MXPA99007510A - Process for making and using bisaryl diphosphates - Google Patents

Abstract

Flame retardancy is provided to polymer resins by adding to the resin a bisaryl diphosphate that has not been purified to remove catalyst or catalyst residue from the product. The bisaryl diphosphate may be prepared by a two-step process that starts with the semi-continuous addition of dry bisphenol A to a heated mixture of phosphorous oxychloride and MgCl, and concludes with the addition of dry phenol to the step one intermediate.

Description

PROCESS FOR THE PREPARATION AND USE OF BISARYL DIFFOSPHATES Field of the invention The present invention is generally concerned with the manufacture and use of bisaryl diphosphates and more particularly with an improved process for making and using bisphenol A bis (diphenyl) phosphate. without purification.

BACKGROUND OF THE INVENTION Bisaryl diphosphates such as bisphenol A bis (diphenyl) phosphate can be effective flame retardants for polymer resins. For example, high impact ("PPO / HIPS") and polycarbonate / acrylonitrile-butadiene-styrene ("PC / ABS") blends or mixtures of polyphenylene oxide / high impact polystyrene ("PC / ABS") can be improved with bisaryl diphosphate flame retardants. Due to its commercial utility several processes have been developed for the manufacture of bisaryl diphosphates. For example, it is known that bisphenol A bis (diphenyl) phosphate can be obtained by catalytically reacting a phosphorus oxyhalide with bisphenol A and then reacting the intermediate with phenol. The processes of the prior art for making and using bisaryl diphosphates include one or more steps to remove the catalyst from diphosphate. "The most common method used for catalytic removal has been by REF .: 31111 aqueous wash leading to emulsions with the However, the waste water must be generally separated before use as a flame retardant The processes of the prior art for making and using bisaryl diphosphates also describe that the triaryl phosphate content of the final products must be reduced. Thus, the prior art processes normally employed a non-reactive solvent to reduce the triaryl phosphates In view of the above it can be seen that there is a need for improved methods of flame retardant polymer resins with bisaryl diphosphate compounds. Deal with that need.

BRIEF DESCRIPTION OF THE INVENTION In briefly describing an aspect of the present invention, there is provided a method for effectively and economically developing flame retardant polymer resins by adding to the polymeric resin a catalytically synthesized bisaryl diphosphate that has not been purified to remove the catalyst. of the product, in such a way that the synthesized bisaryl diphosphate provided to the resin contains the catalyst (or the catalyst residue) used to make the bisaryl diphosphate.

In another aspect of the invention, the flame retardant polymer resins referred to above are made by using a bisaryl diphosphate which is the product of a process in which a dihydric aromatic compound (such as bisphenol A) is added in a manner semicontinuous to the heated catalyst / phosphorus oxyhalide mixture (such as a mixture of phosphorus oxychloride and MgCl) for a period of 0.5 hours to 12.0 hours. Then the resulting intermediate is reacted with an alcohol (such as phenol) to form the desired bisaryl diphosphate. Another aspect of the present invention provides flame retardant polymer resins by using bisaryl diphosphates prepared by using other process limitations. In one method the aromatic dihydric compound (for example bisphenol A) contains less than about 200 ppm of water. In another method the alcohol (for example phenol) contains less than about 300 ppm of water. It is an object of the present invention to provide improved methods of flame retardant polymer resins. Another object of the present invention is to provide new polymeric resins that have become flame retardant at minimal cost. Still another object of the present invention is to provide improved methods of manufacturing bisaryl diphosphate compounds for use as flame retardants in polymer resins. Objects and related advantages of the present invention will become apparent from the following description.

Description of the preferred embodiment For the purposes of promoting an understanding of the principles of the invention, reference will now be made to specific modalities and specific language will be used to describe them. However, it will be understood that no limitation of the scope of the invention is proposed, such alterations and further modifications to the illustrated device, and such further applications of the principles of the invention as illustrated herein are contemplated as it is normally intended. would present to the skilled in the art with which the invention is concerned. As indicated above, one aspect of the present invention provides a method for making flame retardant polymer resins by combining or mixing a bisaryl diphosphate catalytically prepared to a polymeric resin without separating the catalyst (or catalyst residue) from the bisaryl diphosphate. Surprisingly, polymer resins that have become flame retardant in this manner possess characteristics that compare favorably with those of resins made with bisaryl diphosphates only after separating the catalyst from the bisaryl diphosphate. While it was expected that the catalytic MgCl 2 residue would cause problems with PC / ABS stability, it was found that the resin formulated with the bisaryl diphosphate and the remaining catalyst were stable. With respect to the polymeric resins that can be used in the present invention, the bisaryl diphosphate / catalyst mixture can be used as a flame retardant in a wide variety of polymer resins. Preferred polymeric resins include polyphenylene oxide (PPO), high impact polystyrene (HIPS), polycarbonate (PC), polyurethane (PU), polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene (ABS) and polybutylene terephthalate ( PBT) but a wide range of other polymer resins can also be used. Combinations or mixtures of these and other resins, such as blends or blends of polyphenylene oxide / high impact polystyrene (PPO / HIPS) and blends or polycarbonate / acrylonitrile-butadiene-styrene blends (PC / ABS) are also they can make and use advantageously. The flame retardant can be added in the range of 5-30%, preferably 10-20%.

As for the bisaryl diphosphate / catalyst mixtures which are formulated to the polymer resins, in the preferred embodiments, the bisaryl diphosphate is made by the two-step process illustrated below.

Step 1 1. A phosphorus oxyhalide is reacted with an aromatic dihydric compound in the presence of a catalyst. The aromatic dihydric compound is preferably added in a semicontinuous manner to a heated mixture of phosphorus oxyhalide and catalyst in a period of 0.5 hours to 12 hours. 2. The reaction mixture is heated to reflux temperatures in order to release the by-product hydrogen chloride gas and convert the aromatic dihydric compound to the corresponding diphosphorotetrachloridate. 3. Phosphorus oxyhalide that did not react is separated by distillation under reduced pressure to leave the intermediate product of stage 1.

Step 2 1. The crude intermediate of step 1 is reacted with an alcohol to form the desired flame retardant product. 2. The reaction is heated to sufficient temperatures to convert the intermediate to the product. 3. A bubbling of subsurface nitrogen is introduced to separate the byproduct of hydrogen chloride. 4. Excess alcohol is separated by distillation under reduced pressure if necessary. The product is used without any additional purification. As for the components used in the preferred embodiments, the phosphorus oxyhalide is of the formula P0X3, wherein X is bromine or chlorine. The most preferred phosphorus oxyhalide is phosphorus oxychloride, although phosphorus oxybromide can be used. As for the aromatic dihydric compound used in the first stage of the process, preferred dihydric aromatic compounds include resorcinol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, bisphenol methane, bisphenols and other substituted dihydric aromatic compounds. It is preferred that there be no more than one ortho substituent for each hydroxyl group on the aromatic dihydric compound. The most preferred dihydric aromatic compound is bisphenol A. The proportion of the oxyhalide e phosphorus to the dihydric compound is used to control the degree of polymerization in the final product. The preferred range is between one-half to five moles of phosphorus oxyhalide per mole of the dihydric compound, although proportions outside this range can be used. The preferred rank is only representative of the process in its preferred modalities. Preferred catalysts promote the reaction and are soluble in the final product, although insoluble catalysts can be used. Many of the preferred catalysts are metal halide salts, but other types of compounds can also be used to catalyze the reaction. Examples of preferred catalysts include aluminum chloride, magnesium chloride, calcium chloride, zinc chloride and titanium tetrachloride. The most preferred catalyst for use in this invention is magnesium chloride. The amount of catalyst needed in the reaction is in the range of 0.01 - 2.0% by weight based on the weight of the aromatic dihydric compound. The most preferred range is 0.1-0.75% by weight. It will be appreciated that the heat is maintained in the reaction mixture until the aromatic dihydric compound has essentially been converted to the diphosphorotetrachloridate. This normally requires aging periods of 1-3 hours, depending on the particular dihydric compound chosen. After the reaction is complete, the excess phosphorus oxyhalide can be separated by distillation. The distillation can be at reduced pressure or at atmospheric pressure when using elevated temperatures. Preferably, the phosphorus oxyhalide is separated under reduced pressure and elevated temperatures. More preferably, the pressure is less than 20 torricellis and the temperature is between 150 and 180 ° C. As for the alcohol used in the second stage of the process, any alcohol can be used. Preferred alcohols are aromatic alcohols, although aliphatic alcohols can also be used - either alone or in combination with an aromatic alcohol. Preferred alcohols for use in the invention include ortho-cresol, meta-cresol, para-cresol, xylene, phenol, halo-phenols and other substituted phenols. It is preferred that there be no more than one ortho substituent for each hydroxyl group on an aromatic alcohol. The most preferred alcohols are monohydric aromatic alcohols, more preferably phenol. The proportion of alcohol to the diphosphorotetrachloridate intermediate is preferably at least 4 moles per mole based on the stoichiometry of the reaction.

Excesses of up to 10% are desirable to increase the reaction rate and to take into account the loss of the aromatic compound from the reactor. The preferred range is an excess of 1 - 3% more than the previous stoichiometric requirements. The alcohol is preferably added to the hot mixture of the first stage in a semi-continuous manner. The compound is added in the course of 0.5 to 12 hours. The reaction is carried out at a temperature such that the alcohol reacts with the intermediate of step 1. The temperature varies according to the substituents in the alcohol and the aromatic dihydric compound of the first stage. When the reaction components are bisphenol A, phosphorus oxychloride and phenol, the preferred temperature range for the reaction of the intermediate of step 1 is 140-240 ° C, the most preferable range is 150-180 ° C. The reaction temperature can be maintained constant after the alcohol addition or can be increased to increase the reaction rate. After essentially all of the intermediate of step 1 has been converted to the final product, the excess alcohol is distilled from the mixture, preferably under reduced pressure. The temperature, pressure and other reaction conditions for the distillation depend on the aromatic dihydric compound and the alcohol used, but when the reaction components are bisphenol A and phenol, the most preferred method is distillation in a falling film evaporator or rubbing film. when using absolute pressures of less than 10 torricellis and temperatures of 165 -220 ° C. Alternatively, the present invention can be implemented in a process for the preparation of a bisaryl diphosphate as described below: 1. A phosphoryl compound of formula (R0) 2P0X, wherein X is bromine or chlorine and R is aromatic or aliphatic is reacted with approximately 0.5 molar amount of a dihydric aromatic compound in the presence of an appropriate catalyst. 2. The reaction mixture is heated to promote the reaction and release the secondary product of hydrogen chloride gas. A bubbling of nitrogen can be introduced into the reaction to improve the evolution of hydrogen chloride. 3. The resulting product is distilled under reduced pressure to remove any volatile component. The product is used without further purification. In this alternative embodiment, the aliphatic / aromatic group in the phosphoryl compound (the "R" group in the above formula) is derived from the reaction of an alcohol with a phosphorus oxyhalide. The appropriate alcohols are identical to those listed above. The aromatic dihydric compound is also selected from those listed above. Also in the alternative embodiment, the aromatic dihydric compound is added to the hot phosphoryl compound in the temperature range of 100-240 ° C. Typical addition times range from 0.5 to 12 hours. When the reaction is complete any volatile compounds are separated by distillation under reduced pressure in a rubbing film evaporator or falling film in the temperature range of 165-220 ° C. In the most preferred aspect of the present invention, the bisaryl diphosphate used to return flame retardant to the polymeric resin is the product of a specific process for catalytically preparing bisaryl diphosphates. The process includes the semicontinuous addition of the aromatic dihydric compound to the phosphorus oxyhalide to reduce the content of triaryl phosphate, the semicontinuous addition consists of the addition of the aromatic dihydric compound to the heated mixture of catalyst / phosphorus oxyhalide in a period of 0.5 hours at 12.0 o'clock. The resulting product is then reacted with an alcohol to form the desired bisaryl diphosphate. The semicontinuous addition of the aromatic dihydric compound reduces the decomposition of this compound, particularly in the case of bisphenol A. Accordingly, the intermediate product of stage 1 contains less decomposition products. Since these decomposition products are converted to triaryl phosphates in the second reaction, the use of semicontinuous addition is effective to minimize the content of triaryl phosphate in the final product. This is especially true when bisphenol A is used as the aromatic dihydric compound. In another preferred aspect of the present invention, the bisaryl diphosphate used to return flame retardant to the polymeric resin is the product of a process for catalytically preparing bisaryl diphosphates in which a dry dihydric aromatic compound (for example dry BPA) is used. More preferably, the aromatic dihydric compound has a moisture content of <; 200 ppm of water. By using this technique it is possible to produce a supply of aryl diphosphate esters in which the monomer content is increased from about 60% to about 80%. This improves the physical properties of the formulated polymer, which includes melt flow, impact resistance and flame retardancy. In another preferred aspect of the present invention, the bisaryl diphosphate used to make the polymeric resin flame retardant is the product of a process for catalytically preparing bisaryl diphosphates in which an anhydrous alcohol (eg, anhydrous phenol) is used. More preferably, phenol has a moisture content of < 300 ppm. The effect of "excess water is an increase in the acidity of the final product that causes hydrolytic instability when formulated in PC / ABS.The effect of water on phenol is thus different than the effect of water on BPA. In the above discussion of the importance of keeping water out of BPA and phenol, it must also be recognized that it is also important to keep water out of P0C 13. It is known in the art that P0C13 reacts with water to form undesirable products, such as show below.

POCI3 + H2O || + HCl CI2POH O O || + POCÍ3 ll II + HCI CI2POH CI2POPCÍ2 Acid Dimer of P0C13 Accordingly, water is essentially eliminated from P0C13 in the most preferred modes. In certain preferred embodiments, P0C13 is sufficiently free of water to ensure that the levels of dimer and acid in P0C13 are less than 0.2% by weight.

Reference will now be made to specific examples that use the processes described above. It will also be understood that the examples are provided to more fully describe the preferred embodiments and that no limitation to the scope of the invention is intended thereby.

Example 1 Bulk addition of bisphenol A Stage 1: Phosphorus oxychloride (3347.8 g, 21. 881 moles), magnesium chloride (2.85 g, 0.030 moles) and bisphenol A (1425.4 g, 6.24 moles) to a flask equipped with a stirrer, heating mantle, temperature controller and ventilated reflux condenser to a caustic gas scrubber . The contents were heated to reflux for 6.75 hours and the reaction was verified as to the completion by liquid chromatography. After the reaction was complete, the flask was equipped for distillation and a vacuum was applied gradually until the pressure was less than 20 torricellis. The temperature of the contents of the flask is allowed to increase to 180 ° C during this process. When the temperature reaches 180 ° C, the distillation was stopped and the material was subsequently used in the second stage.

Step 2: A portion of the intermediate from step 1 (1095.8 g) of the above reaction was charged to a flask equipped with stirrer, heating mantle, temperature controller and vented reflux condenser to a caustic gas scrubber. The contents were heated to a temperature of 180 ° C and phenol (832.7 g, 8.85 mol) was charged to an addition funnel. The phenol was added in the course of 3.5 hours. One hour after the addition was complete, a bubbling of subsurface nitrogen is introduced to the reactor. The reaction was verified as to the completion by liquid chromatography. When the reaction was complete, a vacuum was applied to the reactor for 1.0 hour to remove most of the excess phenol. The product was analyzed by liquid chromatography and found to contain 96.1% by area of bisaryl diphosphate (monomer and higher oligomers) and 4.5% by weight of triphenyl phosphate.

Example 2 Semi-continuous addition of bisphenol A Stage 1: Phosphorus oxychloride (671.0 g, 4. 38 moles) and magnesium chloride (0.58 g, 0.0061 moles) to a flask equipped with a stirrer, heating mantle, temperature controller and reflux condenser ventilated to a water absorber. The contents of the flask were heated to 100 ° C. Bisphenol A (288.5 g, 1.26 moles) is placed in a funnel of solid addition and added to the flask in the course of 3 hours. At that time, the contents of the flask were heated to reflux and the reaction was verified as to the completion by liquid chromatography. After the reaction was complete, the flask was equipped for distillation and a vacuum was applied gradually until the pressure was less than 20 torricellis. The temperature of the contents of the flask is allowed to increase to 180 ° C during this process. When the temperature reached 180 ° C, the distillation was stopped and the material was subsequently used in the second stage. Stage 2: The contents of the flask from stage 1 was heated to a temperature of 165 ° C. Phenol (432.6 g, 4.60 moles) is charged in an addition funnel wrapped with heating tape. The phenol was added to the reactor in the course of 2 hours. One hour after the addition was complete, a bubbling of subsurface nitrogen is introduced to the reactor. The reaction was verified as to the completion by liquid chromatography. When the reaction was complete, a vacuum was applied to the evaporator to separate the remaining phenol. The final product was analyzed by liquid chromatography and found to contain 98.7% by area of bisaryl diphosphate (monomer and higher oligomers) and 0.76% by weight of triphenyl phosphate.

Example 3 Use of dry BPA Step 1: Phosphorus oxychloride and bisphenol A are reacted under magnesium chloride catalysis as described in example 2, step 1 (semicontinuous addition of BPA). Bisphenol A was analyzed for moisture before the reaction. Two different reactions were carried out using two different water levels in bisphenol A. The product of both reactions was analyzed by liquid chromatography to determine the amount of monomeric and dimeric product. The table below shows that the use of anhydrous bisphenol A results in an intermediate product of stage 1 having a higher content of the monomeric product in relation to the dimeric product.

Example 4 Use of anhydrous phenol Step 1: Two reactions were carried out to generate the intermediate product from step 1 as described in example 2, step 1 (semicontinuous addition of BPA). In both cases Bisphenol A with a moisture content of < 200 ppm of water. The% monomer content of the normalized area of the final product was > 81%. Step 2: The material from each of the reactions of step 1 was reacted with phenol as described in example 2, step 2. The two reactions used phenol which had two different levels of moisture. The product was analyzed by liquid chromatography in terms of the content of monomeric and dimeric product and was analyzed by titration in terms of acidity. The data in the table below shows that the content increased in phenol had no impact on the monomer content normalized in the final product. However, the acidity of the final product was affected.

Example 5 It can also be seen that the use of anhydrous phenol (<300 ppm of water) and the use of anhydrous BPA (<200 ppm of water) results in a flame retardant polycarbonate which is hydrolytically more stable than that obtained when using BPA or wet phenol. Polymeric resin bars were composed and molded from PC / ABS with bis (diphenyl) phosphate bisphenol A as described in Example 6. The formulated bars were subjected to accelerated test conditions (100 ° C and 100% relative humidity) to determine hydrolytic stability. The molecular weight of the polycarbonate portion of the resin was verified by gel permeation chromatography with respect to time. The increased hydrolytic stability is indicated by the lower molecular weight loss with respect to time.

Molecular weight of polycarbonate with respect to time EXAMPLE 6 Composition of Bisaryl Diphosphates to Polymer Resins Bisphenol A bis (diphenyl) phosphate produced in the above examples was combined into several polymer resins by using a Berstorff 25 mm twin screw extruder equipped with a current driven band feeder. direct (CD) variable speed 10.2 cm (4 inches) wide. The twin screw extruder settings are tabulated below.

Barrel temperature 2 (° C) 240 - 260 Barrel temperature 3 (° C) 240 - 260 Barrel temperature 4 (° C) 240 - 260 Barrel temperature 5 (° C) 240 - 260 Barrel temperature 6 (° C) 240 - 260 Barrel temperature 7 (° C) 240 - 260 Nozzle temperature (° C) 240 - 260 Melt temperature (° C) 240 - 270 Melt pressure (Kg / cm2 (psi)) 16.9-39.4 (240-560) Torque moment (Kilowatts) 0.17 - 0.25 Speed Extruder (rpm) 18-200 Bisphenol A bis (diphenyl) phosphate is heated in a 4 liter stainless steel resin kettle at a temperature of about 80 ° C. While the bis (diphenyl) phosphate of bisphenol A is heated, the band feeder containing the polymeric resin is calibrated to provide the required feed rate to the throat of the extruder. Once the bis (diphenyl) phosphate of bisphenol A has reached the temperature, the heated Zenith pump is calibrated to provide the desired feed rate of bis (diphenyl) phosphate of bisphenol A to the third barrel of the twin screw extruder. Then the pumping system is connected to the extruder by joining the feed lines to the injection hole located in the third barrel. After the feed rates have been adjusted, the polymer resin is fed into the twin screw extruder in the throat. The resin is allowed to pass through the extruder for several minutes before the bisphenol A bis (diphenyl) phosphate is added, in order to ensure that any residual cleaning material is purged from the extruder. After the purge step is completed, the pumping system is started and Bisphenol A bis (diphenyl) phosphate is injected into the extruder through the feed lines and the injection orifice. The melt pressure, measured at the interface between the seventh barrel and the nozzle, is used as an indication that the bis (diphenyl) phosphate of bisphenol A is incorporated into the polymer resin. The base polymer resin generally has a melt pressure reading of 7.03 -14.1 Kg / cm (100-200 psi) greater than the polymer resin formulated with bis (diphenyl) phosphate of bisphenol A. Once the bis (diphenyl) Bisphenol A phosphate is incorporated into the polymer resin, the melt pressure drops to 7.03 -14.1 Kg / cm2 (100 - 200 psi) due to the ability of Bisphenol A bis (diphenyl) phosphate to improve the flow properties of the polymer resin. Once bisphenol A bis (diphenyl) phosphate has been incorporated into the polymer resin, the material passes through the extruder nozzle and forms strands through a water bath used for cooling. The cooled strands of the polymeric resin formulated are transformed into pellets and pellets and are used to mold flammability test bars and for physical tests. The same procedure is used for each individual polymer resin system. The main difference is the amount of bis (diphenyl) phosphate of bisphenol A added to the individual polymer resin systems. Representative examples are provided below. All of these formulations were tested using the standard procedure of UL 94 and found to be less flammable than the base resin. 1. PPO / HIPS: 20% Bisphenol A bis (diphenyl) phosphate and 80% PPO / HIPS. 2. PC / ABS: 11% bisphenol A bis (diphenyl) phosphate and 89% PC / ABS. 3. PBT: 10% Bisphenol A bis (diphenyl) phosphate and 90% PBT. While the invention has been illustrated and described in detail in the foregoing description, it is to be construed as illustrative and not restrictive in character, it will be understood that only the preferred embodiment has been shown and described and that it is desired to protect all changes and modifications that are in the spirit of the invention. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (16)

1. Claims Having described the invention as above, it is claimed as property, contained in the following claims: 1. A flame retardant polymer resin, characterized in that it comprises a polymeric resin, a bisaryl diphosphate prepared catalytically and at least 10% (by weight) of the catalytic residue of the catalytic preparation.
2. 2. The flame retardant polymer resin according to claim 1, characterized in that the bisaryl diphosphate prepared catalytically is a bis (diphenyl) phosphate of bisphenol A prepared catalytically.
3. 3. The flame retardant polymeric resin according to claim 1, characterized in that the bisaryl diphosphate is a product obtained by a process that includes semicontinuously adding a dihydric aromatic compound to a heated mixture of phosphorus oxyhalide and a catalyst; wherein the semicontinuous addition is carried out in a period from about 0.5 hours to about 12.0 hours.
4. 4. The flame retardant polymer resin according to claim 3, characterized in that the aromatic dihydric compound is bisphenol A.
5. 5. The flame retardant polymeric resin according to claim 1, wherein the product of
6. 'Bisaryl diphosphate is obtained by a process characterized in that it comprises the steps of: (a) reacting a dihydric aromatic compound with a catalyst / phosphorus oxyhalide mixture to produce a diphosphorotetrahalide intermediate, wherein the aromatic dihydric compound contains less of approximately 200 ppm of water; and (b) reacting the diphosphorotetrahalide intermediate with an alcohol to form the desired bisaryl diphosphate. 6. The flame retardant polymeric resin according to claim 5, characterized in that the resin is a combination or mixture of a polymeric resin and the bisaryl diphosphate product is obtained by a process that includes: (a) reacting bisphenol A with a catalyst / phosphorus oxyhalide mixture to produce a diphosphorotetrahalide intermediate, wherein the bisphenol A contains less than about 200 ppm of water and (b) reacting the diphosphoro-tetrahalide intermediate with phenol to form bisphenol A bis (diphenyl) phosphate.
7. 7. The flame retardant polymer resin according to claim 1, wherein the bisaryl diphosphate product is obtained by a process characterized in that it comprises the steps of: (a) reacting a dihydric aromatic compound with a catalyst / phosphorus oxyhalide mixture for produce a diphosphorotetrahalide intermediate; and (b) reacting the diphosphorotetrahalide intermediate with an alcohol to form the desired bisaryl diphosphate, wherein the alcohol contains less than about 300 ppm of water. The flame retardant polymeric resin according to claim 7, wherein the resin comprises a polymeric resin and the bisaryl diphosphate product is obtained by a process characterized in that it comprises the steps of: (a) reacting bisphenol A with a catalyst / phosphorus oxyhalide mixture to produce a diphosphorotetrahalide intermediate; and (b) reacting the diphosphorotetrahalide intermediate with phenol to form bis (diphenyl) phosphate of bisphenol A, wherein the phenol contains less than about 300 ppm of water. 9. A method for making flame retardant polymer resins, characterized in that it comprises combining a bisaryl diphosphate catalytically prepared in a polymeric resin without separating the catalytic residue from the bisaryl diphosphate. The method according to claim 9, characterized in that the combining step comprises combining a bis (diphenyl) phosphate of bisphenol A prepared catalytically to a polymeric resin before separating substantial quantities of the catalytic residue of the bis (diphenyl) phosphate of bisphenol. A. 11. The method of compliance with the claim 9, characterized in that the bisaryl diphosphate is prepared by a process that includes semicontinuously adding a dihydric aromatic compound to a heated mixture of phosphorus oxyhalide and a catalyst, wherein the semicontinuous addition is carried out over a period of about 0.5. hours at approximately 12.0 hours. The method according to claim 11, characterized in that the aromatic dihydric compound is bisphenol A. 13. The method according to claim 9, characterized in that the bisaryl diphosphate is prepared by a process that includes: (a) reacting a dihydric aromatic compound with a catalyst / phosphorus oxyhalide mixture to produce a diphosphorotetrahalide intermediate, wherein the aromatic dihydric compound contains less than approximately 200 ppm of water; and (b) reacting the diphosphorotetrahalide intermediate with an alcohol to form the desired bisaryl diphosphate. The method according to claim 13, characterized in that the combination comprises combining in a polymeric resin the bisaryl diphosphate product which is obtained by a process that includes: (a) reacting bisphenol A with a mixture of catalyst / oxyhalide of phosphorus to produce a diphosphorotetrahalide intermediate, wherein the bisphenol A contains less than about 200 ppm of water; and (b) reacting the diphosphorotetrahalide intermediate with phenol to form bis (diphenyl) phosphate of bisphenol A. 15. The method according to claim 9, characterized in that the bisaryl diphosphate is prepared by a process that includes: (a) ) reacting a dihydric aromatic compound with a catalyst / phosphorus oxyhalide mixture to produce a diphosphorotetrahalide intermediate; and (b) reacting the diphosphorotetrahalide intermediate with an alcohol to form the desired bisaryl diphosphate, wherein the alcohol contains less than about 300 ppm of water. The method according to claim 15, characterized in that the method comprises adding to a polymeric resin the bisaryl diphosphate product which is obtained by a process that includes: (a) reacting bisphenol A with a mixture of catalyst / oxyhalide of phosphorus to produce a diphosphorotetrahalide intermediate; and (b) reacting the diphosphorotetrahalide intermediate with phenol to form bis (diphenyl) phosphate of bisphenol A, wherein the phenol contains less than about 300 ppm of water.