WO2008073871A1

WO2008073871A1 - Organophosphonate oligomers and mixtures thereof useful as flame retardants

Info

Publication number: WO2008073871A1
Application number: PCT/US2007/086932
Authority: WO
Inventors: Anne M. Sauer; Arthur G. Mack; Techen Tsao; Jeffrey Todd Aplin
Original assignee: Albemarle Corp
Current assignee: Albemarle Corp
Priority date: 2006-12-11
Filing date: 2007-12-10
Publication date: 2008-06-19
Anticipated expiration: 2009-06-11
Also published as: TW200902542A; TW200838870A; WO2008073872A1

Abstract

Organophosphonate oligomers, and mixtures thereof, useful as flame retardants.

Description

ORGANOPHOSPHONATE OLIGOMERS AND MIXTURES THEREOF USEFUL AS FLAME RETARDANTS

BACKGROUND

[0001] Over the years, numerous proposals regarding possible reactive flame retardant additives for use in polyurethanes have been made. Oftentimes, in actual practice, the proposals have been unsuccessful. See, for example, the background discussion presented in U.S. Pat. No. 3,840,622. In Example 4 of that patent, a recipe is given for the preparation of a reaction product of dipropylene glycol and trimethyl phosphite in a 1 to 1.1 mole ratio, respectively, followed by reaction with benzyl chloride, the overall proportions of trimethyl phosphite:dipropylene glycohbenzyl chloride being 1,1: 1:0.65, respectively, or when normalized on benzyl chloride content, 1.69:1.54:1, respectively, Unfortunately, this material is unsuitable for preparing useful polyurethane foams.

SUMMARY OF THE INVENTION

[0002] This invention involves, inter alia, the discovery that when certain components are reacted together in appropriate proportions and subjected to appropriate reaction conditions, organophosphonate oligomers can be produced that are capable of providing flame retarded polyurethane foams of very desirable quality. In fact, such oligomers have been found capable of producing high-quality flexible polyetherpolyol-based polyurethane foams and also, flexible high-quality polyesterpolyol-based polyurethane foams.

[0003] Accordingly, this invention provides, in one of its embodiments, a process for producing an organophosphonate oligomer, which process comprises: a) bringing together (i) trimethyl phosphite and (ii) diethylene glycol in a (i):(ii) mole ratio of about 6:5, about 7:6, about 8:7, or about 9:8 to form a first reaction mixture, and heating the first reaction mixture to a temperature in the range of about 75⁰C to about 13O⁰C for a period in the range of about 1 hour to about 4 hours and removing methanol coproduct from this heated reaction mixture to form a first reaction product mixture; b) bringing together benzyl chloride and/or benzyl bromide and first reaction product mixture, to form a second reaction mixture and maintaining this mixture at a temperature in the range of about 9O⁰C to about 150⁰C, preferably in the range of about 110⁰C to about 13O⁰C for a period in the range of about 1 hour to about 3 hours and then adding a catalytic quantity of alkyl iodide to the resultant reaction product mixture; c) heating resultant reaction product mixture of b) at a temperature in the range of about 60⁰C to about 14O⁰C for a period in the range of about 2 hours to about 12 hours and then distilling the resultant reaction product mixture under reduced pressure to remove volatiles from the reaction product mixture.

[0004] In another embodiment of this invention, there is provided a process for producing an organophosphonate oligomer, which process comprises: a) bringing together (i) trimethyl phosphite and (ii) diethylene glycol in a (i):(ii) mole ratio of about 5+n:5, about 6+n:6, about 7+n:7, or about 8+n:8, where n is a fractional number less than 1, to form a first reaction mixture, and heating the first reaction mixture to a temperature in the range of about 75⁰C to about 13O⁰C for a period in the range of about 1 hour to about 4 hours and removing methanol coproduct from this heated reaction mixture to form a first reaction product composition; b) bringing together an additional quantity of trimethyl phosphite and first reaction product composition, with the temperature of the first reaction product composition being below about 130⁰C to form a second mixture, said additional quantity of trimethyl phosphite being an amount in moles equal to the fractional number of n in a) such that the total (i):(ii) mole ratio used in a) and b) is about 6:5, about 7:6, about 8:7, or about 9:8, and heating second mixture to a temperature in the range of about 9O⁰C to about 13O⁰C for a period in the range of about 1 hour to about 4 hours and removing methanol coproduct from this heated mixture to form a second reaction product composition; c) bringing together benzyl chloride and/or benzyl bromide with second reaction product composition of b), to form a third mixture and maintaining this mixture at a temperature in the range of about 9O⁰C to about 150⁰C, preferably in the range of about HO⁰C to about 130°C for a period in the range of about 1 hour to about 3 hours to form a third product composition and then adding a catalytic quantity of alkyl iodide to third product composition; d) heating third product composition of c) at a temperature in the range of about 6O⁰C to about 140⁰C for a period in the range of about 2 hours to about 12 hours and then distilling the resultant reaction product mixture under reduced pressure to remove volatiles from the reaction product mixture.

[0005] Further embodiments of this invention are organophosphonate oligomers formed by the above processes, which oligomers are characterized by having the capability of forming flame retarded flexible polyetherpolyol-based polyurethane foams, when employed in a polyurethane prepolymerization formulation at a level of 8 wt%, that exhibit virtually no shrinkage, that produce less than 30 mg of fog when subjected to the DIN 75201 test procedure and that achieve an FMVSS 302 rating of SE/NBR.

[0006] Still another embodiment of this invention is a process for producing a flame retarded polyetherpolyol-based polyurethane foam, which process comprises introducing a polymerization catalyst into a precursor mixture formed from at least an isocyanate, a polyetherpolyol, a surfactant, a catalyst, a blowing agent, and a flame retarding amount of an organophosphonate oligomer of this invention.

[0007] Yet another embodiment of this invention is process for producing a flame retarded polyester polyurethane foam, which process comprises introducing a polymerization catalyst into a precursor mixture formed from at least an isocyanate, a polyesterpolyol, a surfactant, a catalyst, a blowing agent, and a flame retarding amount of an organophosphonate oligomer mixture of this invention. [0008] The above and other embodiments and features of this invention will be still further apparent from the ensuing description and appended claims. For example, in some embodiments, preferably when the polyurethane foams and/or flame retarded polyurethane foam comprises 8 wt%, based on the total weight of the polyurethane foam, of said an organophosphonate oligomer or an organophosphonate oligomer mixture of the present invention, the flame retarded polyurethane foam or polyurethane foam exhibits virtually no shrinkage and produces less than 30 mg of fog when subjected to the DIN 75201 test procedure and that achieve an FMVSS 302 rating of SE/NBR.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Fig. 1 is a drawn copy of a photograph of a flexible polyetherpolyol-based polyurethane foam of this invention prepared as in Example 1 hereof. [0010] Fig. 2 is a drawn copy of a photograph of a flexible polyetherpolyol-based polyurethane foam not of this invention prepared as in Comparative Example A hereof. [0011] Fig. 3 is a drawn copy of a photograph of a flexible polyetherpolyol-based polyurethane foam not of this invention prepared as in Comparative Example B hereof. [0012] Fig. 4 is a drawn copy of a photograph of a flexible polyetherpolyol-based polyurethane foam not of this invention prepared as in Comparative Example C hereof.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[0013] It will be noted that very specific components are utilized in the preparation of the organophosphonate oligomer mixtures pursuant to this invention. These components are trimethyl phosphite, polyethylene glycol, and benzyl chloride or benzyl bromide. Similar products made from polypropylene glycol are unsuitable for producing polyurethanes having good properties. In addition, organophosphonate oligomer mixtures produced pursuant to this invention have been found capable of providing both polyether polyurethanes and polyester polyurethanes having desirable properties. Also, because of the availability and low cost of diethylene glycol, the practice of this invention is also of economic advantage. [0014] The organophosphonate oligomer mixtures of the present invention are copolymeric polyphosphonates having a suitable quantity of hydroxy-terminated end groups, thus enabling them to be utilized as reactive flame retardants in polyurethanes. As those skilled in the art readily appreciate, the organophosphonate oligomer mixtures of the present invention are typically mixtures of individual oligomers, and because these oligomers are mixtures of individual oligomers produced in a series of reactions, a depiction of the products is at best an approximation. Nevertheless, the following depiction will enable a visualization of a presumed general structure of the individual oligomers organophosphonate oligomer mixtures of the present invention:

where each Ri is independently selected from methyl, benzyl, or HOC₂H₄OC₂H₄ ^"; each Ei is the same or different and is either HOC₂H₄OC₂H₄ ^" or methyl; and n is a whole or fractional number. In some embodiments, one Ej is HOC₂H₄OC₂H₄ ^" and the other Ei is methyl. In some embodiments, each Ri is methyl or benzyl. In these embodiments, methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 10 methyl groups per each benzyl group. In preferred embodiments the ratio is 3:8. In these embodiments, methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 8 methyl groups per each benzyl group.

[0015] Typically, n is about 20 or less, and preferably, is about 10 or less, and these values can be average values because the products are usually a mixture of oligomers. In the case of mixtures of oligomers, the average value of n is usually in the range of from about 1 to about 10; in some embodiments in the range of from about 1 to about 5; in some embodiments in the range of from about 2 to about 3; in still other embodiments, in the range of from about 5 to about 10. As noted above, at least a portion of EjO contains terminal hydroxyl groups. The above formula is not intended to depict any particular stereoisomeric configuration for the oligomer depicted and consequently, the above formula does not constitute any representation, let alone limitation, concerning the geometric configuration of the oligomer.

[0016] In some embodiments, the mixtures of organophosphonate oligomers of the present invention further comprise organophosphonate oligomers wherein each Ei of is methyl.

[0017] In any given product, the hydroxyl number can be determined by a standard analytical procedure. Typically, the polyphosphonate oligomers produced pursuant to this invention have hydroxyl numbers in the range of about 10 to about 100, but can have hydroxyl numbers in the range of 0 to 100.

[0018] The organophosphonate oligomer mixtures of the present invention can be characterized as having at least two, in some embodiments more than two, and in other embodiments all, of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 150 to about 25O⁰C, in some embodiments in the range of from about 175 to about 225⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 400 to about 1000, in some embodiments in the range of from about 500 to about 900; iii) a viscosity at 25⁰C in the range of from about 2000 to about 10,00OcP, in some embodiments in the range of from about 3000 to about 900OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 15 to about 20wt.%, in some embodiments in the range of from about 16 to about 18 wt.%; v) a TGA (thermogravimetric analysis), profile, of:

[0019] The organophosphonate oligomer mixtures of the present invention are useful as flame retardants in a variety of applications. In some embodiments, the organophosphonate oligomer mixtures of the present invention are used as flame retarding agents in polyurethane foams. To form flame retarded polyurethane foams pursuant to this invention, the fundamental components used are isocyanates, polyols, and an organophosphonate oligomer mixtures of the present invention. The polyols are polyether polyols or polyester polyols. The reaction readily occurs at room temperature in the presence of a blowing agent such as water, a volatile hydrocarbon, halocarbon, or halo hydrocarbon, or mixtures of two or more such materials. Catalysts used in effecting the reaction include amine catalysts, tin-based catalysts, bismuth-based catalysts or other organometallic catalysts, and the like. Surfactants such as substituted silicone compounds are often used in order to maintain homogeneity of the cells in the polymerization system. Hindered phenolic antioxidants, e.g., 2,6-di-tert- butyl-para-cresol and methylenebis(2,6-di-tert-butylphenol), can be used to further assist in stabilization against oxidative degradation. These and other ingredients that can be used, and the proportions and manner in which they are used are reported in the literature. See for example: Herrington and Hock, Flexible Polyurethane Foams, The Dow Chemical Company, 1991, 9.25-9.27 or Roegler, M ASlabstock Foams@; in Polyurethane Handbook; Oertel, G., Ed.;Hanser Munich, 1985, 176-177 or Woods, G. Flexible Polyurethane Foams, Chemistry and Technology; Applied Science Publishers, London, 1982, 257-260.

[0020] In forming flame retarded polyurethanes using a organophosphonate oligomer formed pursuant to this invention, amounts of the organophosphonate oligomer mixtures of the present invention in the range of about 4 to about 15 wt% based on the total weight of the polyurethane formulation, are typically used.

[0021] The organophosphonate oligomer products of this invention are typically pale yellow or slightly off-white in color. Light color is advantageous as it simplifies the end-users task of insuring consistency of color in the articles that are flame retarded with the oligomeric products. [0022] The organophosphonate oligomer mixtures of the present invention can also be used as flame retardants in, or in connection with, polyurethane resins and composites, rigid polyurethane foams, phenolic resins, paints, varnishes, and textiles.

[0023] Further, the organophosphonate oligomer mixtures of the present invention may be used as additive flame retardants in formulations with other flammable materials. The flammable material may be macromolecular, for example, a cellulosic material or a polymer. Illustrative polymers are: olefin polymers, cross-linked and otherwise, for example homopolymers of ethylene, propylene, and butylene; copolymers of two or more of such alkene monomers and copolymers of one or more of such alkene monomers and other copolymerizable monomers, for example, ethylene/propylene copolymers, ethylene/ethyl acrylate copolymers and ethylene/propylene copolymers, ethylene/acrylate copolymers and ethylene/vinyl acetate copolymers; polymers of olefinically unsaturated monomers, for example, polystyrene, e.g. high impact polystyrene, and styrene copolymers; polyamides; polyimides; polycarbonates; polyethers; acrylic resins; polyesters, especially poly(ethyleneterephthalate) and poly(butyleneterephthalate); thermosets, for example, epoxy resins; elastomers, for example, butadiene/styrene copolymers and butadiene/acrylonitrile copolymers; terpolymers of acrylonitrile, butadiene and styrene; natural rubber; butyl rubber and polysiloxanes. The polymer may be, where appropriate, cross-linked by chemical means or by irradiation. The organophosphonate oligomer products of this invention also can be used in textile applications, such as in latex-based back coatings.

[0024] The amount of an organophosphonate oligomer mixtures of the present invention used in a formulation will be that quantity needed to obtain the flame retardancy sought. It will be apparent to those skilled in the art that for all cases no single precise value for the proportion of the product in the formulation can be given, since this proportion will vary with the particular flammable material, the presence of other additives and the degree of flame retardancy sought in any give application. Further, the proportion necessary to achieve a given flame retardancy in a particular formulation will depend upon the shape of the article into which the formulation is to be made, for example, electrical insulation, tubing, electronic cabinets and film will each behave differently. In general, however, the formulation, and resultant product, may contain from about 1 to about 30 wt%, preferably from about 5 to about 25 wt% of an organophosphonate oligomer mixture of the present invention. Masterbatches of polymer containing an organophosphonate oligomer mixture of the present invention, which are blended with additional amounts of substrate polymer, typically contain even higher concentrations of the organophosphonate oligomer mixtures of the present invention, e.g., up to 50 wt % or more.

[0025] Any of several conventional additives used in thermoplastic formulations may be used, in their respective conventional amounts, with the oligomeric flame retardants of this invention, e.g., plasticizers, antioxidants, fillers, pigments, UV stabilizers, etc.

[0026] Thermoplastic articles formed from formulations containing a thermoplastic polymer and an oligomeric product of this invention can be produced conventionally, e.g., by injection molding, extrusion molding, compression molding, and the like. Blow molding may also be appropriate in certain cases.

[0027] The practice and advantages of this invention will be still further apparent from the following illustrative examples. These examples are not intended to limit the invention to only the scope of the subject matter described.

[0028] The preparation of a preferred organophosphonate oligomer pursuant to this invention is described in Example 1.

EXAMPLE 1

[0029]Diethylene glycol (381.6 g; 3.6 mole) and trimethyl phosphite (520 g; 4.2 mole) were charged to the reactor. The mixture was heated to HO⁰C for 1 hour. The temperature was reduced to below IOOEC and additional trimethyl phosphite (26 g; 0.2 mole) was added. The resultant reaction mixture was heated at 12O⁰C to 130⁰C until no more methanol was distilled (about 230 g). Benzyl chloride (72.9 g; 0.6 mol) was charged to the reaction vessel while the temperature was maintained at 120⁰C. After addition of the benzyl chloride, the temperature was maintained at 12O⁰C for 1 hour. The reaction mixture was cooled to 6O⁰C and 2 mL of methyl iodide was added. The reaction mixture was heated at 120⁰C for 6 hours. An additional 1 mL of methyl iodide was added during the heating. The reaction progress was monitored via ³¹P NMR. Upon completion of the reaction, vacuum (5 mm) was applied at 12O⁰C for 1 hour. After cooling the reactor contents to < 6O⁰C, 50 mL of propylene oxide was added in one portion, and the reaction mixture was heated at 100⁰C for 2 hours. A vacuum was applied to the reactor at 12O⁰C/ 10 mm for 1 hour. The oligomeric product remaining in the reactor was found to have an acid value below 0.1. Vacuum distillation was applied to the reactor at 130°C/about 1 mmHga for 2 hours. The final oligomeric product (66.7% overall yield based on phosphorus) was a colorless liquid with an acid value of less than 0.1, an OH number of 32, viscosity of 4,231 cP and %P of 16.8, This product had an onset temperature, as determined by DSC-RHE₅ of 195.5 ⁰C and TGA values (10 ⁰C / min in air) of: 1% = 52 ⁰C, 5% = 202 ⁰C, 10% = 245 ⁰C, 25% = 280 ⁰C, 50% = 302 ⁰C.

[0030] Examples A, B, and C are presented for the purposes of comparison. They describe the formation of organophosphonate oligomers similar to that of Example 1 but not of this invention.

EXAMPLE A (COMPARATIVE)

[0031] Diethylene glycol (381.6 g; 3.6 mol) and trimethyl phosphite (520.8 g; 4.2 mol) were charged to the reactor. The mixture was heated to HO⁰C for 1 hour. The temperature was reduced to 105⁰C and trimethyl phosphite (26 g; 0.2 mole) was added. The resultant mixture was heated at 13O⁰C during a period of 2 hours. A total of 220 g of methanol was evolved and collected. The temperature was reduced to 12O⁰C and benzyl chloride (145.8 g; 1.2 mole) was added during a 1 hour period. After heating at 12O⁰C for 2 hours, methyl iodide (2 mL) was added. The mixture was heated at 12O⁰C for 6 hours. ³¹P NMR showed all phosphite had been converted to phosphonate. This product was found to have an acid value of 2.0. After reducing the temperature to 6O⁰C, propylene oxide 50 mL was added. After heating at 100°C for 2 hours, the acid value was reduced to below 0.1. Vacuum distillation of the product mixture was conducted at 130°C/about 1 mmHga for 2 hours. The resultant product (66.6% overall yield based on phosphorus) was a colorless liquid with an acid value of less than 0.1, an OH number of 43, viscosity of 3,425 cP and %P = 15.1. This product had an onset temperature, as determined by DSC-RHE, of 250.7 ⁰C and TGA values (10 ⁰C / min in air) of: 1% = 90 ⁰C, 5% = 221 ⁰C, 10% = 248 ⁰C, 25% = 279 ⁰C, 50% = 301 ⁰C.

EXAMPLE B (COMPARATIVE)

[0032] Dipropylene glycol (48.2 g; 0.36 mol), and trimethyl phosphite (52.1 g; 0.42 mol) were charged to the reactor. The mixture was heated at 115⁰C during a 2 hour period. Then, with the temperature at 115⁰C, additional trimethyl phosphite 3.0 mL was added. The mixture was heated to 125⁰C and kept at this temperature until 23.0 g of methanol was collected. Methyl iodide (1.2 mL) was added in 3 portions during a 7 hour period. ³¹P NMR showed all phosphite had been converted to phosphonate. Vacuum was applied at 120°C/about 1 mmHga for 1.5 hour. The resultant mixture was cooled to 6O⁰C and 13 mL of propylene oxide was added. The mixture was re-heated to and held between 100°C and HO⁰C for 2 hours. Then, vacuum was applied at 125°C/about 1 mmHga for 1.5 hours, and then the reactor was purged with nitrogen for 2 hours at 13O⁰C. This yielded a colorless liquid with an acid value of 0.1 and an OH number of 32.

EXAMPLE C (COMPARATIVE)

[0033] Dipropylene glycol (40.2 g; 0.3 mol) and trimethyl phosphite (43.4 g; 0.35 mol) were charged to the reactor. The mixture was heated to and held at 113⁰C during 1 hour. The temperature was kept at 105⁰C to HO⁰C, and trimethyl phosphite 3.0 mL was added. The mixture was heated to 13O⁰C and kept at this temperature until 21.0 g of methanol was collected. The temperature was lowered to 12O⁰C and benzyl chloride (6.1 g; 0.05 mole) was charged at 12O⁰C during a period of 20 minutes. Heating was continued at 12O⁰C to 122⁰C for 2 more hours. The temperature was then reduced to 60⁰C. After adding methyl iodide (0.5 mL), the temperature was maintained at 12O⁰C for 6 hours. ³¹P NMR showed all phosphite had been converted to phosphonate. After heating to and at 12O⁰C under 5mm vacuum for 1 hour, this colorless liquid had an acid value of 0.9. The temperature was lowered to 6O⁰C. Propylene oxide 4 mL was added. The mixture was heated at 100⁰C for 3 hours. Vacuum was applied at 130°C/about 1 mmHga. The product was a colorless liquid with an acid value of 0.1 and an OH number of 41.6. [0034] Photographs were taken of the four buns from the above tests, and drawings prepared from these photographs appear as Figs. 1-4, respectively. Each of these figures depicts the upper portion of a container in which is disposed a polyurethane foam, the foam of Fig. 1 being a foam of this invention whereas the foams of Figs. 2, 3, and 4 are not of this invention. Referring to Fig. 1, it can be seen that in container 10 there is a large bun 20 of polyurethane. In order to inspect the quality of the interior of the foam, it was cut vertically into two halves as indicated at 30. The quality of the foam as inspected visually along the vertical cut showed that the foam had substantially uniform pores with no undesirable voids or the like. In Figs. 2, 3, and 4 the foams are similarly displayed within the container except that the foams are shown uncut. It can be seen that these foams are smaller in size due to shrinkage and their respective appearances can be termed Aprune-like@. Subsequent slicing of the respective foams showed that these products had somewhat irregular pore formation and that undesirable void formation had occurred within the body of each of the foams.

EXAMPLE 2

[0035] A flexible polyurethane foam formulation containing a flame retardant was prepared by adding the following components to an open mouth vessel wherein all parts are by weight:

Polyol (Pluracol 1388; BASF Corporation) -83.0 parts

Surfactant (B-8229; Degussa AG) - 0.80 part

Catalyst 1 (A-200; GE Silicones) - 0.10 part

Catalyst 2 (T-9/Kosmos 29; Degussa AG) - 0.2 part

Flame retardant - 11.6 parts

To this mixture was added water (3.7 parts) and the mixture was stirred for about 10 seconds when it achieved a white and foamy appearance. A timer was started and the mixture was agitated for another 50 seconds. Then, toluene diisocyanate (TDI; 45.5 parts) was added, and the mixture was allowed to stir for 10 more seconds. The mixture was then poured into a large open-mouth plastic container in which foam formation occurred. In one such run, the flame retardant used was that formed in Example 1. For comparative purposes, three additional runs were conducted in the same manner but wherein the flame retardant used was that formed in Example A, B, or C, respectively. Once the foam buns were formed, they were evaluated and checked for shrinkage and stability. It was found that the foam buns from Examples B and C were unstable and suffered from severe shrinkage. Thus, they were not even suitable for further evaluation. Thus, samples of foams from Example 1 and from Comparative Example A were subjected to the standard FMVSS302 flame retardancy test and the standard DIN 75201 fog test in which the amount of fog produced is expressed in milligrams. The results of these tests are summarized in the Table.

TABLE

[0036] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and/or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition. Also, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, blending or mixing operations, if conducted in accordance with this disclosure and with ordinary skill of a chemist, is thus of no practical concern. [0037] Except as may be expressly otherwise indicated, the article "a" or "an" if and as used herein is not intended to limit, and should not be construed as limiting, a claim to a single element to which the article refers. Rather, the article "a" or "an" if and as used herein is intended to cover one or more such elements, unless the text expressly indicates otherwise.

[0038] Each and every patent or publication referred to in any portion of this specification is incorporated in toto into this disclosure by reference, as if fully set forth herein.

[0039] This invention is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove.

Claims

THAT WHICH IS CLAIMED IS:

1) A composition comprising:

wherein each Ri is independently selected from methyl, benzyl, or HOC₂H₄OC₂H₄ ^"; each Ei is the same or different and is either HOC₂H4OC2H4^" or methyl; and n is an integer equal to or less than 20.

2) The composition according to claim 1 wherein one E] is HOC2H4OC₂H₄- and the other Ei is methyl.

3) The composition according to claim 1 wherein said composition is characterized as having: a) at least two of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 150 to about 25O⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 400 to about 1000; iii) a viscosity at 25⁰C in the range of from about 2000 to about 10,00OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 15 to about 20wt.%; v) a TGA (thermo gravimetric analysis), profile, of:

or b) at least two of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 175 to about 225⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 500 to about 900; iii) a viscosity at 25⁰C in the range of from about 3000 to about 900OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 16 to about 18 wt.%; v) a TGA (thermogravimetric analysis), profile, of:

4) The composition according to claim 3 wherein each R* is methyl or benzyl, wherein methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 10 methyl groups per each benzyl group.

5) A mixture of organophosphonate oligomers containing two or more organophosphonate oligomers, wherein each of said two or more organophosphonate oligomers are represented by the general formula:

wherein each Ri is independently selected from methyl, benzyl, or HOC₂H₄OC₂HU^"; each Ei is the same or different and is either HOC₂H₄OC₂H₄ ^" or methyl; and the average of all n's is a whole or fractional number equal to or less than 20.

6) The mixture of organophosphonate oligomers according to claim 5 wherein one Ei of at least one of said two or more organophosphonate oligomers is HOC2H4OC2H4- and the other Ei is methyl.

7) The mixture of organophosphonate oligomers according to claim 5 wherein each Ri of said two or more organophosphonate oligomers is methyl or benzyl, wherein methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 10 methyl groups per each benzyl group. 8) The mixture of organophosphonate oligomers according to claim 5 wherein said mixture is characterized as having: a) at least two of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 150 to about 25O⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 400 to about 1000; iii) a viscosity at 25⁰C in the range of from about 2000 to about 10,00OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 15 to about 20wt.%; v) a TGA (thermo gravimetric analysis), profile, of:

9) The mixture of organophosphonate oligomers according to claim 8 wherein the average value of n is in the range of from about 1 to about 5.

10) The mixture of organophosphonate oligomers according to claim 8 wherein the average value of n is in the range of from about 2 to about 3. 11) The mixture of organophosphonate oligomers according to claim 5 wherein said mixture of organophosphonate oligomers contains one or more organophosphonate oligomers wherein each Ei is methyl.

12) A flame retarded formulation comprising at least one synthetic resin and a mixture containing two or more organophosphonate oligomers represented by the general formula:

wherein each Rj is independently selected from methyl, benzyl, or HOC₂H₄OC₂H₄ ^"; each Ei is the same or different and is either HOC₂H₄OC₂H₄ ^' or methyl; and the average of all n's is a whole or fractional number equal to or less than 20.

13) The flame retarded formulation according to claim 12 wherein said mixture of organophosphonate oligomers contains one or more organophosphonate oligomers wherein each Ei is methyl.

14) The flame retarded formulation according to claim 12 wherein each Ri of said mixture of said organophosphonate oligomers is methyl or benzyl, wherein methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 10 methyl groups per each benzyl group.

15) The flame retarded formulation according to claim 12 wherein said mixture of organophosphonate oligomers is characterized as having: a) at least two of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 150 to about 250⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 400 to about 1000; iii) a viscosity at 25⁰C in the range of from about 2000 to about 10,00OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 15 to about 20wt.%; v) a TGA (thermogravimetric analysis), profile, of:

16) The flame retarded formulation according to claim 16 wherein the average value of n of said mixture of organophosphonate oligomers is in the range of from about 1 to about 5.

17) The flame retarded formulation according to claim 16 wherein the synthetic resin is a polyurethane resin.

18) A flame retarded polyurethane foam producable by introducing a polymerization catalyst into a precursor mixture formed from at least an isocyanate, a polyetherpolyol, a surfactant, a catalyst, a blowing agent, and a flame retarding amount of a mixture of organophosphonate oligomers containing two or more organophosphonate oligomers represented by the general formula:

wherein each Rj is independently selected from methyl, benzyl, or HOC₂H₄OC₂ELf; each Ei is the same or different and is either HOC₂H₄OC₂H₄ ^" or methyl; and the average of all n's is a whole or fractional number equal to or less than 20.

19) The flame retarded polyurethane foam according to claim 18 wherein said flame retarded polyurethane foam comprises in the range of from about 4 to about 15 wt%, based on the total weight of the polyurethane foam, of said mixture of organophosphonate oligomers.

20) The flame retarded polyurethane foam according to claim 18 wherein said mixture of organophosphonate oligomers contains one or more organophosphonate oligomers wherein each Ei is methyl.

21) The flame retarded polyurethane foam according to claim 18 wherein each R₁ of said two or more organophosphonate oligomers is methyl or benzyl, wherein methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 10 methyl groups per each benzyl group.

22) The flame retarded polyurethane foam according to claim 18 wherein said mixture of organophosphonate oligomers is characterized as having: a) at least two of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 150 to about 25O⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 400 to about 1000; iii) a viscosity at 25⁰C in the range of from about 2000 to about 10,00OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 15 to about 20wt.%; v) a TGA (thermogravimetric analysis), profile, of:

23) The flame retarded polyurethane foam according to claim 22 wherein the average value of n of said mixture of organophosphonate oligomers is in the range of from about 1 to about 5.

24) The flame retarded polyurethane foam according to claim 22 wherein said flame retarded polyurethane foam exhibits virtually no shrinkage and produces less than 30 mg of fog when subjected to the DIN 75201 test procedure and that achieve an FMVSS 302 rating of SE/NBR.

25) A process for producing a flame retarded polyetherpolyol-based polyurethane foam, which process comprises introducing a polymerization catalyst into a precursor mixture formed from at least an isocyanate, a polyetherpolyol, a surfactant, a catalyst, a blowing agent, and a flame retarding amount of a mixture of organophosphonate oligomers containing two or more organophosphonate oligomers represented by the general formula:

wherein each Ri is independently selected from methyl, benzyl, or HOC₂H₄OC₂H₄ ^"; each E₁ is the same or different and is either HOC₂H₄OC₂H₄ ^" or methyl; and the average of all n's is a whole or fractional number equal to or less than 20. 26) The process according to claim 25 wherein in the range of from about 4 to about 15 wt%, based on the total weight of the polyetherpolyol-based polyurethane foam, of said mixture of organophosphonate oligomers.

27) The process according to claim 25 wherein said mixture of organophosphonate oligomers contains one or more organophosphonate oligomers wherein each Ej is methyl.

28) The process according to claim 25 wherein said mixture of organophosphonate oligomers is characterized as having; a) at least two of i) an onset temperature, as determined by differential scanning calorimetry ("DSC") in the range of from about 150 to about 25O⁰C; ii) a molecular weight, as determined by freeze point depression ("FPD") in the range of from about 400 to about 1000; iii) a viscosity at 25⁰C in the range of from about 2000 to about 10,00OcP; iv) a phosphorous content, as determined by inductively coupled plasma, in the range of from about 15 to about 20wt.%; v) a TGA (thermo gravimetric analysis), profile, of:

29) The process according to any of claims 28 wherein the average value of n of said mixture of organophosphonate oligomers is in the range of from about 1 to about 5.

30) The process according to claim 28 wherein said precursor mixture comprises 8 wt%, based on the total weight of the precursor mixture, of said mixture of organophosphonate oligomers, and said flame retarded polyetherpolyol-based polyurethane foam exhibits virtually no shrinkage and produces less than 30 mg of fog when subjected to the DIN 75201 test procedure and that achieve an FMVSS 302 rating of SE/NBR.

3I) A process for producing an organophosphonate oligomer, which process comprises: a) bringing together (i) trimethyl phosphite and (ii) diethylene glycol in a (i):(ϋ) mole ratio of about 6:5, about 7:6, about 8:7, or about 9:8 to form a first reaction mixture, and heating the first reaction mixture to a temperature in the range of about 75⁰C to about 13O⁰C for a period in the range of about 1 hour to about 4 hours and removing methanol coproduct from this heated reaction mixture to form a first reaction product mixture; b) bringing together benzyl chloride and/or benzyl bromide and first reaction product mixture, to form a second reaction mixture and maintaining this mixture at a temperature in the range of about 9O⁰C to about 15O⁰C, preferably in the range of about HO⁰C to about 13O⁰C for a period in the range of about 1 hour to about 3 hours and then adding a catalytic quantity of alkyl iodide to the resultant reaction product mixture; c) heating the resultant reaction product mixture of b) at a temperature in the range of about 6O⁰C to about 14O⁰C for a period in the range of about 2 hours to about 12 hours and then distilling the resultant reaction product mixture under reduced pressure to remove volatiles from the reaction product mixture.

32) A process for producing an organophosphonate oligomer, which process comprises: a) bringing together (i) trimethyl phosphite and (ii) diethylene glycol in a (i):(ii) mole ratio of about 5+n:5, about 6+n:6, about 7+n:7, or about 8+n:8, where n is a fractional number less than 1, to form a first reaction mixture, and heating the first reaction mixture to a temperature in the range of about 75⁰C to about 13O⁰C for a period in the range of about 1 hour to about 4 hours and removing methanol coproduct from this heated reaction mixture to form a first reaction product composition; b) bringing together an additional quantity of trimethyl phosphite and first reaction product composition, with the temperature of the first reaction product composition being below about 13O⁰C to form a second mixture, said additional quantity of trimethyl phosphite being an amount in moles equal to the fractional number of n in a) such that the total (i):(ii) mole ratio used in a) and b) is about 6:5, about 7:6, about 8:7, or about 9:8, and heating second mixture to a temperature in the range of about 9O⁰C to about 13O⁰C for a period in the range of about 1 hour to about 4 hours and removing methanol coproduct from this heated mixture to form a second reaction product composition; c) bringing together benzyl chloride and/or benzyl bromide with second reaction product composition of b), to form a third mixture and maintaining this mixture at a temperature in the range of about 9O⁰C to about 15O⁰C, preferably in the range of about HO⁰C to about 13O⁰C for a period in the range of about 1 hour to about 3 hours to form a third product composition and then adding a catalytic quantity of alkyl iodide to third product composition; d) heating the third product composition of c) at a temperature in the range of about 6O⁰C to about 140⁰C for a period in the range of about 2 hours to about 12 hours and then distilling the resultant reaction product mixture under reduced pressure to remove volatiles from the reaction product mixture.