Sulfonated Phosphazene Compounds

Abstract

The present invention relates to sulfonated phosphazene compounds, including cyclic, linear or bridged phosphazene compounds. The present invention further relates to a method for preparing such sulfonated phosphazene compounds, and to polymer compositions comprising the phosphazene compounds. The present invention also relates to articles comprising such polymer compositions, and to the use of such sulfonated phosphazene compounds to improve the flame retardancy of polymer compositions.

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS none.

[0002] [Technical field] The present invention relates to the field of phosphazene compounds, more particularly to sulfonated phosphazene compounds suitable as flame retardants in polymer formulations.The present invention further relates to a method for preparing such sulfonated phosphazene compounds and to polymer compositions comprising said phosphazene compounds.The present invention also relates to articles comprising such polymer compositions and to the use of such sulfonated phosphazene compounds to improve the flame retardancy of polymer compositions.

[0003] [Background technology] Flame resistant (FR) additives are commonly added to polymer products used in applications such as construction, automotive, electronics, electrical laminates, wire and cable, and textiles. FR additives improve the limiting oxygen index (LOI) of polymer systems, allowing articles made from those polymer systems to pass standard fire tests. A variety of low molecular weight (~<1500 g / mol) brominated compounds are used as FR additives for organic polymers. Many of these, such as hexabromocyclododecane and polybrominated diphenyl ethers, are under regulatory and societal pressure that could limit their use, so there is an incentive to find alternatives to these.

[0004] In the past, various phosphorus compounds have been used as FR additives. These include organic phosphates, phosphonates, and phosphoramides, some of which are described in U.S. Patents 4,070,336 and 4,086,205, and in "The Chemistry and Use of Flame Retardants", JW Lyons, Chapter 2- Chemistry of Fire Retardants Based on Phosphorous p.29-74 (1987). These compounds tend to provide only moderate ignition resistance and are generally not as effective as hexabromocyclododecane or other brominated FR additives.

[0005] Phosphazenes are a type of phosphorus compound that contain chains of alternating phosphorus and nitrogen atoms. Phosphazenes can be linear or cyclic in structure. Several compounds of both types have been tested as FR additives in certain polymer systems. U.S. Pat. No. 3,994,996 describes compounds with multiple cyclic phosphazene moieties linked together via POP bonds. These compounds are said to be useful as FR additives for rayon. In U.S. Pat. No. 4,864,047, aminophenoxycyclotriphosphazene is said to be useful as a flame retardant for polystyrene. JP 2004-051697A describes several other cyclic phosphazenes as FR additives for various polymers such as polyolefins, polystyrene and styrene copolymers, polycarbonates, poly(ethylene terephthalate), polybutadiene, polyamides, epoxy resins, and unsaturated polyesters. These are described as flame retardants for various polymers, similar to those described in JP 2004-051697A. JP 2001-200151A and US Published Application No. 2005-0245670 all describe several substituted cyclic phosphazenes as FR additives in polycarbonate resin compositions.

[0006] Despite these many attempts, phosphazene compounds have struggled to achieve commercial success. Although phosphazene compounds can provide flame retardancy (as shown by certain standardized tests), they often lack other properties necessary for a good FR additive. In some cases, phosphazene compounds are simply too expensive to be practical. Many of the phosphazene FR additives have been found to be inefficient and require somewhat higher loadings to be effective. In some cases, phosphazene compounds are not miscible enough in certain organic polymers. As a result, it is difficult to disperse the phosphazene compounds uniformly in the polymer. This leads to erratic performance and, in some cases, loss of the FR additive from the polymer over time due to bleeding or other processes. Poor compatibility can also lead to serious processing problems. In some cases, poor compatibility prevents the incorporation of an effective amount of the phosphazene compound into the polymer.

[0007] Another problem with the phosphazene FR additives is that they are not thermally stable at the temperatures at which certain organic polymers are melt processed, especially when the polymers are melt processed at temperatures above 230° C. It has been observed that many of the phosphazene compounds begin to decompose at those temperatures, resulting in the formation of decomposition products and, of course, loss of the additive.

[0008] Therefore, for the above reasons, there remains a need to develop phosphazene compounds that can provide excellent flame retardancy at low loadings in polymer formulations, along with excellent thermal stability suitable for being processed with polymer melts.

[0009] Summary of the Invention Thus, a solution to some or all of the shortcomings in the prior art resides in a sulfonated phosphazene compound selected from the group consisting of: i. Cyclic phosphazene compounds represented by formula 1a: [ka] wherein each of the variables "a", "b" and "c" is an integer ranging from 1 to 5, inclusive, and preferably each of the variables "a", "b" and "c" is 1; ii. A linear phosphazene compound represented by formula (1b): [ka] wherein each of the variables "x", "y" and "z" is an integer ranging from 1 to 500, preferably from 50 to 200, preferably from 100 to 200; and iii. A bridged phosphazene compound represented by formula (1c): [ka] wherein each of the variables "m", "n" and "o" is an integer ranging from 1 to 500, preferably from 50 to 200, and preferably from 100 to 200; wherein each of the substituents "A", "B", "E", "Z", "G", "Q", and "J" are independently the same or different, and each of the substituents "A", "B", "E", "Z", "G", "Q", and "J" is independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a branched or linear alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an ether group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkaryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted amine group, and a substituted sulfonate esterifying group represented by formula (1d): [ka] In the formula, R 1is a substituent selected from the group comprising at least one aryl group containing 6 to 30 carbon atoms, preferably 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably 11 to 18 carbon atoms; In the formula, R 2 is a substituent selected from the group consisting of halogen-substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or linear alkyl groups having 1 to 20 carbon atoms, halogen-substituted aryl groups, hydroxyl-substituted aryl groups, nitro-substituted aryl groups, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; However, at least one of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d), and preferably, each of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d).

[0010] In some embodiments of the present invention, the present invention relates to a method for preparing a sulfonated phosphazene compound, comprising the steps of: i. A diol compound (V) represented by the following formula: [ka] reacting with a sulfonyl halide compound represented by formula (W), [ka] forming a first intermediate compound; 1 and R 2 is defined herein throughout this disclosure; the substituent "X" is halogen; preferably, the substituent "X" is chlorine; ii. reacting the first intermediate compound with a phosphazene compound (T) having at least one phosphorus atom substituted with a nucleophilic leaving group (NLG) to form a sulfonated phosphazene compound; Here, the nucleophilic leaving group (NLG) is selected from the group consisting of a halogen group, a thio group, a cyano group, a tosylate group, an alkoxy group, an aryloxy group, an alkyl ester group, an azide group, and an amine group, and preferably, the nucleophilic leaving group (NLG) is a halogen group.

[0011] In some embodiments of the present invention, the present invention relates to a polymer composition comprising: i. 80.0% to 99.95% by weight, preferably 85.0% to 99.95% by weight, of a thermoplastic polymer, based on the total weight of the composition; and ii. 0.05% to 20.0% by weight, preferably 0.05% to 15.0% by weight, of the sulfonated phosphazene compound of the present invention, based on the total weight of the composition.

[0012] Other objects, features and advantages of the present invention will become apparent from the following drawings, detailed description and examples. It should be understood, however, that the drawings, detailed description and examples, while indicating specific embodiments of the present invention, are given by way of illustration only and are not meant to be limiting.

[0013] Moreover, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from a particular embodiment can be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the particular embodiments described herein.

[0014] Detailed Description of the Invention Listed below are definitions of various terms and phrases used throughout this specification.

[0015] Numerical ranges used throughout this disclosure are intended to include all values ​​and ranges therebetween unless otherwise specified, for example, a boiling point range of 50°C to 100°C includes all temperatures and ranges between, and including, those temperatures at 50°C and 100°C.

[0016] The use of the words "a" or "an" when used in the claims or specification with the terms "comprising," "including," "containing," or "having" can mean "one," but is also consistent with the meanings of "one or more," "at least one," and "one or more." The words "comprising" (and any conjugation of comprising, such as "comprise" and "comprises"), "having" (and any conjugation of having, such as "have" and "has"), "including" (and any conjugation of including, such as "includes" and "include"), or "containing" (and any conjugation of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The processes of the present invention can "comprise," "consist essentially of," or "consist of" certain ingredients, components, compositions, etc. disclosed throughout this disclosure.

[0017] Any formula or structure containing carbon atoms that is not explicitly stated with a particular substituent may be interpreted as including any one of hydrogen substituents, or hydrocarbyl substituents, or heteroatom substituents, or amine substituents.

[0018] The present invention addresses the need to develop non-halogen flame retardants, such as phosphazene compounds, that can provide excellent flame retardancy at low loadings in polymer formulations, along with excellent thermal stability, and that are suitable for processing with polymer melts.

[0019] The phosphazene compound is a sulfonated phosphazene compound. Preferably, such a sulfonated phosphazene compound may be a cyclic phosphazene compound, or a linear phosphazene compound, or a crosslinked phosphazene compound.

[0020] In some preferred embodiments of the present invention, the sulfonated phosphazene compound is a cyclic phosphazene compound represented by formula (1a): [ka] wherein each of the variables "a", "b" and "c" is an integer ranging from 1 to 5, inclusive; each of the substituents "A", "B", "E", "Z", "G", "Q" is independently the same or different; and each of the substituents "A", "B", "E", "Z", "G", "Q" is independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a branched or linear alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an ether group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkaryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted amine group, and a substituted sulfonate esterifying group represented by formula (1d): [ka] In the formula, R 1is a substituent selected from the group comprising at least one aryl group containing 6 to 30 carbon atoms, preferably 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably 11 to 18 carbon atoms; 2 is a substituent selected from the group consisting of halogen-substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or linear alkyl groups having 1 to 20 carbon atoms, halogen-substituted aryl groups, hydroxyl-substituted aryl groups, nitro-substituted aryl groups, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; However, at least one of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate ester group represented by formula (1d). In other words, at least one of the phosphorus atoms in the cyclic phosphazene compound of formula (1a) is substituted with a sulfonate ester group represented by formula (1d).

[0021] Preferably, in some embodiments of the present invention, each of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterifying group represented by formula (1d).

[0022] Preferably, any alkyl group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferably, the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, a pentyl group, a hexyl group.

[0023] Preferably, the alkenyl group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferably, the ether group may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferably, the alkoxy group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

[0024] Preferably, the aryl group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the alkaryl group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the aralkyl group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the cycloalkyl group present as a substituent in the cyclic phosphazene compound of formula (1a) may have 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms.

[0025] [Cyclic phosphazene compounds] In some embodiments of the present invention referring to formula (1a), each of the variables "a", "b" and "c" is 1. Preferably, the sulfonated phosphazene compound is a cyclic phosphazene compound represented by formula (2): [ka] wherein each of the substituents "A", "B", "E", "Z", "G", and "Q" are independently the same or different and are independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, ether groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkenyl-substituted aryl groups having 6 to 30 carbon atoms, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted amine groups, and substituted sulfonate esterifying groups represented by formula (1d): [ka] In the formula, R 1 is a substituent selected from the group comprising at least one aryl group containing 6 to 30 carbon atoms, preferably 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably 11 to 18 carbon atoms; In the formula, R 2 is a substituent selected from the group consisting of halogen-substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or linear alkyl groups having 1 to 20 carbon atoms, halogen-substituted aryl groups, hydroxyl-substituted aryl groups, nitro-substituted aryl groups, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; provided that at least one of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterifying group represented by formula (1d) as defined herein.

[0026] In other words, at least one of the phosphorus atoms in the cyclic phosphazene formula (2) is substituted with a sulfonate esterifying group represented by formula (1d).

[0027] Preferably, in some embodiments of the present invention, each of "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group as represented by formula (1d).

[0028] Preferably, each of "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d): [ka] In the formula, the substituent R 1 is selected from the group consisting of: [ka] JPEG2025500553000013.jpg83169

[0029] Preferably, any alkyl group present as a substituent in the cyclic phosphazene compound of formula (2) may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferably, the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, a pentyl group, a hexyl group.

[0030] Preferably, the alkenyl group present as a substituent in the cyclic phosphazene compound of formula (2) may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferably, the ether group may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferably, the alkoxy group present as a substituent in the cyclic phosphazene compound may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

[0031] Preferably, the aryl group present as a substituent in the cyclic phosphazene compound of formula (2) may have 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the alkaryl group present as a substituent in the cyclic phosphazene compound of formula (2) may have 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the aralkyl group present as a substituent in the cyclic phosphazene compound of formula (2) may have 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the cycloalkyl group present as a substituent in the cyclic phosphazene compound of formula (2) may have 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms.

[0032] Regarding the substituted sulfonate ester group represented by formula (1d): [ka] Substituent R 1 is selected from the group consisting of: [ka] JPEG2025500553000016.jpg83169In the formula, substituent R 3 , R 4 , R 5 are each independently selected from the group consisting of halogen substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, and branched or straight chain alkyl groups having 1 to 10 carbon atoms.

[0033] Preferably, any alkyl group present as a substituent may have from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms. Preferably, the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, a pentyl group, a hexyl group. Preferably, the halogen group is a fluorine group. For each of the formulas and structures shown above, the substituent R1 The two attachment points for are indicated by prominent nodes shown in each of the structures or formulas.

[0034] Preferably, R 1 is a substituent selected from the group comprising at least one aryl group containing 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably 11 to 18 carbon atoms. Preferably, for the substituted sulfonate esterifying group represented by formula (1d): [ka] Substituent R 1 is selected from the group consisting of: [ka] JPEG2025500553000019.jpg83169In the formula, substituent R 3 , R 4 , R 5 are each independently selected from the group consisting of halogen substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, and branched or straight chain alkyl groups having 1 to 10 carbon atoms.

[0035] Preferably, any alkyl group present as a substituent may have from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms. Preferably, the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, a pentyl group, a hexyl group. Preferably, the halogen group is a fluorine group. For each of the formulas and structures shown above, the substituent R 1 The two attachment points for are indicated by prominent nodes shown in each of the structures or formulas.

[0036] Preferably, the substituent R 3 , R 4 , R 5 Each of R is a methyl or ethyl group, and preferably each of R3 , R 4 , R 5 Each of the substituents R 3 , R 4 , R 5 Each of the substituents R 3 , R 4 , R 5 Each of these is a fluorine-substituted alkyl group represented by the formula (-CF3).

[0037] Regarding the substituted sulfonate ester group represented by formula (1d): [ka] Substituent R 2 is selected from the group consisting of: [ka] For each of the formulas and structures shown above, the substituent R 2 One point of attachment for is indicated by a prominent node shown in each of the structures or formulas.

[0038] In some preferred embodiments of the present invention, the sulfonated phosphazene compound is a cyclic phosphazene compound represented by formula (5): [ka] In the formula, the substituent R 1 and R 2 is defined herein.

[0039] Preferably, R 1 is a substituent selected from the group comprising at least one aryl group containing 6 to 30 carbon atoms, preferably 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably 11 to 18 carbon atoms.

[0040] Preferably, in some embodiments of the present invention, the sulfonated phosphazene compound is a cyclic phosphazene compound represented by the formula: [ka]

[0041] Preferably, in some embodiments of the present invention, the sulfonated phosphazene compound is a cyclic phosphazene compound represented by the formula: [ka]

[0042] Preferably, in some embodiments of the present invention, the sulfonated phosphazene compound is a cyclic phosphazene compound represented by the formula: [ka]

[0043] In some preferred embodiments of the present invention, the sulfonated phosphazene compound is hexa(benzenesulfonic acid 4-(4-oxy-benzenesulfonyl)-phenyl ester)cyclotriphosphazene (HSSCP) represented by the formula: [ka]

[0044] In some embodiments of the present invention, the present invention relates to a method for preparing a sulfonated phosphazene compound, comprising the steps of: i. reacting a diol compound (V) represented by the following formula in the presence of a base: [ka] reacting with a sulfonyl halide compound represented by formula (W), [ka] forming a first intermediate compound; 1 and R 2 is defined herein in this disclosure; the substituent "X" is a halogen; preferably, the substituent "X" is chlorine; and ii. reacting the first intermediate compound with a phosphazene compound (T) having at least one phosphorus atom substituted with a nucleophilic leaving group (NLG) in the presence of a base to form a sulfonated phosphazene compound; Wherein, the nucleophilic leaving group (NLG) is selected from the group consisting of a halogen group, a thio group, a cyano group, a tosylate group, an alkoxy group, an aryloxy group, an alkyl ester group, an azide group, and an amine group, and preferably, the nucleophilic leaving group (NLG) is a halogen group. More preferably, the halogen group is chlorine.

[0045] Alternatively, in some embodiments of the present invention, the present invention relates to a method for preparing a sulfonated phosphazene compound, comprising the steps of: i. reacting a diol compound (V) represented by the following formula in the presence of a base: [ka] with a phosphazene compound (T) having at least one phosphorus atom substituted with a nucleophilic leaving group (NLG) to form a second intermediate compound; and ii. reacting the second intermediate compound with a sulfonyl halide compound represented by formula (W) in the presence of a base; [ka] forming a sulfonated phosphazene compound; In the formula, the substituent R 1 and R 2 is defined throughout this disclosure; the substituent "X" is a halogen; preferably, the substituent "X" is chlorine; Wherein, the nucleophilic leaving group (NLG) is selected from the group consisting of a halogen group, a thio group, a cyano group, a tosylate group, an alkoxy group, an aryloxy group, an alkyl ester group, an azide group, and an amine group, and preferably, the nucleophilic leaving group (NLG) is a halogen group. More preferably, the halogen group is chlorine.

[0046] Preferably, the base is selected from KOH, NaOH, LiOH, NaH, KH, K2CO3, Na2CO3, Li2CO3, K3PO4, pyridine, 4-dimethylaminopyridine, trimethylamine, triethylamine, or any combination thereof. Preferably, the bases used in step (i) and step (ii) of the method for preparing a sulfonated phosphazene compound are the same. Preferably, the bases used in step (i) and step (ii) of the method for preparing a sulfonated phosphazene compound are not the same. The expression "nucleophilic leaving group (NLG)" as used throughout this disclosure is a functional group or atom capable of being displaced in a nucleophilic substitution reaction.

[0047] Preferably, the phosphazene compound (T) is a cyclic phosphazene compound represented by the following structure: [ka]

[0048] In the formula, substituent L 1 , L 2 , L 3 , L 4 , L 5 and L 6are independently the same or different and are independently selected from a nucleophilic leaving group (NLG), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a branched or linear alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkaryl group having 6 to 30 carbon atoms, an alkenyl-substituted aryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted amine group, with the proviso that the substituent L 1 , L 2 , L 3 , L 4 , L 5 Or L 6 At least one of the substituents L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are nucleophilic leaving groups (NLG), and preferably, the substituents L 1 , L 2 , L 3 , L 4 , L 5 and L 6 Each of the substituents L 1 , L 2 , L 3 , L 4 , L 5 and L 6 Each of is chlorine. Preferably, the phosphazene compound (T) is hexa-chloro-cyclotriphosphazene (HCC). Preferably, the diol compound (V) is bis(4-hydroxyphenyl)sulfone. Preferably, the sulfonyl halide compound (W) is benzenesulfonyl chloride.

[0049] Preferably, in some embodiments of the present invention, the phosphazene compound (T) is a cyclic phosphazene compound represented by the formula: [ka] The diol compound (V) is represented by the following formula: [ka] The sulfonyl halide compound (W) is represented by the following formula: [ka]

[0050] In some embodiments of the present invention, the present invention relates to a polymer composition comprising: i. 80.0% to 99.95% by weight, preferably 85.0% to 99.95% by weight, of a thermoplastic polymer, based on the total weight of the composition; and ii. 0.05% to 20.0% by weight, preferably 0.05% to 15.0% by weight, preferably 1.0% to 5.0% by weight, of the sulfonated phosphazene compound of the present invention, based on the total weight of the composition.

[0051] Preferably, in some embodiments of the present invention, the present invention relates to a polymer composition comprising: i. from 75.0% to 99.95% by weight, from 80.0% to 99.95% by weight, preferably from 85.0% to 99.95% by weight, of a thermoplastic polymer, based on the total weight of the composition; ii. 0.05% to 20.0% by weight, preferably 0.05% to 15.0% by weight, preferably 1.0% to 5.0% by weight of the sulfonated phosphazene compound of the present invention, based on the total weight of the composition; and iii. Optionally, additives in an amount of from 0.0% to 5.0% by weight, preferably from 0.0% to 1.5% by weight, preferably from 0.4% to 1.0% by weight, based on the total weight of the composition.

[0052] Non-limiting examples of additives may be antioxidants, processing aids, color pigments, light stabilizers, and diffusing particles.Preferably, in some embodiments of the present invention, the thermoplastic polymer is polyethylene terephthalate (PET), impact polypropylene copolymer, propylene ethylene copolymer, propylene ethylene alpha olefin terpolymer, polycarbonate (PC), polybutylene terephthalate (PBT), poly(1,4-cyclohexylidene-cyclohexane-1,4-dicarboxylate) (PCCD), glycol modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), ethylene-C4-C 12 - selected from alpha-olefin copolymers, polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) and derivatives thereof, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamides (PA), polysulfone sulfonates (PSS), sulfonates of polysulfones, polyether ether ketone (PEEK), acrylonitrile butyldiene styrene (ABS), polyether ketone ketone (PEKK), polyphenylene sulfide (PPS), copolymers thereof, or blends thereof.

[0053] Preferably, the thermoplastic polymer is selected from polycarbonate, polyethylene, and polypropylene. Preferably, the thermoplastic polymer is polycarbonate. The polycarbonate may be selected from linear polycarbonate, branched polycarbonate, polycarbonate-siloxane copolymer, and combinations thereof.

[0054] Preferably, the polycarbonate is a linear polycarbonate comprising repeat units derived from bisphenol A carbonate. Preferably, the polycarbonate is a combination of a linear polycarbonate comprising repeat units derived from bisphenol A carbonate and a polycarbonate-siloxane copolymer.

[0055] In some embodiments of the present invention, the present invention relates to an article comprising the polymer composition. The article comprising the polymer composition can be prepared by a process comprising: (i) dry blending a thermoplastic polymer with the sulfonated phosphazene compound of the present invention; and (ii) extruding the blend in an extruder with a melt temperature of less than 240° C. to form the article.

[0056] In some embodiments of the present invention, the present invention relates to the use of sulfonated phosphazene compounds to improve the flame retardancy of polymer compositions.

[0057] Below are given specific examples showing some of the embodiments of the present invention. The examples are for illustrative purposes only and are not intended to limit the present invention. It should be understood that the embodiments and aspects disclosed herein are not mutually exclusive, and such aspects and embodiments can be combined in any manner. Those skilled in the art will readily recognize parameters that can be changed or modified to obtain essentially the same results.

[0058] Example I Objective: For the purposes of this Example section, to synthesize a cyclic sulfonated phosphazene compound, hexa(benzenesulfonic acid 4-(4-oxy-benzenesulfonyl)-phenyl ester)cyclotriphosphazene (HSSCP), also known as compound (II). [ka]

[0059] Material details: The following materials were used: bis(4-hydroxyphenyl)sulfone (98%, Sigma-Aldrich), benzenesulfonyl chloride (BSC) (99%, Sigma-Aldrich), hexachlorocyclotriphosphazene (HCCP, 99%, Sigma-Aldrich), anhydrous trimethylamine (Sigma-Aldrich) and solvents were used without further purification. Fourier transform infrared spectra (FT-IR) were obtained from KBr pellets of the samples using a NICOLET-6700 FT-IR spectrometer. NMR spectra were recorded in deuterated chloroform using a Bruker AVANCE-III 500 MHz spectrometer. Carbon, nitrogen, sulfur and hydrogen contents of the samples were measured by a Flash 2000 CHNS / O organic elemental analyzer (Thermo Fisher Scientific).

[0060] Overall reaction scheme of the synthesis: The following reaction scheme was used for the synthesis. [ka]

[0061] Preparation of benzenesulfonic acid 4-(4-hydroxy-benzenesulfonyl)-phenyl ester (BSPE) (compound I) as intermediate: To a solution of bis(4-hydroxyphenyl)sulfone (20 g, 80 mmol) in anhydrous acetonitrile (300 ml) was added Et3N (16.7 ml, 120 mmol). Then, benzenesulfonyl chloride (BSC) (80 mmol, 10.2 ml BSC in 50 ml anhydrous acetonitrile) was added dropwise. The reaction was refluxed overnight. The reaction was concentrated and precipitated in water. A white solid was obtained. Compound (I) was purified on a silica gel column using ethyl acetate / hexane=1 / 2.

[0062] Spectroscopic analysis of compound I: 1H-NMR (CDCl3, δ, ppm): δ=7.85 (m, 4H, ArH), 7.79 (m, 2H, ArH), 7.72 (m, 1H, ArH), 7.57 (m, 2H, ArH); 7.14 (m, 2H, ArH); 6.93 (m, 2H, ArH); 13 C-NMR (CDCl3, δ, ppm): δ=160.41, 152.53, 141.03, 134.89, 134.75, 132.32, 130.26, 129.44, 129.24, 128.41, 123.17, 116.25; FT-IR (KBr, cm -1 ): ν 3408 s(OH), 3099 m((CH)arom.), 1589, 1490 s(C=C), 1377 s(O=S=O), 1145 s(CO), 1008 s(SO) C 18 H 14 Analyzed and calculated for O6S2: C, 55.37; H, 3.61; S, 16.43. Detected C, 55.78; H, 3.58; S, 17.72.

[0063] Preparation of hexa(benzenesulfonic acid 4-(4-oxy-benzenesulfonyl)-phenyl ester)cyclotriphosphazene (compound II): A solution of benzenesulfonic acid 4-(4-hydroxy-benzenesulfonyl)-phenyl ester or compound (I) (7.77 g, 19.9 mmol in 200 ml of anhydrous acetonitrile) was added to 4 ml of triethylamine (28.7 mmol). A solution of hexachlorophosphazene (HCCP) (1.05 g (3 mmol) in 50 ml of anhydrous acetonitrile) was added dropwise to the above reaction mixture and continued to stir at room temperature, then refluxed overnight. The reaction solution was concentrated and precipitated in water. A white solid was obtained. Compound (II) was purified on a silica gel column using ethyl acetate / hexane=1 / 1.

[0064] Spectroscopic analysis of compound II: 1H-NMR (CDCl3, δ, ppm): δ=7.97 (m, 12H, ArH), 7.86 (m, 24H, ArH), 7.72 (m, 6H, ArH), 7.58 (m, 12H, ArH); 7.21 (m, 12H, ArH); 6.88 (m, 12H, ArH); 13 C-NMR (CDCl3, δ, ppm): δ= 153.34, 153.07, 139.50, 138.95, 134.91, 134.83, 130.00, 129.97, 129.50, 128.38; 31 P-NMR (CDCl3, δ, ppm): δ=7.52 (s, 1P, cyclotriphosphazene). FTIR (KBr, cm -1 ): ν 3099 m((CH)arom.), 1587, 1487 s(C=C), 1380 s(O=S=O), 1293 (P=N), 1153 (CO), 1014 (SO), 949 (PO), MS: m / z = 2514.02 [MH] + +Formic acid adduct. C 108 H 78 N3O 36 P3S 12 Analyzed and calculated: C, 52.49; H, 3.81; N, 1.70; S, 15.57. Found: C, 52.62; H, 3.07; N, 1.95; S, 15.37.

[0065] Spectroscopic analysis proved the synthesis of compound II using intermediate compound I. Spectroscopic analysis also showed that all phosphorus atoms were substituted with sulfonate esterifying groups.

[0066] Example II Objective: To evaluate the flame retardancy of Compound II in polycarbonate compositions. For the purposes of this example, two different polycarbonate (PC) compositions were formulated and evaluated for flame retardancy using the standard UL94 vertical flame test protocol and associated UL rating criteria.

[0067] Materials: The following polycarbonate formulations were prepared, the formulation details are given in the table below. [Table 1]

[0068] Sample preparation process: The samples were prepared by melt blending. All powder additives were mixed with polycarbonate (PC) powder using a paint shaker and fed into an extruder (ZSK25, co-rotating, twin screw extruder) through a feeder.

[0069] Flame Retardant Test Standard: The obtained samples were evaluated for flame retardant properties. The vertical burn test for UL94 flammability level was measured using FTT 0082 (Fire Testing Technology, UK) equipment according to ASTM D3801 test procedure with sample dimensions of 130mm x 13mm x 1.2mm. In the test, five sample bars suspended vertically on surgical cotton were ignited with a 50W methane gas burner. The flammability properties of all the investigated formulations were measured according to the standard UL94 vertical burn test protocol. The relevant UL rating criteria are given in Table 2.

[0070] The flame retardancy of all the formulations investigated was measured by UL94 vertical flame test using 5 flame bars with thickness of 1.2mm for each sample. The flame retardant class can be evaluated based on the rating given to the material along with the degree of flame retardancy. The degree of flame retardancy is indicated as V0>V1>V2, where V0 is the most flame retardant and V2 is the least flame retardant. [Table 2]

[0071] Results and Conclusions: The results of the flame retardancy tests are listed in Table 3. As is evident from the UL-94 rating data, the addition of compound hexa(benzenesulfonic acid 4-(4-oxy-benzenesulfonyl)-phenyl ester)cyclotriphosphazene (compound II) in the polycarbonate compositions (samples 1 and 2) improved the flame retardancy compared to that of the comparative sample (CE) without compound II. For example, the comparative sample (CE) without compound II and containing BPA polycarbonate resin has a UL-94 flame retardancy rating of V-2, while samples I and 2 have better UL-94 ratings.

[0072] In particular, sample 1 containing 3.0% compound II met the UL94 rating of V-1, and sample 2 containing 2.0% compound II met the UL94 rating requirement of V0.

[0073] Furthermore, compound II was subjected to thermal decomposition test. It was found that compound II (HSSCP) exhibited favorable thermal stability. The onset decomposition temperature (T5%, set when mass loss is equal to 5% by weight) was observed during the test to be T5%=402.9°C and 399.08°C for HSSCP under N2 and air. Therefore, compound II can be effectively used as a flame retardant in polymer compositions. [Table 3]

Claims

1. A sulfonated phosphazene compound selected from the group consisting of: i. Cyclic phosphazene compounds represented by formula 1a: 【Chemistry 1】 wherein each of the variables "a", "b" and "c" is an integer ranging from 1 to 5, inclusive, and preferably each of the variables "a", "b" and "c" is 1; ii. A linear phosphazene compound represented by formula (1b): 【Chemistry 2】 wherein each of the variables "x", "y" and "z" is an integer ranging from 1 to 500, preferably from 50 to 200, preferably from 100 to 200; and iii. A bridged phosphazene compound represented by formula (1c): 【Chemistry 3】 wherein each of the variables "m", "n" and "o" is an integer ranging from 1 to 500, preferably from 50 to 200, and preferably from 100 to 200; wherein each of the substituents "A", "B", "E", "Z", "G", "Q", and "J" are independently the same or different, and each of the substituents "A", "B", "E", "Z", "G", "Q", and "J" is independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a branched or straight chain alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an ether group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkaryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted amine group, and a substituted sulfonate esterifying group represented by formula (1d): 【Chemistry 4】 In the formula, R １ is a substituent selected from the group comprising at least one aryl group containing from 6 to 30 carbon atoms, preferably from 8 to 30 carbon atoms, preferably from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, preferably from 11 to 18 carbon atoms; In the formula, R ２ is a substituent selected from the group consisting of halogen-substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or linear alkyl groups having 1 to 20 carbon atoms, halogen-substituted aryl groups, hydroxyl-substituted aryl groups, nitro-substituted aryl groups, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; However, at least one of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d), and preferably, each of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d). Sulfonated phosphazene compounds.

2. The sulfonated phosphazene compound is a cyclic phosphazene compound represented by formula (2): 【Chemistry 5】 wherein each of the substituents "A", "B", "E", "Z", "G", and "Q" are independently the same or different and are independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, ether groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkenyl-substituted aryl groups having 6 to 30 carbon atoms, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted amine groups, and substituted sulfonate esterifying groups represented by formula (1d): 【Chemistry 6】 In the formula, R １ is a substituent selected from the group comprising at least one aryl group containing from 6 to 30 carbon atoms, preferably from 8 to 30 carbon atoms, preferably from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, preferably from 11 to 18 carbon atoms; In the formula, R ２ is a substituent selected from the group consisting of halogen-substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or linear alkyl groups having 1 to 20 carbon atoms, halogen-substituted aryl groups, hydroxyl-substituted aryl groups, nitro-substituted aryl groups, alkaryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; However, at least one of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d) as defined in claim 1, and preferably each of the substituents "A", "B", "E", "Z", "G" and "Q" is a sulfonate esterified group represented by formula (1d). The sulfonated phosphazene compound according to claim 1.

3. substituent R １ is selected from the group consisting of: 【Chemistry 7】 【change】 In the formula, the substituent R ３ , R ４ , R ５ are each independently selected from the group consisting of halogen substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, and branched or linear alkyl groups having 1 to 10 carbon atoms; The sulfonated phosphazene compound according to any one of claims 1 to 3.

4. substituent R ２ is selected from the group consisting of: 【Chemistry 8】 The sulfonated phosphazene compound according to any one of claims 1 to 4.

5. The sulfonated phosphazene compound is a cyclic phosphazene compound represented by the following formula: 【Chemistry 9】 In the formula, the substituent R １ and R ２ is defined in any of the preceding claims, The sulfonated phosphazene compound according to any one of claims 1 to 2.

6. The sulfonated phosphazene compound is a cyclic phosphazene compound represented by the following formula: 【Chemistry 10】 The sulfonated phosphazene compound according to any one of claims 1 to 5.

7. 1. A method for preparing a sulfonated phosphazene compound, comprising the steps of: i. In the presence of a base, a diol compound (V) represented by the following formula: 【Chemistry 11】 reacting with a sulfonyl halide compound represented by formula (W), 【Chemistry 12】 forming a first intermediate compound; １ and R ２ is defined in any of the preceding claims; the substituent "X" is halogen; preferably, the substituent "X" is chlorine; ii. reacting the first intermediate compound with a phosphazene compound (T) having at least one phosphorus atom substituted with a nucleophilic leaving group (NLG) in the presence of a base to form a sulfonated phosphazene compound; wherein the nucleophilic leaving group (NLG) is selected from the group consisting of a halogen group, a thio group, a cyano group, a tosylate group, an alkoxy group, an aryloxy group, an alkyl ester group, an azide group, and an amine group, and preferably, the nucleophilic leaving group (NLG) is a halogen group; method.

8. 1. A method for preparing a sulfonated phosphazene compound, comprising the steps of: i. In the presence of a base, a diol compound (V) represented by the following formula: 【Chemistry 13】 reacting with a phosphazene compound (T) having at least one phosphorus atom substituted with a nucleophilic leaving group (NLG) to form a second intermediate compound; ii. reacting the second intermediate compound with a sulfonyl halide compound represented by formula (W) in the presence of a base; 【Chemistry 14】 forming a sulfonated phosphazene compound; In the formula, the substituent R １ and R ２ is defined in any of the preceding claims; the substituent "X" is halogen; preferably, the substituent "X" is chlorine; wherein the nucleophilic leaving group (NLG) is selected from the group consisting of a halogen group, a thio group, a cyano group, a tosylate group, an alkoxy group, an aryloxy group, an alkyl ester group, an azide group, and an amine group, and preferably, the nucleophilic leaving group (NLG) is a halogen group; method.

9. The phosphazene compound (T) is a cyclic phosphazene compound represented by the following structure: 【Chemistry 15】 In the formula, substituent L １ , L ２ , L ３ , L ４ , L ５ and L ６ are independently the same or different and are independently selected from the nucleophilic leaving groups (NLG), substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, alkaryl groups having 6 to 30 carbon atoms, alkenyl-substituted aryl groups having 6 to 30 carbon atoms, aralkyl groups having 6 to 30 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted amine groups, with the proviso that the substituents L １ , L ２ , L ３ , L ４ , L ５ Or L ６ At least one of the substituents L １ , L ２ , L ３ , L ４ , L ５ and L ６ are nucleophilic leaving groups (NLG), and preferably the substituents L １ , L ２ , L ３ , L ４ , L ５ and L ６ Each of the substituents L １ , L ２ , L ３ , L ４ , L ５ and L ６ each of which is chlorine; The method according to claims 7 to 8.

10. The phosphazene compound (T) is a cyclic phosphazene compound represented by the following formula: 【Chemistry 16】 The diol compound (V) is represented by the following formula: 【Chemistry 17】 The sulfonyl halide compound (W) is represented by the following formula: 【Chemistry 18】 The method according to claims 7 to 9.

11. The base is KOH, NaOH, LiOH, NaH, KH, K ２ CO ３ , Na ２ CO ３ , Li ２ CO ３ , K ３ P.O. ４ , pyridine, 4-dimethylaminopyridine, trimethylamine, triethylamine, or any combination thereof; The method according to any one of claims 7 to 10.

12. 1. A polymer composition comprising: i. 80.0% to 99.95% by weight, preferably 85.0% to 99.95% by weight, of a thermoplastic polymer, based on the total weight of the composition; and ii. The sulfonated phosphazene compound according to claim 1, in an amount of 0.05% by weight to 20.0% by weight, preferably 0.05% by weight to 15.0% by weight, based on the total weight of the composition; 1. A polymer composition comprising:

13. The thermoplastic polymers include polyethylene terephthalate (PET), impact polypropylene copolymer, propylene ethylene copolymer, propylene ethylene alpha olefin terpolymer, polycarbonate (PC), polybutylene terephthalate (PBT), poly(1,4-cyclohexylidene-cyclohexane-1,4-dicarboxylate) (PCCD), glycol modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), ethylene-C ４ -C １２ selected from alpha-olefin copolymers, polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) and derivatives thereof, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamides (PA), polysulfone sulfonates (PSS), sulfonates of polysulfones, polyetheretherketone (PEEK), acrylonitrile butyldiene styrene (ABS), polyetherketoneketone (PEKK), polyphenylene sulfide (PPS), copolymers thereof, or blends thereof; The polymer composition of claim 11.

14. An article comprising the polymer composition according to claims 12-13.

15. Use of the sulfonated phosphazene compounds according to claims 1 to 6 for improving the flame retardancy of polymer compositions.

Images