycol jacketed baffled reactor was charged with 500 g of 11% aqueous _Na2CO3 and 2065 g of the alkylated triaryl phosphates of Table 13. The mixture was stirred briefly at 85-92°C and then left to separate the phases. The bottom aqueous layer was removed along with a moderately dense layer of clarified debris. The washing step was repeated through 4 washes. To completely remove the suspended debris layer mainly comprising sodium and magnesium phenoxides, 2000 ml of toluene were added. The IPP/toluene mixture was then washed with tap water (2 x 500ml).

Into the same 5 liter ethylene glycol jacketed baffled reactor was charged 540 g of 4% aqueous NaOH, 2478 g of the crude mixture and 1750 g of toluene. The mixture was stirred briefly at 45-50°C and then heated to 65°C without stirring. The resulting bottom aqueous layer was removed along with suspended Mg(OH) ₂ suspended therein. A second wash was performed at 65°C with 608 g of 1% NaOH. The product mixture was then washed with 532 g of tap water at 85° C. (pH of the resulting aqueous fraction = 10). The IPP/toluene mixture was contaminated with a microsuspension of trace Mg(OH) ₂ . This contamination was removed by washing with 514 g 0.7% _H3PO4 at 90°C (resulting aqueous fraction _pH = 3.5). A final 212 g tap water wash (90°C) gave an aqueous phase with pH = 4.5.

The washed and stripped crude IPP from the two separation check steps above were combined. The mixture was heated to 180°C and sparged with nitrogen to remove traces of toluene, moisture and phenol. An analytical sample (500 g) was removed for the analysis reported in Table 16 below. The remainder of the material was mixed with the product from Example 16 and then flashed at 1 mmHg and 220-240°C (see Example 17 for final product analysis). All weight percentages are absolute and based on the total mass of analyte (indicated in the table). the

Table 16

analyze flash product HPLC Wt% phenol 0.81 Triphenyl Phosphate 0.15 Cumyl phenyl diphenyl phosphate 94.1 Diisopropylated Triaryl Phosphate 4.58 Triisopropylated Triaryl Phosphate 0.45 acid value 0.45mg KOH/g APHA Chromaticity 149.00 Density(20℃) 1.1725g/ml Flashpoint (Cleveland Open Cup) 229°C moisture 46ppm Wt% Phosphorus (NMR) 8.40 [Al] <2.0ppm [Mg] <0.90ppm [Na] 1.2ppm Kinematic viscosity (25℃) 47.81 cSt

Embodiment 16

塔排空到碱洗气器。用N₂吹扫该反应器并装入3385g(22.08摩尔)再循环的POCl₃和8.90g(0.85摩尔％)MgCl₂。将反应器的内含物加热到85℃。经3小时的时间将OIP(Aldrich)、PIP(Aldrich)和MIP(Aldrich)的67∶32∶1混合物(1503.3g，11.04摩尔)送到反应器中。在进料期间逐渐将反应温度升高到130℃。4小时的总反应时间之后，开始POCl₃的蒸镏。当POCl₃蒸镏速率降低时逐渐降低反应器压力。将蒸镏持续到150℃和50mmHg的最终条件。然后装入甲苯(2×250ml)并在150℃(50mmHg)下汽提。汽提的反应混合物的磷NMR证实了POCl₃的完全脱除并表明ArOPOCl₂∶(ArO)₂POCl的相对比是100∶4。  The 5 liter reactor was equipped with addition funnel, hot wall and distillation equipment. Distillation equipment through Drierite

The column is evacuated to a caustic scrubber. The reactor was purged with _N2 and charged with 3385 g (22.08 moles) of recycled _POCl3 and 8.90 g (0.85 mole %) _{of MgCl2} . The contents of the reactor were heated to 85°C. A 67:32:1 mixture of OIP (Aldrich), PIP (Aldrich) and MIP (Aldrich) (1503.3 g, 11.04 moles) was fed to the reactor over a period of 3 hours. The reaction temperature was gradually increased to 130°C during the feed. After a total reaction time of 4 hours, the distillation of _POCl3 was started. The reactor pressure was gradually reduced as the POCl ₃ distillation rate decreased. Distillation was continued to final conditions of 150 °C and 50 mmHg. Toluene (2 x 250ml) was then charged and stripped at 150°C (50mmHg). Phosphorus NMR of the stripped reaction mixture confirmed complete removal of _POCl3 and showed a relative ratio of _ArOPOCl2 :(ArO) _2POCl of 100:4.

The contents of the reactor were cooled to 130°C. 1984.97 g (20.75 moles) of molten phenol (99.6%) were fed to the reactor over a period of 5 hours. The reaction temperature was raised to 150°C near the end of the feed. Phosphorus NMR analysis of the reactor contents confirmed completion of the reaction within 1 hour of the end of the feed. The contents of the reactor, 3847 g, were transferred to a 5 liter storage bottle by means of _N2 . The HPLC analysis of the contents is in Table 17 below. As indicated in this table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated triaryl phosphate.

Table 17

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 mixture of Table 15. The mixture was briefly stirred at from 85 to 92°C and then left to separate the phases. The bottom aqueous layer was removed along with a moderate density cloudy debris layer. The organic layer was washed (2 x 1000 g) with 2% aqueous NaOH at 85°C, followed by tap water (4 x 800 g) until a neutral pH wash was obtained. The above procedure was repeated with the remainder of the starting material (1897 g). The washed crude mixture was combined and transferred to a third reactor where toluene and moisture were removed in vacuo, final conditions were 180°C and 1 mmHg. The analyzed samples were found to have the properties listed in Table 18 below. All weight percentages are absolute and based on the total mass of analyte. The remainder of the material remaining after analysis was mixed with the product from Example 15 and then flashed at 1 mmHg and 220-240°C (see Example 17 for final product analysis). the

Table 18

analyze Strip crude product HPLC Wt% phenol 407ppm Triphenyl Phosphate 0.16wt% Cumyl phenyl diphenyl phosphate 94.6wt% Diisopropylated Triaryl Phosphate 4.6wt% Triisopropylated Triaryl Phosphate 0.01wt% acid value 0.05mg KOH/g APHA Chromaticity 221 Wt% Phosphorus (NMR) 8.32 [Al] <3.6ppm [Mg] 1.41ppm [Na] 1.68ppm

Example 17

The stripped crude mixtures from Examples 15 and 16 were combined and flashed under vacuum from 220 to 240°C and <1 mmHg. The product thus obtained had the properties listed in Table 19 below. All weight percentages are absolute and based on the total mass of analytes in the table.

Table 19

analyze flash product HPLC Wt% phenol 200ppm Triphenyl Phosphate 0.17 Cumyl phenyl diphenyl phosphate 94.93 Diisopropylated Triaryl Phosphate 4.87 Triisopropylated Triaryl Phosphate 0.02 acid value 0.03mg KOH/g APHA Chromaticity 27.00 Density(20℃) 1.1729g/ml Flashpoint (Cleveland Open Cup) 236°C moisture 24ppm Wt% Phosphorus (NMR) 8.36 [Al] <0.1ppm [Mg] <0.06ppm [Na] <0.56ppm Kinematic viscosity (25℃) 48.74 cSt

Example 18

The 5 liter reactor was equipped with addition funnel, hot wall and distillation equipment. Distillation equipment through Drierite The column is evacuated to a caustic scrubber. The reactor was purged with N2 and charged with 900.00 g (5.88 mol) of recycled POCl3, 21.0 g (3.94 mol%) of dry pyridine and double-distilled OIP (Aldrich), PIP (Aldrich) and MIP (Aldrich) 67:32:1 mixture 916.1 g (6.73 moles). The stirred contents of the reactor were heated to a temperature of 114°C, the temperature at which HCl evolution first begins. The reaction temperature was gradually increased to 130°C during 7 hours. After a total reaction time of 8 hours, a sample was removed and analyzed by phosphorus NMR, indicating that the relative ratio of _ArOPOCl2 :(ArO) _2POCl was 93.6:18.5.

The contents of the reactor were allowed to stand overnight and then reheated to 130°C with stirring. 996.46 g (10.59 moles) of molten phenol (99.6%) were fed to the reactor over a period of 5 hours. The reaction temperature was raised to 170°C near the end of the feed. Phosphorus NMR analysis of the reactor contents confirmed completion of the reaction within 3 hours after the end of the feed. The contents of the reactor, 2055 g, were transferred to a 5 liter storage bottle by means of _N2 . HPLC analysis showed it to have the properties listed in Table 20 below. As indicated in the table, normalized or relative weight percentages are based on the combined weight of phenol and alkylated phenyl phosphate.

Table 20

A 5 liter ethylene glycol jacketed baffled reactor was charged with 650 g of tap water, 1750 ml of toluene and 2055 g of the crude mixture. The mixture was briefly stirred at from 85 to 92°C and then left to separate the phases. The bottom aqueous layer was removed along with a moderate density cloudy debris layer. The organic layer was washed (2 x 1000 g) with 2% aqueous NaOH at 85°C, then tap water (4 x 800 g) until a neutral pH wash was obtained. The washed crude mixture was then transferred to a third reactor where toluene, moisture and phenol were removed in vacuo, final conditions 180°C and 1 mmHg. Analytical samples were removed and characterized. The results are reported in Table 21 below. All weight percentages are absolute and based on the total mass of analytes in the table. the

Table 21

analyze flash product HPLC Wt% phenol 0.07 Triphenyl Phosphate 0.14 Cumyl phenyl diphenyl phosphate 72.2 Diisopropylated Triaryl Phosphate 27.0 Triisopropylated Triaryl Phosphate 0.61 acid value 0.01mg KOH/g APHA Chromaticity 92 Wt% Phosphorus (NMR) 8.1%

The rest of the reactor contents were flashed at 1 mmHg and 220-240°C. The product thus obtained was analyzed and found to exhibit the properties listed in Table 22 below. All weight percentages are absolute and based on the total mass of analyte in the table. the

Table 22

analyze flash product HPLC Wt% phenol <100ppm Triphenyl Phosphate 0.14 Cumyl phenyl diphenyl phosphate 72.16 Diisopropylated Triaryl Phosphate 27.10 Triisopropylated Triaryl Phosphate 0.61 acid value <0.01mg KOH/g APHA Chromaticity 35 Density(20℃) 1.1631 Wt% Phosphorus (NMR) 8.22% Kinematic viscosity (25℃) 55.80cSt

Example 18

Several test formulations were prepared by mixing the stated amounts of materials listed below. Each formulation was prepared by mixing the components in a #5 Brabender cup at 160-165°C and compression molding at 165°C into test specimens of appropriate thickness. ASTM Type IV Tensile Bars are die cut from extruded sheet at 1/16" thickness. All formulations are based on 75 Shore Type A hardness, 60°C flexible PVC formulation. Resin molecular weight is suitable for thick wall injection molding or thin wall Wall profile or wire extrusion or film. Each test in this paper contains the following:

Amount of components in recipe:

Flame retardant evaluation:

519  TS-06-9A-

519

TS-06-9B-Chemtura Reofos

TS-06-9C- ^SuprestaTM Phosflex31L

TS-06-9D-flame retardant according to the invention

TS-06-9E-flame retardant according to the invention

TS-06-9F-flame retardant according to the invention

Table 23 - Mechanical, Electrical and Compatibility Results of Shore A Flexible PVC

Claims (8)

1. A method for the manufacture of alkylated triaryl phosphates, comprising: a) in the presence of a first catalyst, an alkylated phenol stream comprising less than 1 mole % phenol and up to 25 mole % dialkylphenol is combined with POCl reaction, both based on the total weight of the alkylated phenol, thereby producing a first _reaction product comprising greater than 75 mole percent monoalkylated phenyl dichlorophosphate, the molar amount based on the first reaction product In terms of total moles; from said first reaction product, excess POCl ₃ is removed such that the amount of POCl ₃ based on the total amount of phosphorus in the first reaction product is less than 1 mole %, and wherein, i) In the presence of a second catalyst, according to the second reaction conditions including the temperature range of 90°C to 260°C, the first reaction product is mixed with an alcohol selected from the group consisting of aryl alcohol, alkyl alcohol, alkylated aryl alcohol and mixtures thereof Alcohol reaction, thereby producing alkylated triaryl phosphates; or ii) In the presence of a second catalyst, according to the second reaction conditions including a temperature range of 70°C to 260°C, the first reaction product is sequentially mixed with an alcohol selected from aryl alcohol, alkyl alcohol, alkylated aryl alcohol and The reaction of various alcohols of their mixtures, thereby producing alkylated triaryl phosphates; or iii) reacting the first reaction product with a first alcohol, thereby producing a partially reacted product, and then reacting the partially reacted product with a second alcohol, wherein, until it is determined by means of ^P NMR that the first alcohol has When exhausted, a second alcohol is added, wherein the first alcohol and the second alcohol are independently selected from aryl alcohols, alkyl alcohols, alkylated aryl alcohols. 2. The method according to claim 1, wherein the alkyl portion of the alkylated phenol is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, tert-amyl, cyclohexylalkyl moieties, isopropylalkyl, and combinations thereof. 3. The method of claim 1, wherein the alkyl moiety of the alkylated phenol is an isopropyl alkyl moiety. 4. The process according to claim 1, wherein the alkylated phenol stream comprises OIP in the range of 64 to 68 wt%, MIP in the range of 0.5 to 2.5 wt%, and PIP in the range of 31 to 35 wt%, all based on alkyl based on the total weight of the phenols. the 5. The method according to claim 1 , wherein the first reaction product comprises monoalkylated phenyl in the range of 70 to 99.9 mole % based on the total molar amount of the first reaction product other than unreacted _POCl Dichlorophosphates and bis(monoalkylated)phenyl chlorophosphates ranging from 0.1 mole % but less than 30 mole %. 6. The method according to claim 1, wherein said method further comprises: a) Adding an additional amount of an alcohol selected from monoisopropylated phenol, diisopropylated phenol, phenol and mixtures thereof to the alkylated aryl phosphate, and/or to the alkylated triaryl phosphate adding an additional amount of the second catalyst, thereby producing an alcohol-rich alkylated phenylphosphate product comprising excess alcohol; b) recovering said alcohol-rich alkylated phenylphosphate product; and c) removing at least a portion of excess alcohol from the alcohol-rich alkylated phenylphosphate product; Therein, excess alcohol is removed by a method selected from phase separation, stripping, distillation and combinations thereof. 7. The method according to claim 1, wherein the method further comprises i) dividing the first alcohol into first and second portions; ii) reacting the first reaction product with the first portion of the first alcohol until passing The method of ^P31 NMR confirms that the first part of the first alcohol is substantially completely consumed; the second part of the first alcohol is added; the product from ii) is reacted with the second part of the first alcohol until the method of ^P31 NMR determining that the second portion of the first alcohol is substantially completely consumed, thereby producing a first intermediate reaction product comprising at least an aryl dichlorophosphate and a chlorodiaryl phosphate; iii) combining the first intermediate reaction product with an effective The amount of the second alcohol reacts. 8. The method according to claim 7, wherein said effective amount of the second alcohol is obtained after converting substantially all of the aryl dichlorophosphates and chlorodiarylphosphates to the alkylated triaryl phosphates according to the present invention. The amount of secondary alcohol that is effective in terms of phosphate ester. the