Process for preparation of phosphites

Abstract

The present disclosure relates to a process for preparing phosphites. The method comprises reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof with a phosphorus halide to produce a product mixture comprising a hydrohalide and a reaction product comprising a phosphite and a halogenated phosphite, and removing the hydrohalide from the product mixture.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Application No. 18 / 189,516, filed on March 24, 2023, and U.S. Provisional Patent Application No. 63 / 356,749, filed on June 29, 2022, the entire contents of which are hereby incorporated by reference. Background of the Invention

[0004] Phosphites (e.g., organophosphites) have many industrial applications. In this regard, phosphites can be used as additives for many chemical conversions, such as catalysts for accelerating reaction rates, and antioxidants for improving polymer durability, weatherability, material properties, and recyclability for sustainability.

[0005] In addition, these phosphites can use the various technical synthesis of this area.For example, some reaction schemes may need catalyzer.Other reaction schemes may need relatively high temperature.In this respect, in order to obtain the product with gratifying yield and / or purity, such reaction may be more complicated than expectation usually.In addition, along with method being adjusted to more economical and effective, energy friendly and environmentally friendly, can expect to find not too complicated and / or more effective method for making phosphites.

[0006] Thus, there remains a need for more efficient and / or less complex methods of preparing phosphites. SUMMARY OF THE INVENTION

[0008] According to one embodiment of the present invention, a method for preparing a phosphite is disclosed. The method comprises: reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof with a phosphorus halide at a temperature of about 200° C. or less, wherein the hydroxy-substituted compound and the phosphorus halide are reacted in a molar ratio of about 2.3 to about 5 to prepare a product mixture comprising a hydrohalide and a reaction product, wherein the reaction product comprises a phosphite and one or more compounds having the following structure (I) and present in an amount of about 0.3 wt % or more to about 15 wt % or less based on the weight of the reaction product:

[0009] (I)

[0010] wherein R1 is alkyl or aryl, R2 is alkyl or aryl, Y is -Z or -OH, and Z is a halide; and removing the hydrohalide from the product mixture.

[0011] According to another embodiment of the present invention, a method for preparing a phosphite is disclosed. The method includes: reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof with a phosphorus halide, wherein the hydroxy-substituted compound and the phosphorus halide are reacted in a molar ratio of about 2.3 to about 5 to prepare a product mixture comprising a hydrohalide and a reaction product, wherein the reaction product comprises a phosphite and a phosphohalodite, wherein the phosphohalodite is present in an amount of about 0.5 wt % or more to about 15 wt % or less based on the weight of the reaction product; and removing the hydrohalide from the product mixture using a vacuum.

[0012] According to another embodiment of the present invention, a method for preparing phosphite is disclosed. The method includes: reacting a hydroxyl-substituted compound comprising a hydroxyl-substituted alkyl compound, a hydroxyl-substituted aryl compound or a mixture thereof with a phosphorus halide, wherein the hydroxyl-substituted compound and the phosphorus halide are reacted in a molar ratio of about 2.3 to about 5 to prepare a product mixture comprising a hydrohalide and a reaction product, wherein the reaction product comprises a phosphite and a halogenated phosphite, wherein the halogenated phosphite is present in an amount of about 0.5 wt % or more to about 15 wt % or less based on the weight of the reaction product; and removing the hydrohalide from the product mixture using nitrogen sparging and / or nitrogen purging.

[0013] According to another embodiment of the present invention, a method for preparing phosphite is disclosed. The method includes: reacting a hydroxyl-substituted compound comprising a hydroxyl-substituted alkyl compound, a hydroxyl-substituted aryl compound or a mixture thereof with a phosphorus halide, wherein the hydroxyl-substituted compound and the phosphorus halide are reacted in a molar ratio of about 2.3 to about 5 to prepare a product mixture comprising a hydrohalide and a reaction product, wherein the reaction product comprises a phosphite and a halogenated phosphite, wherein the reaction product has a predetermined halide content, wherein the halogenated phosphite is present in an amount of about 0.5 wt % or more to about 15 wt % or less based on the weight of the reaction product; and removing the hydrohalide from the product mixture using a nitrogen purge.

[0014] Other features and aspects of the present disclosure are set forth in greater detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present disclosure will now be described by way of example with reference to the accompanying drawings, in which:

[0017] Figure 1A illustrates a reaction scheme according to one embodiment of the present disclosure;

[0018] Figure 1B illustrates a reaction scheme according to another embodiment of the present disclosure;

[0019] Figure 2 graphically illustrating temperature versus time for a reaction scheme according to one embodiment of the present disclosure, the embodiment comprising a relatively high chloride content;

[0020] Figure 3 graphically illustrating temperature versus time for a reaction scheme according to one embodiment of the present disclosure, the embodiment comprising a relatively low chloride content;

[0021] Figure 4 Graph illustrating the percentage of TTP formation as a function of cresol / PCl3 molar ratio according to one embodiment of the present disclosure;

[0022] Figure 5 Graph illustrating the percentage of phosphochlorodite formation as a function of cresol / PCl3 molar ratio according to one embodiment of the present disclosure;

[0023] Figure 6 Graph illustrating the percentage of cresol remaining as a function of the cresol / PCl3 molar ratio;

[0024] Figure 7 Graph illustrating the chloride ppm in the reaction product as a function of the cresol / PCl3 molar ratio according to one embodiment of the present disclosure;

[0025] Fig. 8A and 8B illustrates a nitrogen sparge tube according to one embodiment of the present disclosure;

[0026] Fig. 9 a process diagram illustrating a reaction scheme according to one embodiment of the present disclosure; and

[0027] Fig.10 A reaction vessel according to one embodiment of the present disclosure is illustrated.

[0028] definition

[0029] It should be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present disclosure.

[0030] "About" means within 5% of the disclosed value.

[0031] "Alkyl" refers to a linear, branched or cyclic monovalent saturated aliphatic hydrocarbon group, and "C q -C r"Alkyl" refers to an alkyl group having q to r carbon atoms. By way of example, the term includes straight chain, branched or cyclic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, and the like.

[0032] "Aryl" refers to an aromatic hydrocarbon group. For example, "C q -C r "Aryl" refers to an aromatic radical having q to r carbon atoms. By way of example, the term includes straight and branched chain hydrocarbon radicals such as phenyl, naphthyl, indenyl, azulenyl, fluorenyl, anthracenyl, phenanthrenyl, tetrahydronaphthyl, indanyl, phenanthridinyl, and the like.

[0033] Details

[0034] Those of ordinary skill in the art will appreciate that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0035] Generally speaking, the present disclosure relates to a method for preparing phosphite. That is, by control methods and treatment conditions, the inventors have found that the method disclosed herein can achieve more effective and efficient reaction. For example, the reaction can be carried out at a relatively low temperature, which itself has its own benefits. In addition, the reaction and the post-reaction step if any can be carried out in a single container. In this regard, the inventors have found that the method disclosed herein can be environmentally friendly and energy friendly. In addition, the method described herein can be carried out in the absence of or in the absence of distillation, circulation or further purification of the reaction product comprising phosphite and any halogenated phosphite such as chlorophosphite. In particular, the method can be carried out in the absence of the distillation for purifying the product mixture or reaction product as defined herein.

[0036] The method according to the present disclosure includes the step of reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound or a mixture thereof with a phosphorus halide. Typically, the hydroxy-substituted compound can be referred to as an alcohol. In one embodiment, the reaction includes a hydroxy-substituted alkyl compound. In another embodiment, the reaction includes a hydroxy-substituted aryl compound. In a further embodiment, the reaction includes a mixture of a hydroxy-substituted alkyl compound and a hydroxy-substituted aryl compound.

[0037] In addition, with respect to the above-mentioned hydroxy-substituted compounds, in one embodiment, such compounds may have only one hydroxy-substituted. In another embodiment, such compounds may have two hydroxy-substituted.

[0038] The alkyl group of the hydroxy-substituted alkyl compound may be C1-C 10 In this regard, the alkyl group may be C1-C 10 Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0039] In addition to the hydroxyl(s) substitution, in one embodiment, the above alkyl group may not include any further substitution. In another embodiment, in addition to the hydroxyl(s) substitution, the above alkyl group may include further substitution. For example, the alkyl group may be an aralkyl group (i.e., an alkyl group substituted with an aryl group). The aryl group may be a C3-C 12 In this regard, the aryl group can be C3-C 12 Aryl, such as C4-C 12 Aryl, such as C6-C 12 Aryl, such as C6-C 10 Aryl, such as C6-C8 aryl, such as C6 aryl.For example, aryl can have 3 or more, such as 4 or more, such as 5 or more, such as 6 or more carbon atoms.Aryl can have 12 or less, such as 10 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.In a specific embodiment, aryl can be phenyl.In addition, in one embodiment, aryl can be polycyclic.Polycyclic aryl can include fused ring, bridged ring and spiro ring system.

[0040] In any case, the hydroxy substituted alkyl compound can be a hydroxy substituted alkyl compound known in the art. For example, the compound can be methanol, ethanol, propanol, butanol, amyl alcohol, cyclopentanol, hexanol, cyclohexanol, etc. and mixtures thereof. In one embodiment, the compound can be methanol, ethanol, propanol, butanol, amyl alcohol, hexanol or mixtures thereof. In further embodiments, the compound can be a cycloalkyl, such as cyclopentanol, cyclohexanol or mixtures thereof.

[0041] The aryl group of the above hydroxy-substituted aryl compound can be C3-C 12 In this regard, the aryl group can be C3-C 12 Aryl, such as C4-C 12 Aryl, such as C6-C 12 Aryl, such as C6-C 10 Aryl, such as C6-C8 aryl, such as C6 aryl.For example, aryl can have 3 or more, such as 4 or more, such as 5 or more, such as 6 or more carbon atoms.Aryl can have 12 or less, such as 10 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.In a specific embodiment, aryl can be phenyl.In addition, in one embodiment, aryl can be polycyclic.Polycyclic aryl can include fused ring, bridged ring and spiro ring system.

[0042] In addition to the hydroxyl substitution(s), in one embodiment, the above aryl may not include any further substitution. In another embodiment, in addition to the hydroxyl substitution(s), the above aryl may include further substitution. For example, the aryl may be an alkaryl (i.e., an aryl substituted with an alkyl group). The alkyl may be C1-C 10 In this regard, the alkyl group may be C1-C 10Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0043] In any case, the hydroxy-substituted aryl compound can be a hydroxy-substituted aryl compound known in the art. For example, the compound can be phenol, benzyl alcohol, etc. In one embodiment, the compound can be phenol. For example, the compound can be phenol, such as phenol without any further substitution. In another embodiment, the phenol can be an alkyl-substituted phenol, such as a dialkyl-substituted phenol. For example, the phenol can include cresol (e.g., o-cresol, m-cresol, p-cresol, or a mixture thereof), xylenol (e.g., 2,6-xylenol, 2,5-xylenol, 2,4-xylenol, 2,3-xylenol, 3,4-xylenol, 3,5-xylenol, or a mixture thereof), or a mixture thereof. In this regard, in one embodiment, the hydroxy-substituted aryl compound can include phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, 2,5-xylenol, 2,4-xylenol, 2,3-xylenol, 3,4-xylenol, 3,5-xylenol, or a mixture thereof. In another embodiment, the hydroxy-substituted aryl compound can include phenol, o-cresol, m-cresol, p-cresol or its mixture. More generally, the hydroxy-substituted aryl compound can include phenol, cresol or its mixture. In this respect, in one embodiment, the hydroxy-substituted aryl compound can include a mixture of phenol and cresol. In a further embodiment, the hydroxy-substituted aryl compound can include cresol, particularly o-cresol, m-cresol, p-cresol or its mixture. In another further embodiment, the hydroxy-substituted aryl compound can include m-cresol, p-cresol or its mixture. In a further embodiment, the hydroxy-substituted aryl compound can include a mixture of m-cresol and p-cresol. In a specific embodiment, the hydroxy-substituted compound, such as the hydroxy-substituted aryl compound, can not include o-cresol.

[0044] When more than one hydroxy-substituted compound is used, such as a first hydroxy-substituted compound and a second hydroxy-substituted compound, the ratio between any two may be within a predetermined ratio. For example, the ratio may be about 0.1 or greater, such as about 0.2 or greater, such as about 0.3 or greater, such as about 0.5 or greater, such as about 0.8 or greater, such as about 1 or greater, such as about 1.2 or greater, such as about 1.4 or greater, such as about 1.5 or greater, such as about 1.6 or greater, such as about 1.7 or greater, such as about 1.8 or greater, such as about 2 or greater, such as about 2.3 or greater, such as about 2.5 or greater, such as about 3 or greater, such as about 4 or greater, such as about 5 or greater. The predetermined ratio may be about 20 or less, such as about 18 or less, such as about 16 or less, such as about 15 or less, such as about 13 or less, such as about 11 or less, such as about 10 or less, such as about 9 or less, such as about 8 or less, such as about 7 or less, such as about 6 or less, such as about 5 or less, such as about 4 or less, such as about 3.8 or less, such as about 3.5 or less, such as about 3.2 or less, such as about 3 or less, such as about 2.8 or less, such as about 2.5 or less, such as about 2.3 or less, such as about 2.1 or less, such as about 2 or less, such as about 1.9 or less, such as about 1.8 or less, such as about 1.7 or less, such as about 1.6 or less, such as about 1.5 or less, such as about 1.3 or less, such as about 1.1 or less, such as about 1 or less. In one embodiment, the above ratio may refer to a weight ratio. In another embodiment, the above ratio may refer to a molar ratio.

[0045] As an example, the hydroxy-substituted compound can be a hydroxy-substituted aromatic compound comprising a combination of meta-cresol and p-cresol. In this regard, as an example, the above ratio can refer to the weight ratio between meta-cresol and p-cresol. In another embodiment, the above ratio can refer to the molar ratio between meta-cresol and p-cresol.

[0046] In one embodiment, the hydroxy-substituted aryl compound may not include phenol (i.e., unsubstituted phenol—phenol with only hydroxy-substituted phenol). In this regard, the hydroxy-substituted compound, particularly the hydroxy-substituted aryl compound, may include about 15 wt % or less, such as about 12 wt % or less, such as about 10 wt % or less, such as about 8 wt % or less, such as about 6 wt % or less, such as about 4 wt % or less, such as about 2 wt % or less, such as about 1 wt % or less, such as about 0.5 wt % or less, such as about 0.3 wt % or less, such as about 0.2 wt % or less, such as about 0.1 wt % or less, such as about 0.05 wt % or less, such as about 0 wt % of phenol. However, for the sake of clarity, the reaction may still include substituted phenols, such as cresol or xylenol, as hydroxy-substituted compounds, particularly hydroxy-substituted aryl compounds. Although the aforementioned hydroxy-substituted aryl compounds are mentioned, it should be understood that, in one embodiment, such restrictions may also be applied to any other reaction feeds (input) or reagents for preparing phosphites. In this regard, in one embodiment, the aforementioned percentages can be applied to any single reaction feed or reagent. In addition, in another embodiment, the aforementioned percentages can be applied to a combination of other reaction feeds or reagents.

[0047] As mentioned above, the reaction includes a phosphorus halide. In this regard, the halide can be a fluoride, a chloride, a bromide, an iodide or a mixture thereof. In one embodiment, the halide can be a chloride. In addition, the phosphorus halide can be a phosphorus trihalide. For example, the phosphorus halide can be phosphorus trifluoride, phosphorus trichloride, phosphorus tribromide, phosphorus triiodide or a mixture thereof. In one embodiment, the phosphorus halide can be phosphorus trichloride.

[0048] The hydroxyl-substituted compound and the phosphorus halide may be used in the reaction in a specific amount. For example, the molar ratio of the hydroxyl-substituted compound to the phosphorus halide may be about 0.1 or more, such as about 0.2 or more, such as about 0.3 or more, such as about 0.5 or more, such as about 0.7 or more, such as about 0.8 or more, such as about 1 or more, such as about 1.2 or more, such as about 1.5 or more, such as about 1.7 or more, such as about 1.9 or more, such as about 2 or more, such as about 2.3 or more, such as about 2.5 or more, such as about 2.7 or more, such as about 2.8 or more, such as about 2.81 or more, such as about 2.82 or more. or greater, such as about 2.83 or greater, such as about 2.84 or greater, such as about 2.85 or greater, such as about 2.86 or greater, such as about 2.87 or greater, such as about 2.88 or greater, such as about 2.89 or greater, such as about 2.9 or greater, such as about 2.91 or greater, such as about 2.92 or greater, such as about 2.93 or greater, such as about 2.94 or greater, such as about 2.95 or greater, such as about 2.96 or greater, such as about 2.97 or greater, such as about 2.98 or greater, such as about 2.99 or greater, such as about 3 or greater. The molar ratio may be about 20 or less, such as about 18 or less, such as about 16 or less, such as about 14 or less, such as about 12 or less, such as about 10 or less, such as about 9 or less, such as about 8 or less, such as about 7 or less, such as about 6 or less, such as about 5 or less, such as about 4.5 or less, such as about 4 or less, such as about 3.5 or less, such as about 3 or less, such as about 2.99 or less, such as about 2.98 or less, such as about 2.97 or less, such as about 2.96 or less, such as about 2.95 or less, such as about 2.94 or less. , such as about 2.93 or less, such as about 2.92 or less, such as about 2.91 or less, such as about 2.9 or less, such as about 2.89 or less, such as about 2.88 or less, such as about 2.87 or less, such as about 2.86 or less, such as about 2.85 or less, such as about 2.84 or less, such as about 2.83 or less, such as about 2.82 or less, such as about 2.81 or less, such as about 2.8 or less, such as about 2.7 or less, such as about 2.5 or less, such as about 2 or less, such as about 1.8 or less, such as about 1.5 or less. For example, the molar ratio can be about 2.3 to about 5, such as about 2.3 to about 4, such as about 2.3 to about 3.5, such as about 2.3 to less than about 3. The minimum value in the aforementioned range can be any one of about 2.5, about 2.6, about 2.7, and about 2.8. In one embodiment, the molar ratio may be from about 2.8 to about 2.9, such as from about 2.85 to about 2.9. In another embodiment, the molar ratio may be from about 2.9 to less than about 3, such as from about 2.95 to less than about 3.

[0049] In this regard, the hydroxyl-substituted compound may be present in an amount of about 50 mol% or more, such as about 55 mol% or more, such as about 60 mol% or more, such as about 65 mol% or more, such as about 70 mol% or more, such as about 75 mol% or more, such as about 80 mol% or more, such as about 85 mol% or more, such as about 90 mol% or more, such as about 95 mol% or more, based on the total moles of the hydroxyl-substituted compound and the phosphorus halide. The hydroxyl-substituted compound may be present in an amount of less than about 100 mol%, such as about 95 mol% or less, such as about 90 mol% or less, such as about 85 mol% or less, such as about 80 mol% or less, such as about 75 mol% or less, based on the total moles of the hydroxyl-substituted compound and the phosphorus halide.

[0050] In addition, the phosphorus halide may be present in an amount of about 50 mol% or less, such as about 45 mol% or less, such as about 40 mol% or less, such as about 35 mol% or less, such as about 30 mol% or less, such as about 25 mol% or less, such as about 20 mol% or less, such as about 15 mol% or less, such as about 10 mol% or less, based on the total moles of the hydroxyl-substituted compound and the phosphorus halide. The phosphorus halide may be present in an amount greater than 0 mol%, such as about 1 mol% or greater, such as about 2 mol% or greater, such as about 5 mol% or greater, such as about 10 mol% or greater, such as about 15 mol% or greater, such as about 20 mol% or greater, such as about 25 mol% or greater, based on the total moles of the hydroxyl-substituted compound and the phosphorus halide.

[0051] As described herein, the reaction can occur in a container, particularly a single container. The reaction vessel can be any container that is commonly used for such a reaction. For example, the container can be a container that realizes batch processing. In any case, in one embodiment, the mode of introducing reactants is not necessarily limited. In another embodiment, at least some, such as all hydroxyl-substituted compounds can be first provided in the container. After this, the phosphorus halide can be provided or loaded into the container. In one embodiment, the phosphorus halide can be provided or loaded under the surface (i.e., under the surface of cresol-cresol / gas interface).

[0052] As an example, the reaction vessel may be Fig.10Container illustrated. For example, container 1000 may include a stirrer 1002, such as an impeller or a mixer. The container may also include an inlet 1004 for introducing a hydroxy-substituted compound such as cresol, and an optional second inlet 1006 for adding a phosphorus halide. In addition, the container may also include an inlet 1008, such as an inlet for introducing a phosphorus halide such as phosphorus trichloride under the surface. The container may also include an outlet 1010 for removing hydrogen halides such as hydrogen chloride and any nitrogen that may be introduced via a nitrogen purge 1012 and / or a nitrogen injection 1014. The container may also include one or more inlets 1008 for passing through a subsurface nitrogen injection of a reaction mass. In addition, the container may include a port or inlet 1012 for realizing a negative pressure or vacuum.

[0053] In addition, phosphorus halide can be provided or loaded over a period of time. For example, phosphorus halide can be provided in about 0.1 hours or longer, such as about 0.5 hours or longer, such as about 1 hour or longer, such as about 1.5 hours or longer, such as about 2 hours or longer, such as about 3 hours or longer, such as about 4 hours or longer, such as about 5 hours or longer. Phosphorus halide can be provided in about 10 hours or less, such as about 8 hours or less, such as about 6 hours or less, such as about 5 hours or less, such as about 4 hours or less, such as about 3 hours or less.

[0054] Similarly, based on the total volume of the phosphorus halide to be introduced, it can be introduced at a certain rate. For example, the introduction rate of the phosphorus halide can be at least 0.1% / minute, such as at least 0.2% / minute, such as at least 0.3% / minute, such as at least 0.5% / minute, such as at least 0.6% / minute, such as at least 0.8% / minute, such as at least 1% / minute, such as at least 1.1% / minute, such as at least 1.2% / minute, such as at least 1.5% / minute, wherein % is based on the total volume of the phosphorus halide to be loaded. In addition, the rate can be 10% / minute or less, such as 9% / minute or less, such as 8% / minute or less, such as 7% / minute or less, such as 6% / minute or less, such as 5% / minute or less, such as 4% / minute or less, such as 3% / minute or less, such as 2.8% / minute or less, such as 2.5% / minute or less, such as 2.2% / minute or less, such as 2% / minute or less, such as 1.8% / minute or less, such as 1.5% / minute or less, such as 1.3% / minute or less, such as 1.1% / minute or less, such as 1% / minute or less, wherein the % is based on the total volume of the phosphorus halide to be loaded.

[0055] In addition, the phosphorus halide can be introduced or loaded at a relatively low temperature. In other words, the contents of the container can be at a reduced temperature. For example, the temperature can be about 150°C or lower, such as about 140°C or lower, such as about 130°C or lower, such as about 120°C or lower, such as about 110°C or lower, such as about 100°C or lower, such as about 90°C or lower, such as about 80°C or lower, such as about 70°C or lower, such as about 60°C or lower. The temperature can be room temperature or higher. For example, the temperature can be about 20°C or higher, such as about 25°C or higher, such as about 30°C or higher, such as about 40°C or higher, such as about 50°C or higher, such as about 60°C or higher, such as about 70°C or higher, such as about 80°C or higher, such as about 90°C or higher. If necessary, cooling methods known in the art can be used to maintain such a temperature of the container.

[0056] By using the method disclosed herein, the reaction itself can also be carried out at a relatively low temperature. For example, the reaction can be carried out at about 250°C or lower, such as about 230°C or lower, such as about 210°C or lower, such as about 200°C or lower, such as about 180°C or lower, such as about 160°C or lower, such as about 150°C or lower, such as about 140°C or lower, such as about 130°C or lower, such as about 120°C or lower, such as about 110°C or lower, such as about 100°C or lower, such as about 90°C or lower, such as about 80°C or lower, such as about 70°C or lower, such as about 60°C or lower. The reaction temperature can be room temperature or higher. For example, the temperature may be about 20°C or higher, such as about 25°C or higher, such as about 30°C or higher, such as about 40°C or higher, such as about 50°C or higher, such as about 60°C or higher, such as about 70°C or higher, such as about 80°C or higher, such as about 90°C or higher, such as about 100°C or higher, such as about 110°C or higher, such as about 120°C or higher, such as about 130°C or higher, such as about 140°C or higher. In one embodiment, the reaction temperature may be a temperature higher than the temperature at which the phosphorus halide is introduced.

[0057] Thus, after the loading of the phosphorus halide is complete, the temperature can be raised to the reaction temperature. Typically, such a temperature increase can use any heating method known in the art. For example, as an example, this can include a heating jacket.

[0058] In one embodiment, the reaction can be carried out in a solvent. For example, the solvent can be an aprotic solvent. The solvent can include an aliphatic solvent, an aromatic solvent or a mixture thereof. Examples of such solvents can include toluene, xylene, ethylbenzene, etc. However, in another embodiment, the reaction can be carried out in the absence of a solvent.

[0059] In one embodiment, the reaction can be carried out in the absence of a catalyst such as an amine-based catalyst. In this regard, the hydroxy-substituted compound and the phosphorus halide can react based on the reaction conditions themselves so that no catalyst is required to form a product mixture comprising a hydrohalide and a reaction product, wherein the reaction product comprises a phosphite, wherein the reaction product has a predetermined halide content.

[0060] In addition, the reaction can be carried out under any pressure that allows to form phosphite.For example, the reaction can be carried out under about 0.5 atm or higher, such as about 0.6 atm or higher, such as about 0.7 atm or higher, such as about 0.8 atm or higher, such as about 0.9 atm or higher, such as about 1 atm or higher pressure.Pressure can be about 1.5 atm or less, such as about 1.4 atm or less, such as about 1.3 atm or less, such as about 1.2 atm or less, such as about 1.1 atm or less.Pressure can be about 1 atm.

[0061] In addition, the reaction times may be relatively shorter than some traditional methods.For example, the reaction times can be about 15 hours or less, such as about 14 hours or less, such as about 13 hours or less, such as about 12 hours or less, such as about 11 hours or less, such as about 10 hours or less, such as about 9 hours or less, such as about 8 hours or less, such as about 7 hours or less, such as about 6 hours or less, such as about 5 hours or less, such as about 4 hours or less, such as about 3 hours or less, such as about 2 hours or less.The reaction times can be about 0.5 hour or longer, such as about 1 hour or longer, such as about 2 hours or longer, such as about 3 hours or longer, such as about 4 hours or longer, such as about 5 hours or longer, such as about 6 hours or longer, such as about 7 hours or longer, such as about 8 hours or longer, such as about 9 hours or longer, such as about 10 hours or longer, such as about 11 hours or longer, such as about 12 hours or longer.

[0062] In general, the reaction between the hydroxy substituted compound and the phosphorus halide will produce a product mixture comprising a hydrohalide and a reaction product. The reaction product comprises at least one phosphite. In another embodiment, the reaction product comprises a phosphite and one or more halogenated phosphites. In a specific embodiment, the reaction product comprises a phosphite and a halogenated phosphite. A reaction scheme according to one embodiment of the present disclosure is shown in Figure 1AThis reaction scheme illustrates the reaction between m-cresol / p-cresol and phosphorus trichloride for the synthesis of tritolyl phosphite and the corresponding chlorophosphite. However, as shown herein, it should be understood that the reaction can also be carried out using phenol with one or more hydroxy-substituted compounds such as one or more cresols and phosphorus trichloride, such as Figure 1B shown.

[0063] As mentioned above, the reaction may result in the formation of a hydrohalide, usually as a byproduct. The halide may be determined by the halide used in the phosphorus halide used for the reaction. In this regard, the hydrohalide may be hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide or a mixture thereof. In one embodiment, the hydrohalide may be hydrogen chloride (HCl). In this regard, and without intending to be limited by theory, the inventors have found that effectively removing the hydrohalide can achieve the reaction to proceed in an effective manner. For example, without intending to be limited by theory, such removal can achieve an accelerated reaction rate.

[0064] In this regard, the present disclosure may also include a step of removing the hydrohalide. In one embodiment, such removal may begin after the phosphorus halide, particularly all of the phosphorus halide, has been loaded. In one embodiment, such removal may begin before the reaction temperature reaches the final temperature. For example, when the temperature of the contents is raised to the final reaction temperature (e.g., about 150° C.), the hydrohalide may be removed using the methods disclosed herein. Without intending to be limited by theory, such a method may achieve a reduction in cycle time.

[0065] Typically, in one embodiment, the removal will be carried out in a container for the reaction. Various methods for removing hydrohalides such as hydrogen chloride may include vacuum, inert gas injection, inert gas purge, catalyst, or a combination thereof. In one embodiment, the removal may include inert gas injection and vacuum. For example, a vacuum may be used first; thereafter, the vacuum may be stopped, and an inert gas injection may be performed. In a further embodiment, the removal may include vacuum and inert gas purge. For example, a vacuum may be used first, and then the vacuum may be stopped before the inert gas purge is started; however, it is understood that such steps may also be reversed. In a further embodiment, the removal may include inert gas injection and inert gas purge. For example, before the inert gas injection is started, an inert gas purge may be started and then stopped; however, it is understood that such steps may also be reversed in one embodiment. In a further embodiment, the removal may include vacuum, inert gas injection, and inert gas purge.

[0066] As described above, injection and / or purging may include an inert gas. The inert gas may be an inert gas commonly used in the art, and there is no need to limit it. For example, the inert gas may be a rare gas. In one embodiment, the inert gas may be helium. In another embodiment, the inert gas may be nitrogen. In this regard, the aforementioned inert gas injection may refer to nitrogen injection. Similarly, the aforementioned inert gas purge may refer to nitrogen purge.

[0067] In one embodiment, the removal can use a vacuum. Based on absolute values, in one embodiment, the vacuum pressure is less than 760 mmHg, such as 750 mmHg or less, such as 700 mmHg or less, such as 650 mmHg or less, such as 600 mmHg or less, such as 550 mmHg or less, such as 500 mmHg or less, such as 450 mmHg or less, such as 400 mmHg or less, such as 350 mmHg or less, such as 300 mmHg or less, such as 250 mmHg such as 200 mmHg or less, such as 150 mmHg or less, such as 100 mmHg or less, such as 50 mmHg or less. The vacuum pressure may be 0 mmHg or higher, such as 25 mmHg or higher, such as 50 mmHg or higher, such as 100 mmHg or higher, such as 150 mmHg or higher, such as 200 mmHg or higher, such as 250 mmHg or higher, such as 300 mmHg or higher, such as 350 mmHg or higher, such as 400 mmHg or higher, such as 450 mmHg or higher. In addition, when using vacuum, the final vacuum pressure may be achieved via one or more steps. For example, the pressure may be reduced to a first reduced pressure and then reduced to a second reduced pressure. The pressure may be maintained at the first reduced pressure for a period of time and then maintained at the second reduced pressure for a period of time. The time period maintained at the first reduced pressure may be 2% or more of the total time of using vacuum, such as 5% or more, such as 8% or more, such as 10% or more, such as 12% or more, such as 15% or more, such as 20% or more. The time period may be 50% or less of the total time the vacuum is used, such as 40% or less, such as 30% or less, such as 25% or less, such as 20% or less, such as 15% or less, such as 10% or less. In this regard, such a pressure drop may be a step drop, rather than a gradual drop to the final vacuum pressure over a period of time.

[0068] In another embodiment, the removal may be performed using an inert gas sparge, such as a nitrogen sparge. In this regard, the sparge is typically a subsurface sparge, wherein the inert gas is introduced and moved through the reaction medium, which typically contains the reactants, reagents, and any byproducts / products of synthesis (product mixture). As just one example, a sintered nitrogen sparge tube may be used to provide the nitrogen (e.g., Fig. 8A and 8B As shown). In the embodiment of continuous use of nitrogen purge and nitrogen injection, the tube can be used for one purpose on the surface or under the surface, and then transferred for another purpose under the surface or on the surface, respectively. The pressure of an inert gas such as nitrogen is a relatively low pressure. For example, the pressure can be 1 psi or higher, such as 2 psi or higher, such as 3 psi or higher, such as 5 psi or higher, such as 10 psi or higher, such as 15 psi or higher, such as 20 psi or higher, such as 30 psi or higher, such as 40 psi or higher. The pressure can be 50 psi or less, such as 45 psi or less, such as 40 psi or less, such as 35 psi or less, such as 30 psi or less, such as 25 psi or less, such as 20 psi or less, such as 15 psi or less, such as 10 psi or less, such as 8 psi or less, such as 6 psi or less, such as 4 psi or less, such as 3 psi or less, such as 2 psi or less, such as 1.5 psi or less. The flow rate may be 0.1 L / min or more, such as 0.2 L / min or more, such as 0.3 L / min or more, such as 0.5 L / min or more, such as 0.8 L / min or more, such as 1 L / min or more, such as 1.1 L / min or more, such as 1.3 L / min or more, such as 1.5 L / min or more. The space velocity may be 0.01 s -1 or higher, such as 0.05 s -1 or higher, such as 0.1 s -1 or higher, such as 0.2 s -1 or higher, such as 0.3 s -1 or higher, such as 0.4 s -1 or higher, such as 0.5 s -1 or higher, such as 0.7 s -1 or higher, such as 0.9 s -1 or higher, such as 1 s -1 or higher, such as 1.1 s -1 or higher, such as 1.3s -1 or higher, such as 1.5 s -1 or higher, such as 1.7 s -1 or higher, such as 1.9 s -1or higher, such as 2 s -1 or higher, such as 3 s -1 or higher, such as 5 s -1 or higher, such as 10 s -1 or higher. The airspeed can be 50 s -1 or smaller, such as 40s -1 or less, such as 30 s -1 or less, such as 25 s -1 or less, such as 20 s -1 or less, such as 15 s -1 or less, such as 10 s -1 or smaller, such as 9 s -1 or smaller, such as 8 s -1 or smaller, such as 7 s -1 or smaller, such as 6 s -1 or less, such as 5 s -1 or smaller, such as 4 s -1 or less, such as 3 s -1 or less, such as 2 s -1 or less, such as 1.5 s -1 or smaller, such as 1 s -1 or smaller, such as 0.8 s -1 or smaller, such as 0.6 s -1 or smaller, such as 0.5 s -1 or smaller, such as 0.4s -1 The maximum flow rate and / or space velocity need not be limited as long as the flow does not adversely affect the reaction conditions and the vessel contents.

[0069] In further embodiments, removal can use inert gas purging, such as nitrogen purging. In this respect, nitrogen purging is typically nitrogen purging on the surface, wherein nitrogen is introduced and typically moves above the reaction medium, and the reaction medium typically comprises reactants, reagents and any synthetic byproducts / products (product mixtures). The pressure of an inert gas such as nitrogen is a relatively low pressure. For example, the pressure can be 1 psi or higher, such as 2 psi or higher, such as 3 psi or higher, such as 5 psi or higher, such as 10 psi or higher, such as 15 psi or higher, such as 20 psi or higher, such as 30 psi or higher, such as 40 psi or higher. The pressure may be 50 psi or less, such as 45 psi or less, such as 40 psi or less, such as 35 psi or less, such as 30 psi or less, such as 25 psi or less, such as 20 psi or less, such as 15 psi or less, such as 10 psi or less, such as 8 psi or less, such as 6 psi or less, such as 4 psi or less, such as 3 psi or less, such as 2 psi or less, such as 1.5 psi or less. The flow rate may be 1 mL / min or more, such as 2 mL / min or more, such as 5 mL / min or more, such as 10 mL / min or more, such as 15 mL / min or more, such as 20 mL / min or more, such as 25 mL / min or more, such as 30 mL / min or more, such as 40 mL / min or more, such as 50 mL / min or more, such as 60 mL / min or more, such as 70 mL / min or more, such as 80 mL / min or more, such as 90 mL / min or more. The airspeed can be 0.01 s -1 or higher, such as 0.05s -1 or higher, such as 0.1 s -1 or higher, such as 0.2 s -1 or higher, such as 0.3 s -1 or higher, such as 0.4 s -1 or higher, such as 0.5 s -1 or higher, such as 0.7 s -1 or higher, such as 0.9 s -1 or higher, such as 1 s- 1 or higher, such as 1.1 s -1 or higher, such as 1.3 s -1 or higher, such as 1.5 s -1 or higher, such as 1.7 s -1 or higher, such as 1.9 s -1 or higher, such as 2 s -1 or higher, such as 3 s-1 or higher, such as 5 s -1 or higher, such as 10 s -1 or higher. The airspeed can be 50 s -1 or less, such as 40 s -1 or less, such as 30 s -1 or less, such as 25 s -1 or less, such as 20 s -1 or less, such as 15 s -1 or less, such as 10 s -1 or smaller, such as 9 s -1 or smaller, such as 8 s -1 or smaller, such as 7 s -1 or smaller, such as 6 s -1 or less, such as 5 s -1 or smaller, such as 4 s -1 or less such as 3 s -1 or less, such as 2 s -1 or less, such as 1.5 s -1 or smaller, such as 1 s -1 or smaller, such as 0.8 s -1 or smaller, such as 0.6 s -1 or smaller, such as 0.5 s -1 or smaller, such as 0.4 s -1 or less. The maximum flow rate need not be limited as long as the flow does not adversely affect the reaction conditions and the vessel contents.

[0070] In further embodiments, the removal may use a catalyst. For example, the catalyst may be a base catalyst. The catalyst may react with the hydrohalide to form an amine salt. In this regard, the base catalyst may be a nitrogen-containing catalyst. In addition to removing the hydrohalide, the catalyst may also help to accelerate the reaction rate.

[0071] Catalyst can include alkylamine, nitrogen-containing heterocyclic compound or its mixture.In one embodiment, catalyst can include alkylamine, such as monoalkylamine, dialkylamine, trialkylamine or its mixture.In one embodiment, alkylamine can include monoalkylamine.In another embodiment, alkylamine can include dialkylamine.In a further embodiment, alkylamine can include trialkylamine.Alkylamine can include triethylamine, dimethyl dodecylamine, dimethyl laurylamine, N-methyl octadecylamine, dibutylamine etc. and its mixture.In one embodiment, alkylamine can include triethylamine.

[0072] In addition, amines can include nitrogen-containing heterocyclic compounds, such as saturated heterocyclic compounds and / or unsaturated heterocyclic compounds. The compound can include pyrrolidine, pyrrole, imidazolidine, pyrazolidine, triazole, tetrazole, piperidine, pyridine, triazine, etc. and mixtures thereof. In one embodiment, the compound can include pyrrolidine, such as N-methylpyrrolidine. In addition, nitrogen-containing heterocyclic compounds can include fused rings or condensed rings. For example, this can include compounds with 7 or more, such as 8 or more, such as 9 or more atoms in the inner ring structure, including at least one nitrogen. This can include compounds with 12 or less, such as 11 or less, such as 10 or less, such as 9 or less atoms in the inner ring structure, including at least one nitrogen. As an example, amines including fused heterocycles can include diazabicycloundecene.

[0073] The removal of the aforementioned hydrohalide can be carried out while the reaction is carried out. In this respect, it can be carried out while introducing a phosphorus halide. In another embodiment, it can be introduced into a phosphorus halide, such as being completely introduced into a container and then removed. In addition, such as by using an inert gas jet, removal can last for a certain period of time. For example, the time can be about 0.1 hours or longer, such as about 0.2 hours or longer, such as about 0.5 hours or longer, such as about 1 hour or longer, such as about 1.5 hours or longer, such as about 2 hours or longer, such as about 3 hours or longer, such as about 4 hours or longer, such as about 5 hours or longer. The time can be about 10 hours or less, such as about 8 hours or less, such as about 6 hours or less, such as about 5 hours or less, such as about 4 hours or less, such as about 3 hours or less, such as about 2 hours or less, such as about 1.5 hours or less, such as about 1 hour or less, such as about 0.8 hours or less, such as about 0.5 hours or less.

[0074] As described above, the removal of the hydrohalide can start before the reaction temperature reaches the final temperature. In this regard, such removal can start at about 150°C or lower, such as about 140°C or lower, such as about 130°C or lower, such as about 120°C or lower, such as about 110°C or lower, such as about 100°C or lower, such as about 90°C or lower, such as about 80°C or lower, such as about 70°C or lower, such as about 60°C or lower. For example, the temperature can be about 20°C or higher, such as about 25°C or higher, such as about 30°C or higher, such as about 40°C or higher, such as about 50°C or higher, such as about 60°C or higher, such as about 70°C or higher, such as about 80°C or higher, such as about 90°C or higher.

[0075] Once the reaction has been completed and the hydrohalide has been removed, the hydrohalide can be treated with methods known in the art. In addition, after the hydrohalide is removed from the container, the reaction product can be cooled. Thereafter, the reaction product can be stored. It can be stored in an inert atmosphere. For example, the inert gas used for storage can be an inert gas disclosed herein.

[0076] Method disclosed herein can also have a relatively short cycle time.Generally, the cycle time can be defined as the time from the time of introducing the hydroxy-substituted compound to the time when the product is discharged from the reaction vessel.For example, the cycle time can be about 15 hours or less, such as about 14 hours or less, such as about 13 hours or less, such as about 12 hours or less, such as about 11 hours or less, such as about 10 hours or less, such as about 9 hours or less, such as about 8 hours or less, such as about 7 hours or less, such as about 6 hours or less, such as about 5 hours or less, such as about 4 hours or less, such as about 3 hours or less, such as about 2 hours or less.The cycle time can be about 0.5 hours or more, such as about 1 hour or more, such as about 2 hours or more, such as about 3 hours or more, such as about 4 hours or more, such as about 5 hours or more, such as about 6 hours or more, such as about 7 hours or more, such as about 8 hours or more, such as about 9 hours or more, such as about 10 hours or more, such as about 11 hours or more, such as about 12 hours or more.

[0077] In addition, about reaction, can determine reaction completion based on the residual amount of the compound of remaining hydroxyl substitution.For example, when the compound of hydroxyl substitution is with about 5 weight % or less, such as about 4 weight % or less, such as about 3 weight % or less, such as about 2.5 weight % or less, such as about 2 weight % or less, such as about 1.5 weight % or less amount existence, can determine reaction completion.

[0078] As described above, the reaction produces a product mixture comprising a reaction product. The reaction product comprises a phosphite. Typically, the phosphite may have the following structure:

[0079]

[0080] in

[0081] R 21 , R 22 and R 23 Each is independently an alkyl group or an aryl group.

[0082] In one embodiment, R 21 , R 22 and R 23 In another embodiment, at least one of R 21 , R22 and R 23 In a further embodiment, at least two of R 21 , R 22 and R 23 All three of the above may be alkyl. In one embodiment, the alkyl may be an unsubstituted alkyl. In another embodiment, the alkyl may be a substituted alkyl. For example, the alkyl may be an aralkyl (i.e., an alkyl substituted with an aryl group).

[0083] For example, the alkyl group may be C1-C 10 In this regard, the alkyl group may be C1-C 10 Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0084] With regard to the substituted alkyl, in one embodiment, it can be an aralkyl (i.e., an alkyl substituted with an aryl group). The aryl group can be C3-C 12 In this regard, the aryl group can be C3-C 12 Aryl, such as C4-C 12 Aryl, such as C6-C 12 Aryl, such as C6-C 10 Aryl, such as C6-C8 aryl, such as C6 aryl.For example, aryl can have 3 or more, such as 4 or more, such as 5 or more, such as 6 or more carbon atoms.Aryl can have 12 or less, such as 10 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.In a specific embodiment, aryl can be phenyl.In addition, in one embodiment, aryl can be polycyclic.Polycyclic aryl can include fused ring, bridged ring and spiro ring system.

[0085] In one embodiment, R 21 , R 22 and R 23 In another embodiment, at least one of R 21 , R 22 and R 23 In a further embodiment, at least two of R 21 , R 22 and R 23 All three of can be aryl. In one embodiment, the aryl can be an unsubstituted aryl. In another embodiment, the aryl can be a substituted aryl. For example, the aryl can be an alkaryl (i.e., an aryl substituted by an alkyl group).

[0086] For example, the aryl group can be C3-C 12 In this regard, the aryl group can be C3-C 12 Aryl, such as C4-C 12 Aryl, such as C6-C 12 Aryl, such as C6-C 10 Aryl, such as C6-C8 aryl, such as C6 aryl.For example, aryl can have 3 or more, such as 4 or more, such as 5 or more, such as 6 or more carbon atoms.Aryl can have 12 or less, such as 10 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.In a specific embodiment, aryl can be phenyl.In addition, in one embodiment, aryl can be polycyclic.Polycyclic aryl can include fused ring, bridged ring and spiro ring system.

[0087] As for the substituted aryl, it may be an alkaryl (i.e., an aryl substituted with an alkyl group). The alkyl group may be C1-C 10 In this regard, the alkyl group may be C1-C 10Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0088] In this regard, in one embodiment, the phosphite can be a trialkyl phosphite. In another embodiment, the phosphite can be a triaryl phosphite. In another embodiment, the phosphite can be a dialkyl monoaryl phosphite. In a further embodiment, the phosphite can be a diaryl monoalkyl phosphite.

[0089] In particular, when R 21 , R 22 and R 23 When the phosphite is an aromatic group (e.g., an alkaryl group), the phosphite may have the following structure:

[0090]

[0091] in

[0092] R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 is independently hydrogen or alkyl.

[0093] In this regard, in one embodiment, the substituents of the foregoing structures may all be hydrogen. However, as described above, the substituents may independently be alkyl groups. The alkyl groups may correspond to those mentioned herein. For example, the alkyl group may be C1-C 10 In this regard, the alkyl group may be C1-C 10Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0094] In addition, each aryl group may have at least one alkyl substitution. In this regard, at least one, such as at least two, such as all three aryl groups may have at least one alkyl substitution. Thus, in one embodiment, at least one of R4, R5, R6, R7 and R8 may be an alkyl group. In one embodiment, R9, R 10 , R 11 , R 12 and R 13 At least one of may be an alkyl group. 14 , R 15 , R 16 , R 17 and R 18 In this regard, at least one of R4, R5, R6, R7 and R8, R9, R 10 , R 11 , R 12 and R 13 At least one of R 14 , R 15 , R 16 , R 17 and R 18 At least one of may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group.

[0095] As described herein, the hydroxy substituted compound used to prepare the phosphite can be p-cresol. In this regard, R6, R 11 and R 16 At least one of R6, R11 and R 16 At least two of R6 and R4 may be alkyl groups, such as C1-C4 alkyl groups, such as methyl groups. 11 and R 16 Each is an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. In such an embodiment, the remaining substituents may independently be hydrogen.

[0096] Also as described herein, the hydroxy substituted compound used to prepare the phosphite can be m-cresol. In this regard, at least one of R5 and R7 can be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. In one embodiment, R 10 and R 12 At least one of may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. In a further embodiment, R 15 and R 17 At least one of R5 and R7 may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. 10 and R 12 At least one of R 15 and R 17 At least one of the substituents may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. In such an embodiment, the remaining substituents may independently be hydrogen.

[0097] In addition, as described herein, the hydroxy-substituted compound used to prepare the phosphite can be m-cresol, p-cresol, or a mixture thereof. In this regard, at least one of R5, R6, and R7 can be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. Similarly, R 10 , R 11 and R 12 At least one of may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. 15 , R 16 and R 17 At least one of R5, R6 and R7 may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. 10 , R 11 and R 12 At least one of R 15 , R 16 and R 17 At least one of the substituents may be an alkyl group, such as a C1-C4 alkyl group, such as a methyl group. In such an embodiment, the remaining substituents may independently be hydrogen.

[0098] Although the foregoing structure is used to depict phosphites, it will be appreciated that a variety of phosphites may be produced in view of such structure, as long as they meet the structure and corresponding definitions. In this regard, the reaction product may include phosphites, such as a mixture of phosphites having the foregoing structure.

[0099] Generally, in one embodiment, the phosphite may include a compound having the following structure:

[0100]

[0101] In particular, when a hydroxy-substituted compound containing p-cresol is used, the phosphite may include a compound having the following structure:

[0102]

[0103] As mentioned above, the reaction product comprises phosphite. However, the reaction product may also comprise the compound of one or more structures (I). In this respect, the reaction product may also comprise halogenated phosphite. In this respect, in one embodiment, the reaction product comprises phosphite and halogenated phosphite.

[0104] Regarding the halophosphite, the compound can be based on the specific type of phosphorus halide used in the reaction. For example, when the phosphorus halide is a phosphorus chloride, such as phosphorus trichloride, the halophosphite can be a chlorophosphite.

[0105] In this regard, the reaction product may include a compound having the following structure (I):

[0106] (I)

[0107] in

[0108] R1 is an alkyl group or an aryl group;

[0109] R2 is an alkyl group or an aryl group;

[0110] Y is -Z; and

[0111] Z is a halide.

[0112] As described above, Z is a halide. The halide may be a fluoride, a chloride, a bromide, an iodide, or a mixture thereof. In one embodiment, the halide may be a chloride.

[0113] As described above, R1 and R2 are each independently an alkyl or aryl group. In one embodiment, one or both may be an alkyl group. In another embodiment, one or both may be an aryl group. In addition, in one embodiment, R1 and R2 may correspond to R above. 21 and R 22.

[0114] In one embodiment, at least one of R1 and R2 can be an alkyl group. In another embodiment, both R1 and R2 can be an alkyl group. In one embodiment, the alkyl group can be an unsubstituted alkyl group. In another embodiment, the alkyl group can be a substituted alkyl group. For example, the alkyl group can be an aralkyl group (i.e., an alkyl group substituted with an aryl group).

[0115] For example, the alkyl group may be C1-C 10 In this regard, the alkyl group may be C1-C 10 Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0116] With regard to the substituted alkyl, in one embodiment, it can be an aralkyl (i.e., an alkyl substituted with an aryl group). The aryl group can be C3-C 12 In this regard, the aryl group can be C3-C 12 Aryl, such as C4-C 12 Aryl, such as C6-C 12 Aryl, such as C6-C 10 Aryl, such as C6-C8 aryl, such as C6 aryl.For example, aryl can have 3 or more, such as 4 or more, such as 5 or more, such as 6 or more carbon atoms.Aryl can have 12 or less, such as 10 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.In a specific embodiment, aryl can be phenyl.In addition, in one embodiment, aryl can be polycyclic.Polycyclic aryl can include fused ring, bridged ring and spiro ring system.

[0117] In one embodiment, at least one of R1 and R2 can be an aryl group. In another embodiment, both R1 and R2 can be an aryl group. In one embodiment, the aryl group can be an unsubstituted aryl group. In another embodiment, the aryl group can be a substituted aryl group. For example, the aryl group can be an alkaryl group (i.e., an aryl group substituted by an alkyl group).

[0118] For example, the aryl group can be C3-C 12 In this regard, the aryl group can be C3-C 12 Aryl, such as C4-C 12 Aryl, such as C6-C 12 Aryl, such as C6-C 10 Aryl, such as C6-C8 aryl, such as C6 aryl.For example, aryl can have 3 or more, such as 4 or more, such as 5 or more, such as 6 or more carbon atoms.Aryl can have 12 or less, such as 10 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.In a specific embodiment, aryl can be phenyl.In addition, in one embodiment, aryl can be polycyclic.Polycyclic aryl can include fused ring, bridged ring and spiro ring system.

[0119] As for the substituted aryl, it may be an alkaryl (i.e., an aryl substituted with an alkyl group). The alkyl group may be C1-C 10 In this regard, the alkyl group may be C1-C 10 Alkyl, such as C1-C8 alkyl, such as C1-C6 alkyl, such as C1-C4 alkyl, such as C1-C3 alkyl, such as C1-C2 alkyl, such as C1 alkyl. For example, alkyl can have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. Alkyl can have 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In this respect, alkyl can be heptyl, hexyl, pentyl (such as n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl), butyl (such as n-butyl, sec-butyl, isobutyl, tert-butyl), propyl (such as n-propyl, isopropyl), ethyl, methyl etc. In a specific embodiment, alkyl can be methyl. In addition, alkyl can be straight chain, branched or cyclic. In one embodiment, alkyl is straight chain. In another embodiment, alkyl is branched. In a further embodiment, the alkyl group is cyclic (or cycloalkyl).

[0120] When R1 is an aryl group, the aforementioned compound may have the following structure:

[0121]

[0122] in

[0123] R2, R4, R5, R6, R7, R8 and Z are as defined above.

[0124] In particular, the aforementioned compounds may have the following structure, wherein the aryl group includes alkyl substitution, in particular methyl substitution:

[0125]

[0126] in

[0127] R2 and Z are as defined above.

[0128] When R1 and R2 are aryl groups, the aforementioned compound may have the following structure:

[0129]

[0130] in

[0131] R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and Z are as defined above.

[0132] In particular, the aforementioned compounds may have the following structure, wherein the aryl group includes alkyl substitution, in particular methyl substitution:

[0133]

[0134] in

[0135] Z is as defined above.

[0136] Although the foregoing structures are used to depict additional compounds in the reaction product, such as (multiple) halogenated phosphites, it should be understood that a variety of compounds can be made in view of such structures, as long as they meet the structures and corresponding definitions. In this invention, the reaction product can include, for example, a mixture of halogenated phosphites having the foregoing structures.

[0137] As described above, the product mixture comprises a hydrohalide and a reaction product comprising a phosphite. The reaction product may also comprise a halogenated phosphite. The purity of the phosphite may be relatively high.

[0138] Furthermore, as is generally understood in the art, a halophosphite will include at least one halide, such as chloride, directly bonded to a central phosphorus atom.

[0139] Based on reaction product, the purity of phosphite can be about 70% or higher, such as about 75% or higher, such as about 80% or higher, such as about 85% or higher, such as about 88% or higher, such as about 90% or higher.In addition, phosphite can be with about 100 % by weight or less, such as about 99 % by weight or less, such as about 98 % by weight or less, such as about 97 % by weight or less, such as about 95 % by weight or less, such as about 93 % by weight or less, such as about 90 % by weight or less amount exists.In one embodiment, such purity can be based on mole %.In another embodiment, such purity can be based on weight %.For clarity, such purity can be based on the combination of phosphite and halogenated phosphite.

[0140] Phosphite can be with about 75 % by weight or higher based on the weight of reaction product, such as about 78 % by weight or higher, such as about 80 % by weight or higher, such as about 82 % by weight or higher, such as about 84 % by weight or higher, such as about 86 % by weight or higher, such as about 88 % by weight or higher, such as about 90 % by weight or higher, such as about 92 % by weight or higher, such as about 94 % by weight or higher, such as about 95 % by weight or higher, such as about 96 % by weight or higher, such as about 97 % by weight or higher, such as about 98 % by weight or higher amount exists.Phosphite can be with about 100 % by weight or less based on the weight of reaction product, such as about 98 % by weight or less, such as about 96 % by weight or less, such as about 94 % by weight or less, such as about 92 % by weight or less, such as about 90 % by weight or less amount exists.

[0141] One or more compounds of structure (I) may be present in an amount of about 0.1 wt % or more, such as about 0.3 wt % or more, such as about 0.5 wt % or more, such as about 1 wt % or more, such as about 2 wt % or more, such as about 3 wt % or more, such as about 4 wt % or more, such as about 5 wt % or more, such as about 6 wt % or more, such as about 7 wt % or more, based on the total weight of the reaction product. One or more compounds of structure (I) may be present in an amount of about 20 wt % or less, such as about 15 wt % or less, such as about 12 wt % or less, such as about 11 wt % or less, such as about 10 wt % or less, such as about 9 wt % or less, such as about 8 wt % or less, such as about 7 wt % or less, such as about 6 wt % or less, such as about 5 wt % or less, such as about 4 wt % or less, such as about 3 wt % or less, such as about 2 wt % or less, such as about 1 wt % or less, such as about 0.5 wt % or less. For example, one or more compounds of structure (I) may be present in an amount of about 0.3% by weight to about 15% by weight, such as about 0.5% by weight to about 15% by weight, such as about 1% by weight to about 12% by weight, such as about 2% by weight to about 12% by weight, such as about 5% by weight to about 10% by weight, such as about 7% by weight to about 10% by weight, based on the total weight of the reaction product. In another embodiment, one or more compounds of structure (I) may be present in an amount of about 0.3% by weight to about 15% by weight, such as about 0.5% by weight to about 15% by weight, such as about 1% by weight to about 10% by weight, such as about 1% by weight to about 8% by weight, such as about 1% by weight to about 6% by weight, such as about 2% by weight to about 5% by weight, such as about 2% by weight to about 4% by weight, based on the total weight of the reaction product. As described herein, one or more compounds of structure (I) may be halogenated phosphites. In addition, in one embodiment, such aforesaid weight percentages may be applicable to any single compound of structure (I), or in another embodiment, may be applicable to one or more compounds of structure (I) together.

[0142] (Multiple) halogenated phosphites can be present in an amount of about 0.1 wt % or more based on the total weight of the reaction product, such as about 0.5 wt % or more, such as about 1 wt % or more, such as about 2 wt % or more, such as about 3 wt % or more, such as about 4 wt % or more, such as about 5 wt % or more, such as about 6 wt % or more, such as about 7 wt % or more. (Multiple) halogenated phosphites can be present in an amount of about 20 wt % or less based on the total weight of the reaction product, such as about 15 wt % or less, such as about 12 wt % or less, such as about 11 wt % or less, such as about 10 wt % or less, such as about 9 wt % or less, such as about 8 wt % or less, such as about 7 wt % or less, such as about 6 wt % or less, such as about 5 wt % or less, such as about 4 wt % or less, such as about 3 wt % or less, such as about 2 wt % or less, such as about 1 wt % or less, such as about 0.5 wt % or less. For example, (multiple) halogenated phosphorous acid ester can be with the gross weight about 0.5 % by weight to about 15 % by weight based on reaction product, such as 1 % by weight to about 12 % by weight, such as about 2 % by weight to about 12 % by weight, such as about 5 % by weight to about 12 % by weight or about 5 % by weight to about 10 % by weight, such as about 7 % by weight to about 12 % by weight or about 7 % by weight to about 10 % by weight amount exists. In another embodiment, (multiple) halogenated phosphorous acid ester can be with the gross weight about 0.5 % by weight to about 15 % by weight based on reaction product, such as about 1 % by weight to about 10 % by weight, such as about 1 % by weight to about 8 % by weight, such as about 1 % by weight to about 6 % by weight, such as about 2 % by weight to about 5 % by weight, such as about 2 % by weight to about 4 % by weight amount exists.

[0143] The phosphite of combination and halogenated phosphite can be with about 75 % by weight or higher based on the weight of reaction product, such as about 78 % by weight or higher, such as about 80 % by weight or higher, such as about 82 % by weight or higher, such as about 84 % by weight or higher, such as about 86 % by weight or higher, such as about 88 % by weight or higher, such as about 90 % by weight or higher, such as about 92 % by weight or higher, such as about 94 % by weight or higher, such as about 95 % by weight or higher, such as about 96 % by weight or higher, such as about 97 % by weight or higher, such as about 98 % by weight or higher amount exists.The phosphite of combination and halogenated phosphite can be with about 100 % by weight or less based on the weight of reaction product, such as about 98 % by weight or less, such as about 96 % by weight or less, such as about 94 % by weight or less, such as about 92 % by weight or less, such as about 90 % by weight or less amount exists.

[0144] In some embodiments of the present disclosure, in addition to one or more phosphites and one or more hydrohalides, (multiple) phosphite halogenated esters are desired reaction products. Advantageously, by controlling the stoichiometric ratio of p-cresol to m-cresol to phosphorus trichloride, cycle time, temperature, nitrogen sparge, nitrogen purge and / or vacuum, in addition to controlling the amount of hydrohalide, the level of total chloride in the product can also be controlled and predetermined by controlling the amount of phosphite halogenated ester.

[0145] In addition to or in place of the aforementioned halogenated phosphites, the reaction product may comprise a phosphite hydrolysate. In this respect, as also described above, Y may be -OH. Without intending to be limited by theory, a hydrolysis reaction may have occurred, cracking the corresponding R group or halide and replacing hydrogen. Typically, an example of such a product may have the following structure:

[0146]

[0147] in

[0148] R1 and R2 are as defined above.

[0149] In particular, the product may have the following structure, wherein R1 and R2 are each aryl:

[0150]

[0151] in

[0152] R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 As defined above.

[0153] Although the aforementioned structure is used to describe other compounds in the reaction product, such as phosphite hydrolysate, in view of such structure, it should be understood that a variety of compounds can be made as long as they meet the structure and corresponding definitions. In this respect, the reaction product can include a mixture of phosphite hydrolysate, for example a mixture of phosphite hydrolysate with the aforementioned structure.

[0154] In this respect, reaction product disclosed herein can also comprise phosphite hydrolysate except phosphite and if the halogenated phosphite exists.Such phosphite hydrolysate can be the hydrolysate of phosphite synthesized according to the disclosure.But, may expect to minimize the concentration of phosphite hydrolysate in the reaction product.In this respect, the amount of phosphite hydrolysate can be about 5 % by weight or less, such as about 4 % by weight or less, such as about 3 % by weight or less, such as about 2.5 % by weight or less, such as about 2 % by weight or less, such as about 1.8 % by weight or less, such as about 1.5 % by weight or less, such as about 1.3 % by weight or less, such as about 1.1 % by weight or less, such as about 1 % by weight or less, such as about 0.8 % by weight or less, such as about 0.5 % by weight or less, such as about 0.3 % by weight or less. The amount of phosphite hydrolysate can be 0 wt % or more, such as about 0.1 wt % or more, such as about 0.3 wt % or more, such as about 0.5 wt % or more, such as about 0.8 wt % or more, such as about 1 wt % or more, such as about 1.3 wt % or more.

[0155] The amount of phosphite hydrolyzate can be according to moisture content, particularly the moisture content of initial reactant is controlled.For example, moisture content can be based on reactant about 2000 ppm or less, such as about 1800 ppm or less, such as about 1500 ppm or less, such as about 1300 ppm or less, such as about 1000 ppm or less, such as about 800 ppm or less, such as about 600 ppm or less, such as about 500 ppm or less, such as about 400 ppm or less, such as about 300 ppm or less, such as about 200 ppm or less, such as about 100 ppm or less.Moisture content can be based on reactant about 1 ppm or more, such as about 5 ppm or more, such as about 10 ppm or more, such as about 50 ppm or more, such as about 100 ppm or more, such as about 200 ppm or more, such as about 300 ppm or more, such as about 400 ppm or more. In particular, the moisture content can be about 1500 ppm or less based on the hydroxyl-substituted compound, such as about 1300 ppm or less, such as about 1000 ppm or less, such as about 800 ppm or less, such as about 600 ppm or less, such as about 500 ppm or less, such as about 400 ppm or less, such as about 300 ppm or less, such as about 200 ppm or less, such as about 100 ppm or less. The moisture content can be about 1 ppm or more based on the hydroxyl-substituted compound, such as about 5 ppm or more, such as about 10 ppm or more, such as about 50 ppm or more, such as about 100 ppm or more, such as about 200 ppm or more, such as about 300 ppm or more, such as about 400 ppm or more.

[0156] The reaction product may include a certain halide content, such as chloride content. In particular, this reaction may be controlled to obtain a certain halide content, such as chloride content. For example, in one embodiment, it may be desirable to have a relatively high halide content, such as about 10000 ppm to about 15000 ppm. In another embodiment, it may be desirable to have a relatively low halide content, such as less than about 10000 ppm, particularly about 3000 ppm to about 5000 ppm.

[0157] In any case, the halide content, such as the chloride content, can be about 50 ppm or more, such as about 100 ppm or more, such as about 200 ppm or more, such as about 300 ppm or more, such as about 500 ppm or more, such as about 1000 ppm or more, such as about 2000 ppm or more, such as about 3000 ppm or more, such as about 5000 ppm or more, such as about 7000 ppm or more, such as about 9000 ppm or more, such as about 10000 ppm or more, such as about 11000 ppm or more, such as about 12000 ppm or more, such as about 13000 ppm or more, such as about 15000 ppm or more. The halide content, such as chloride content, may be about 25,000 ppm or less, such as about 23,000 ppm or less, such as about 21,000 ppm or less, such as about 20,000 ppm or less, such as about 18,000 ppm or less, such as about 17,000 ppm or less, such as about 16,000 ppm or less, such as about 15,000 ppm or less, such as about 14,000 ppm or less, such as about 13,000 ppm or less, such as about 12,000 ppm or less, such as about 11,000 ppm or less, such as about 10,000 ppm or less, such as about 8,000 ppm or less, such as about 6,000 ppm or less, such as about 5,000 ppm or less.

[0158] In addition, in one embodiment, the reaction product may not include phenol (that is, unsubstituted phenol--phenol with only hydroxyl substitution). In this respect, the reaction product may include about 2 wt % or less, such as about 1.8 wt % or less, such as about 1.5 wt % or less, such as about 1.3 wt % or less, such as about 1 wt % or less, such as about 0.8 wt % or less, such as about 0.5 wt % or less, such as about 0.3 wt % or less, such as about 0.2 wt % or less, such as about 0.1 wt % or less, such as about 0.05 wt % or less, such as about 0 wt % of phenol. However, for clarity, the reaction product may still include substituted phenol, such as cresol or xylenol. If included, they can be with about 15 wt % or less, such as about 10 wt % or less, such as about 8 wt % or less, such as about 6 wt % or less, such as about 4 wt % or less, such as about 2 wt % or less, such as about 1.8 wt % or less, such as about 1.5 wt % or less, such as about 1.3 wt % or less, such as about 1 wt % or less, such as about 0.8 wt % or less, such as about 0.5 wt % or less, such as about 0.2 wt % or less amount exists. If present, reaction product can be with greater than 0 wt %, such as about 0.1 wt % or higher, such as about 0.2 wt % or higher, such as about 0.3 wt % or higher, such as about 0.4 wt % or higher, such as about 0.5 wt % or higher, such as about 0.6 wt % or higher, such as about 1 wt % or higher, such as about 1.5 wt % or higher, such as about 2 wt % or higher amount comprises substituted phenol. Similarly, in another embodiment, the reaction product can include phenol (that is, unsubstituted phenol-only phenol substituted with hydroxyl) in an amount of about 15 wt % or less, such as about 10 wt % or less, such as about 8 wt % or less, such as about 6 wt % or less, such as about 4 wt % or less, such as about 2 wt % or less, such as about 1.8 wt % or less, such as about 1.5 wt % or less, such as about 1.3 wt % or less, such as about 1 wt % or less, such as about 0.8 wt % or less, such as about 0.5 wt % or less, such as about 0.2 wt % or less. If present, the reaction product can include phenol in an amount greater than 0 wt %, such as about 0.1 wt % or higher, such as about 0.2 wt % or higher, such as about 0.3 wt % or higher, such as about 0.4 wt % or higher, such as about 0.5 wt % or higher, such as about 0.6 wt % or higher, such as about 1 wt % or higher, such as about 1.5 wt % or higher.In addition, reaction product can be with about 15 % by weight or less, such as about 10 % by weight or less, such as about 8 % by weight or less, such as about 6 % by weight or less, such as about 4 % by weight or less, such as about 2 % by weight or less, such as about 1.8 % by weight or less, such as about 1.5 % by weight or less, such as about 1.3 % by weight or less, such as about 1 % by weight or less, such as about 0.8 % by weight or less, such as about 0.5 % by weight or less, such as about 0.2 % by weight or less amount comprises the phenol of combination and the phenol of replacement. If present, reaction product can be with greater than 0 % by weight, such as about 0.1 % by weight or higher, such as about 0.2 % by weight or higher, such as about 0.3 % by weight or higher, such as about 0.4 % by weight or higher, such as about 0.5 % by weight or higher, such as about 0.6 % by weight or higher, such as about 1 % by weight or higher, such as about 1.5 % by weight or higher amount comprises the phenol of combination and the phenol of replacement.

[0159] As described above, the method disclosed herein provides a reaction product comprising a phosphite. The reaction product may also include additional components, such as one or more compounds of structure (I). For example, the reaction product may include a first compound of structure (I) and a second compound of structure (I), wherein the two are different. In this regard, the reaction product may include (multiple) halogenated phosphites. In addition, the reaction product may also include a phosphite hydrolyzate. Therefore, structure (I) can be used to describe a halogenated phosphite and / or a phosphite hydrolyzate. In this regard, the reaction product may include a halogenated phosphite of structure (I) wherein Y is -X, a phosphite hydrolyzate of structure (I) wherein Y is -OH, or a mixture thereof. In one embodiment, the reaction product may include a halogenated phosphite of structure (I) wherein Y is -X. In one embodiment, the reaction product may include a phosphite hydrolyzate of structure (I) wherein Y is -OH. In another embodiment, the reaction product may include a halogenated phosphite of structure (I) wherein Y is -X and a phosphite hydrolyzate of structure (I) wherein Y is -OH. In addition to the foregoing, such reaction products may also contain unreacted cresol.

[0160] In addition, the reaction product can have a certain halide content. In addition to the method herein, the inventors have also found that controlling various parameters can also achieve the synthesis of a reaction product with a predetermined halide content. For example, such a predetermined halide content can be a relatively high halide content or a relatively low halide content. In one embodiment, the reaction product can have a relatively high halide content, so that the predetermined content is about 10000 ppm to about 15000 ppm. In another embodiment, the reaction product can have a relatively low halide content, so that the predetermined content is about 3000 ppm to about 5000 ppm.

[0161] In addition, the method can also achieve the synthesis of a reaction product with a predetermined phosphite and halogenated phosphite content. For example, the content of the predetermined combination of phosphite and halogenated phosphite can be greater than or equal to about 97 weight %. In addition, the method can achieve the synthesis of a reaction product with a predetermined hydroxyl-substituted compound (e.g., cresol). For example, the predetermined hydroxyl-substituted compound content can be less than or equal to about 1.5 weight %. In addition, the method can achieve the synthesis of a reaction product with a predetermined phosphite hydrolyzate. For example, the predetermined phosphite hydrolyzate content can be less than or equal to about 1.5 weight %. In addition, in one embodiment, the reaction product can also have a predetermined phenol content of about 1.5 weight % or less, such as about 1 weight % or less, such as about 0.5 weight % or less, such as about 0 weight %. Although the foregoing provides 5 different specifications for various components of a predetermined amount, it should be understood that the method disclosed herein can provide a predetermined content of any combination of the foregoing.

[0162] Various factors or parameters may contribute to providing a product with the aforementioned predetermined content. For example, some embodiments may include various parameters such as the stoichiometry of the hydroxy-substituted compound and the phosphorus halide, the method for the removal of the hydrohalide, the control of the beginning, time (for example, reaction hold time) and / or temperature (for example, reaction temperature) of the removal of the hydrohalide. In one embodiment, at least the stoichiometry plays a more important role than some other parameters. In any case, these parameters can be changed to provide a reaction product with a desired specific component content and / or to meet the desired limit. In this respect, in some embodiments, the final product can advantageously include phosphite (for example, tritolyl phosphite), chlorophosphite and halide (for example, chloride) content of a predetermined level.

[0163] For example, but not intended to be limiting, to produce a product with a low halide content, particularly a low chloride content, it may be desirable to use a relatively low stoichiometric / molar ratio of the hydroxy-substituted compound to the phosphorus halide, use a purge, use a sparge, use a vacuum, increase the temperature and / or increase the reaction time. To produce a product with a relatively high halide content, particularly a high chloride content, it may be desirable to use a relatively high stoichiometric / molar ratio of the hydroxy-substituted compound to the phosphorus halide, use a purge, use a sparge, reduce the temperature and / or reduce the reaction time.

[0164] As described herein, the halide content (or total halide), particularly the chloride content (or total chloride), is determined and can be controlled. In general, these halides or chlorides can be derived from any residual hydrohalide present in the reaction product. In addition, this can also include halides or chlorides derived from any halogenated phosphites (e.g., chlorophosphites). Typically, higher concentrations of halogenated phosphites can result in high halide content. The halide content, particularly the chloride content, can be measured using methods well known in the art. For example, it can be measured by titration.

[0165] The phosphites disclosed herein can be used in various applications generally known in the art. For example, in one embodiment, tricresyl phosphite can be used to synthesize a catalyst for forming adiponitrile, which is a key precursor to hexamethylenediamine. The hexamethylenediamine can then be polymerized with an acid such as adipic acid to form a polyamide such as polyamide-6,6. Other uses of the phosphites disclosed herein can include additives for electrolytes (e.g., for batteries such as lithium-ion batteries), stabilizers, plasticizers (e.g., for plastics or vinyl resins), wood preservatives, hydraulic fluid additives, and the like.

[0166] Example 1

[0167] Use clean and dry glassware to react. Initially, 418.44 grams of meta-cresol and p-cresol (3.869 moles) were loaded into a reaction vessel (1L) at a temperature of about 50-60°C. Once the temperature reaches 80-85°C, phosphorus trichloride is loaded into the reaction vessel at a rate of about 1-1.5mL / minute. The total amount of phosphorus trichloride is 186.50 grams (1.358 moles). The molar ratio of cresol to phosphorus trichloride is about 2.85. Once the introduction of cresol and phosphorus trichloride is completed, the reaction vessel is heated to the reaction temperature and maintained for the retention time shown in Table 1 below. In addition, any hydrogen chloride produced is removed using nitrogen injection, nitrogen purge in combination with nitrogen injection, or nitrogen injection in combination with vacuum, or vacuum, as shown in Table 1 below. Once completed, the container is cooled to less than 100°C. The reaction produces 464 grams of tritolyl phosphite, with a yield greater than 99%. In addition, the product contains a generally high chloride content. For example, the final product comprises about 10.17% by weight of phosphorochloridite, 87.73% by weight of tritolyl phosphite, about 1% by weight of cresol and about 1% by weight of phosphite hydrolysate. The resulting product does not require purification. It is stored under an inert atmosphere of ≤90°C.

[0168] Table 1 below summarizes an overview of each of the seven methods and the method of hydrogen chloride removal.

[0169] Table 1. Reaction conditions for preparing phosphites, halophosphites, and phosphite hydrolysates.

[0170]

[0171] Generally, N2 purge is a constant flow of nitrogen above the surface of the reaction mass. It can be provided using methods known in the art. In this embodiment, a sintering gas dispersion tube is placed above the reaction mass to provide nitrogen.

[0172] Generally speaking, N2 injection is a constant flow of nitrogen below the surface of the reaction mass (i.e., below the surface). It can be provided using methods known in the art. In this embodiment, a sintering gas dispersion tube is placed below the reaction mass to provide nitrogen.

[0173] As summarized in Table 1 above, effective N2 sparging (e.g., fine droplets and uniform distribution from near the bottom of the reaction vessel under stirring) facilitates timely preparation of on-spec product. Removal of HCl with N2 sparging, N2 purge, or vacuum assistance reduces the time to prepare on-spec product. In addition, longer heating at the terminal of about 150°C may not be beneficial compared to increased sparging time. In addition, below 150°C, longer heating times and longer sparging times are required.

[0174] Method 1

[0175] The general reaction steps for Method 1 are provided in Tables 2a and 2b below.

[0176] Table 2a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 1.

[0177]

[0178] Table 2b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to method 1.

[0179]

[0180]

[0181] Method 2

[0182] The general reaction steps for Method 2 are provided in Tables 3a and 3b below.

[0183] Table 3a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 2.

[0184]

[0185] Table 3b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 2.

[0186]

[0187] Method 3

[0188] The general reaction steps for Method 3 are provided in Tables 4a and 4b below:

[0189] Table 4a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 3.

[0190]

[0191] Table 4b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to method 3.

[0192]

[0193]

[0194] Method 4

[0195] The general reaction steps for Method 4 are provided in Tables 5a and 5b below.

[0196] Table 5a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 4.

[0197]

[0198] Table 5b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 4.

[0199]

[0200]

[0201] Method 5

[0202] The general reaction steps for Method 5 are provided in Tables 6a and 6b below.

[0203] Table 6a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 5.

[0204]

[0205] Table 6b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 5.

[0206]

[0207]

[0208] Method 6

[0209] The general reaction steps for Method 6 are provided in Tables 7a and 7b below.

[0210] Table 7a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 6.

[0211]

[0212] Table 7b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 6.

[0213]

[0214] Method 7

[0215] The general reaction steps for Method 7 are provided in Tables 8a and 8b below.

[0216] Table 8a. General process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 7.

[0217]

[0218] Table 8b. Detailed process steps for preparing phosphites, halophosphites and phosphite hydrolysates according to Method 7.

[0219]

[0220]

[0221] Example 2

[0222] Figure 2 and Figure 3A temperature-relative-time figure is presented, and an embodiment according to the present disclosure is illustrated for the method for synthesizing high chloride content and low chloride content, respectively. For example, in two figures, meta-cresol / p-cresol is initially loaded into a reaction vessel. Thereafter, PCl3 is loaded into a container over an extended period of time. Once loaded, the container is gradually heated to 150°C, then the N2 injection of the reaction material in the container is started, and the N2 injection is kept in the container for a prescribed duration until the limit is met. (However, as described above, in other embodiments, once PCl3 is loaded, the removal of HCl can start before reaching the final reaction temperature, such as when the final reaction temperature is about 150°C, about 95°C starts.) Thereafter, the contents are cooled, and the reaction product is pumped out. In an alternative embodiment, after loading cresol and PCl3, before being heated to the desired reaction temperature, for example, before 150°C, N2 injection, N2 purge and / or vacuum are started immediately, and N2 injection, N2 purge and / or vacuum are continued during the entire heating process and the holding time at the reaction temperature at the reaction temperature. In some embodiments, N 2 sparging, N 2 purge, and / or vacuum is initiated immediately prior to heating to the desired reaction temperature, e.g., 150° C., and continued at the reaction temperature throughout the heating process and during the hold time at the reaction temperature, surprisingly and unexpectedly further reducing the cycle time, even more than Figure 2 and 3 The times shown are shorter.

[0223] Example 3

[0224] like Figure 4-7 As illustrated, the effect of the molar ratio of cresol to phosphorus trichloride was observed. In particular, the molar ratios were 2.97: 1 and 2.87: 1. In addition, nitrogen sparging was used and the reaction was carried out at 150°C. The effect on the percentage of tritolyl phosphite, percentage of chlorophosphite, percentage of cresol and chloride content of the final reaction product was determined as a function of time. As observed, the percentage of TTP increased over time, while the remaining components decreased over time.

[0225] Example 4

[0226] Fig. 9 A flow chart with an example mass balance is illustrated. In this figure, m-p-cresol and PCl3 are introduced into a reactor. The reaction produces HCl and TTP, along with chlorophosphite, residual cresol, and any phosphite hydrolysis products.

[0227] Example 5

[0228] The following example relates to the synthesis of a low chloride tritolyl phosphite product. A 2275 gallon (304 cubic feet) reactor was used, first loaded with cresol (about 10811 pounds) and then loaded with PCl3 (about 4609 pounds). The reaction was heated to 150°C and then nitrogen sparging was started at 10 cubic feet per minute (gas hourly space velocity of 1.97 / hour). In this example, no purge or vacuum was used; instead, only nitrogen sparging was used when the temperature reached 150°C. The total sparging time was 7-8 hours. The product obtained less than 1.5% residual cresol and a chloride content of 3000-5000 ppm.

[0229] Table 9. Reactant loadings and concentrations sampled during the reaction of Example 5.

[0230]

[0231]

[0232] With the increase in the molar ratio of cresol to PCl3, more residual cresol was observed in the final product and less chloride was observed in the final product. According to this study, the optimal molar ratio of cresol / PCl3 was determined to be 2.975 to 2.98.

[0233] Example 6

[0234] The following examples relate to the synthesis of low chloride tritolyl phosphite products. A 2275 gallon (304 cubic feet) reactor was used, first loaded with cresol (about 11,182 pounds), then loaded with PCl3 (about 4,775 pounds). The reaction was heated to 150°C. In certain embodiments, nitrogen was sprayed at 10 cubic feet per minute (gas hourly space velocity of 1.97 / hour). Similarly, in certain instances, nitrogen was purged at 15 or 25 psi (25 psi–5-6 CFM, 1.1 / hour gas hourly space velocity). In some embodiments, purging and spraying began earlier than reaching a reaction temperature of 150°C. For example, in some cases, it began once PCl3 addition was complete and / or when the temperature was 95°C. The product obtained less than 1.5% residual cresol and a chloride content of 3000-5000 ppm.

[0235] Table 10. Reactant loadings and concentrations sampled during the reaction of Example 6.

[0236]

[0237]

[0238]

[0239]

[0240] Using both purge and sparging can reduce cycle time while bringing the product within certain limits. In addition, the total sparging time can be reduced from 7-8 hours to 4-5 hours to bring the product within certain limits based on residual cresols and total chlorides in the product.

[0241] Example 7

[0242] The following examples relate to the synthesis of high chloride tritolyl phosphite products. A 2275 gallon (304 cubic feet) reactor was used, first loaded with cresol (about 11180-11182 pounds), then loaded with PCl3 (about 4984 pounds). The molar ratio of cresol to PCl3 was about 2.85. The reaction was heated to 150°C. In certain embodiments, nitrogen was sprayed at 10 cubic feet per minute (gas hourly space velocity of 1.97 / hour). Similarly, in certain embodiments, nitrogen was purged at 25 psi (5-6 CFM, 1.1 / hour gas hourly space velocity). In certain embodiments, purging and spraying began earlier than reaching 150°C reaction temperature. For example, in some cases, once PCl3 addition was completed and / or when the temperature was 95°C, it began. In addition, in some embodiments, the reaction temperature was 125°C instead of 150°C. The product has less than 1.5% residual cresol and a chloride content of 10,000-15,000 ppm.

[0243] Using both purging and injection can reduce the cycle time while making the product reach certain limits. In addition, the total injection time can be reduced from 3 hours to 1 hour so that the product reaches certain limits based on residual cresols and total chloride in the product. In addition, through these improvements, the total batch material cycle time can be reduced from 12 hours to 10 hours.

[0244] Without departing from the spirit and scope of the present disclosure, those of ordinary skill in the art may implement these and other modifications and variations of the present disclosure. In addition, it should be understood that the aspects of the various embodiments may be interchangeable in whole or in part. In addition, those of ordinary skill in the art will appreciate that the foregoing description is merely exemplary and is not intended to limit the disclosure further described in the appended claims.

Claims

1. A method for preparing phosphite, the method comprising: A hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof, is reacted with a phosphorus halide at a temperature of about 200° C. or less, wherein the hydroxy-substituted compound and the phosphorus halide are reacted in a molar ratio of about 2.3 to about 5 to produce a product mixture comprising a hydrohalide and a reaction product comprising a phosphite and one or more compounds having the following structure (I) and present in an amount of about 0.3 wt % or more to about 15 wt % or less based on the weight of the reaction product: （I） in R1 is an alkyl group or an aryl group; R2 is an alkyl group or an aryl group; Y is Z or -OH; and Z is a halide; and The hydrohalide is removed from the product mixture.

2. The method of any preceding claim, wherein the phosphorus halide comprises phosphorus trichloride.

3. The method of any preceding claim, wherein the hydroxy-substituted compound comprises a hydroxy-substituted alkyl compound.

4. The method of any preceding claim, wherein the hydroxy-substituted compound comprises a hydroxy-substituted aryl compound.

5. The method of claim 4, wherein the hydroxy-substituted aryl compound comprises a hydroxy-substituted alkaryl compound.

6. The method of claim 5, wherein the hydroxy-substituted alkaryl compound comprises a C1-C4 alkyl group.

7. The method of claim 4, wherein the hydroxy-substituted alkaryl compound comprises a methyl group.

8. The method of any preceding claim, wherein the removing step comprises a vacuum.

9. The method of any preceding claim, wherein the removing step comprises a nitrogen purge.

10. The method of any preceding claim, wherein the removing step comprises nitrogen sparging.

11. The method of any one of claims 1-7, wherein the removing step comprises vacuum and nitrogen sparging.

12. The method of any one of claims 1-7, wherein the removing step comprises nitrogen sparging and nitrogen purging.

13. The method of any preceding claim, wherein the phosphite has the structure: in R 21 , R 22 and R 23 Each is independently an alkyl group or an aryl group.

14. The method of claim 13, wherein R 21 , R 22 and R 23 At least one of them is an aryl group.

15. The method of claim 13, wherein R 21 , R 22 and R 23 Each is an aryl group.

16. The method of claim 13, wherein R 21 , R 22 and R 23 Each is an alkaryl group.

17. The method of any preceding claim, wherein the phosphite has the structure: in R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 is independently hydrogen or alkyl.

18. The method of claim 17, wherein at least one of R4, R5, R6, R7 and R8, R9, R 10 , R 11 , R 12 and R 13 At least one of R 14 , R 15 , R 16 , R 17 and R 18 At least one of them is a C1-C4 alkyl group.

19. The method of claim 18, wherein the C1-C4 alkyl group comprises a methyl group.

20. The method of claim 17, wherein at least one of R5, R6 and R7, R 10 , R 11 and R 12 At least one of R 15 , R 16 and R 17 At least one of them is a C1-C4 alkyl group.

21. The method of claim 20, wherein the C1-C4 alkyl group comprises a methyl group.

22. The method of claim 17, wherein R6, R 11 and R 16 Each is a C1-C4 alkyl group.

23. The method of claim 23, wherein the C1-C4 alkyl group comprises a methyl group.

24. The method of claim 17, wherein at least one of R5 and R7, R 10 and R 12 At least one of R 15 and R 17 At least one of them is a C1-C4 alkyl group.

25. The method of claim 24, wherein the C1-C4 alkyl group comprises a methyl group.

26. The method of any preceding claim, wherein the phosphite has the structure: 。 27. The method of any preceding claim, wherein the phosphite has the structure: 。 28. The method of claim 1, wherein one or more compounds of structure (I) have the following structure: in R1 and R2 are as defined above.

29. The method of claim 1, wherein one or more compounds of structure (I) have the following structure: in R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 are independently hydrogen or alkyl.

30. The method of claim 1, wherein one or more compounds of structure (I) have the following structure: in R1 and R2 are as defined above; Y is Z; and Z is defined as described above.

31. The method of claim 1, wherein one or more compounds of structure (I) have the following structure: in R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 are each independently hydrogen or alkyl; and Z is defined as described above.

32. The method of claim 1, wherein one or more compounds of structure (I) have the following structure: in Z is defined as described above.

33. The method of claim 1, wherein the reaction product comprises a first compound having the structure: in R1 and R2 are as defined above; Y is Z; and Z is defined as above, and a second compound having the structure: in R1 and R2 are as defined above.

34. The method of any preceding claim, wherein the hydrohalide comprises hydrogen chloride.

35. The method of any preceding claim, wherein the phosphite is present in the reaction product in an amount of about 80% by weight or more.

36. The method of any preceding claim, wherein the phosphite is present in the reaction product in an amount of about 85% by weight or more.

37. The method of any preceding claim, wherein the phosphite is present in the reaction product in an amount of about 90% by weight or more.

38. The method of any preceding claim, wherein the compound of structure (I) is present in the reaction product in an amount of about 1 wt% or more to about 12 wt% or less.

39. The method of any one of claims 1 to 37, wherein the compound of structure (I) is present in the reaction product in an amount of about 2 wt% or more to about 4 wt% or less.

40. The method of any one of claims 1 to 37, wherein the compound of structure (I) is present in the reaction product in an amount of about 7 wt% or more to about 10 wt% or less.

41. The method of any preceding claim, wherein the chloride content of the reaction product is from about 3000 ppm to about 15000 ppm.

42. The method of any preceding claim, wherein the chloride content of the reaction product is from about 10,000 ppm to about 15,000 ppm.

43. The method of any preceding claim, wherein the reaction product comprises about 2 wt% or less phenol.

44. The method of any preceding claim, wherein the hydroxy-substituted compound and the phosphorus halide are reacted in a molar ratio of about 2.3 to less than about 3.

45. The method of any preceding claim, wherein the reacting step is performed in the absence of a solvent.

46. ​​The method of any preceding claim, wherein the method does not include distillation for purification of the reaction product.

47. The method of any preceding claim, wherein the reacting step is performed in the absence of a catalyst.

48. The method of any preceding claim, wherein the reacting step is performed at a temperature of about 25°C or greater.

49. A method for preparing a phosphite, the method comprising: reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof, with a phosphorus halide, wherein the hydroxy-substituted compound and the phosphorus halide are present in a molar ratio of about 2.3 to about 5 to produce a product mixture comprising a hydrohalide and a reaction product comprising a phosphite and a halophosphite, wherein the halogenated phosphite is present in an amount of about 0.5 wt % or more to about 15 wt % or less based on the weight of the reaction product; and The hydrohalide is removed from the product mixture under vacuum.

50. A method for preparing a phosphite, the method comprising: reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof, with a phosphorus halide, wherein the hydroxy-substituted compound and the phosphorus halide are present in a molar ratio of about 2.3 to about 5 to produce a product mixture comprising a hydrohalide and a reaction product comprising a phosphite and a halophosphite, wherein the halogenated phosphite is present in an amount of about 0.5 wt % or more to about 15 wt % or less based on the weight of the reaction product; and The hydrohalide is removed from the product mixture using a nitrogen sparge and / or a nitrogen purge.

51. A method for preparing a phosphite, the method comprising: reacting a hydroxy-substituted compound comprising a hydroxy-substituted alkyl compound, a hydroxy-substituted aryl compound, or a mixture thereof, with a phosphorus halide, wherein the hydroxy-substituted compound and the phosphorus halide are present in a molar ratio of about 2.3 to about 5, to produce a product mixture comprising a hydrohalide and a reaction product, wherein the reaction product comprises a phosphite and a halophosphite, wherein the reaction product has a predetermined halide content, wherein the halogenated phosphite is present in an amount of about 0.5 wt % or more to about 15 wt % or less based on the weight of the reaction product; and The hydrohalide is removed from the product mixture.

52. The method of claim 51, wherein the predetermined halide content is from about 10,000 ppm to about 15,000 ppm.

53. The method of claim 51, wherein the predetermined halide content is from about 3000 ppm to about 5000 ppm.

54. The method of any one of claims 51-53, wherein the method is performed to further provide a reaction product comprising a predetermined hydroxy-substituted compound content.

55. The method of claim 54, wherein the predetermined hydroxy-substituted compound content is about 1.5 wt% or less.

56. The method of any one of claims 47-55, wherein the method is performed to further provide a reaction product comprising predetermined amounts of the phosphite and the halophosphite.

57. The method of claim 56, wherein the predetermined content of the phosphite and the halophosphite is about 97% by weight or more.

58. The method of any one of claims 51-57, wherein the reaction product comprises a phosphite hydrolyzate.

59. The method of claim 58, wherein the method is performed to further provide a reaction product comprising a predetermined phosphite hydrolysate content.

60. The method of claim 59, wherein the predetermined phosphite hydrolysate content is about 1.5 wt% or less.

61. The method of any one of claims 51-60, wherein the method is performed to further provide a reaction product comprising a predetermined phenol content.

62. The method of claim 61, wherein the predetermined phenol content is about 1.5 wt% or less.

63. The method of any one of claims 51-62, wherein the predetermined halide content is obtained by controlling the molar ratio of the hydroxy-substituted compound to the phosphorus halide.

64. The method of any one of claims 51-63, wherein the predetermined halide content is obtained by controlling the reaction time.

65. The method of any one of claims 51-64, wherein the predetermined halide content is obtained by controlling the reaction temperature.

66. The method of any one of claims 51-65, wherein the predetermined halide content is obtained by controlling the time used to remove the hydrohalide, removing the hydrohalide via a process comprising removing the hydrohalide including nitrogen sparging, nitrogen purging, applying a vacuum and / or using a catalyst.

Images