Cyclic phosphazene compounds with oxygen-containing phosphaphenanthrene ring structures

Abstract

The novel cyclic phosphazene compound represented by formula (1) useful as a flame retardant for resin materials can improve flame retardancy while suppressing the degradation of physical properties of the resin material and can also achieve good dielectric properties. In formula (1), n is an integer from 3 to 8. 1 and R 2 The following are: (i) each independently represents a nitro group, an alkyl group or alkoxy group having 1 to 8 carbon atoms which may be substituted with an alkyl group or aryl group having 1 to 6 carbon atoms, or an aryl group or aryloxy group having 6 to 20 carbon atoms which may be substituted with an alkyl group or aryl group having 1 to 6 carbon atoms, or (ii) each independently forms a saturated or unsaturated cyclic structure which may be substituted with an alkyl group or carbonyl group having 1 to 6 carbon atoms. a and b are each independently an integer from 0 to 4. The type of oxygen-containing heterophosphaphenanthrene ring structure in each repeating unit is independent. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a cyclic phosphazene compound having an oxaphosphorin ring structure, in particular to a cyclic phosphazene compound having a specific oxaphosphorin ring structure. Background Art

[0002] Materials used in high-capacity, high-speed communication devices supporting fifth-generation (5G) and subsequent generations of high-speed mobile communication systems are required to simultaneously meet dielectric properties of a low dielectric constant (Dk) to reduce signal propagation delay and a low dielectric loss tangent (Df) to reduce signal attenuation (so-called low Dk / Df). Various resin materials have been proposed as materials that can achieve low Dk / Df. However, resin materials are generally flammable, so they are often flame-retarded by adding flame retardants.

[0003] However, while flame retardants can improve the flame retardancy of resin materials, they can also change the physical properties of resin materials, degrading mechanical, electrical, or dielectric properties. For example, in Patent Documents 1 to 3, phosphine oxide is described as a flame retardant incompatible with resins. This phosphine oxide is explained as a substance that can achieve a low Dk / Df for resin materials. However, since phosphine oxide has a low content of phosphorus atoms related to the flame retardancy mechanism of resin materials, in order to achieve the necessary flame retardancy, it is necessary to increase its addition amount relative to the resin material. In addition, in this production method, the incorporation of trace chloride ions is unavoidable. Therefore, when increasing the addition amount to the resin material, the electrical properties of the resin material may be degraded due to the chloride ions.

[0004] Furthermore, Patent Documents 4 to 7 describe trioxybiphenylcyclotriphosphazenes as flame retardants. These phosphazene compounds are described as having high melting points and capable of achieving low Dk / Df ratios. However, these phosphazene compounds are synthesized using chlorocyclotriphosphazenes as starting materials, which may result in residual unsubstituted chlorine in the phosphazene ring. Since the residual chlorine in the phosphazene ring is converted to P-OH groups through hydrolysis, trioxybiphenylcyclotriphosphazenes may reduce their stability over time in resin materials and degrade their electrical properties.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Taiwan Patent Application Publication No. 2015 / 42575;

[0008] Patent Document 2: Japanese Patent Application Publication No. 2019-023263;

[0009] Patent Document 3: Japanese Patent Application Publication No. 2019-044031;

[0010] Patent Document 4: International Publication No. 2019 / 198766;

[0011] Patent Document 5: U.S. Patent Application Publication No. 2019 / 0367727;

[0012] Patent Document 6: Chinese Patent Application Publication No. 110204862;

[0013] Patent document 7: U.S. Patent Application Publication No. 2020 / 0071477. Summary of the Invention

[0014] Problems to be solved by the invention

[0015] The present invention aims to provide a novel cyclic phosphazene compound useful as a flame retardant for resin materials, particularly a novel cyclic phosphazene compound that can improve flame retardancy while suppressing degradation of the physical properties of the resin material and can achieve a low Dk / Df.

[0016] Means for solving problems

[0017] The cyclic phosphazene compound of the present invention is a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure and is represented by the following formula (1).

[0018] [Chemical Formula 1]

[0019]

[0020] In formula (1), n is an integer from 3 to 8. 1 and R 2 The following are: (i) each independently represents a nitro group, an alkyl group or alkoxy group having 1 to 8 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, and an aryl group or aryloxy group having 6 to 20 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group; or (ii) each independently forms a saturated or unsaturated cyclic structure which may be substituted with an alkyl group having 1 to 6 carbon atoms or a carbonyl group. a and b are each independently an integer from 0 to 4. It should be noted that the type of the oxygen-containing phosphaphenanthrene ring structure in each repeating unit is independent.

[0021] In one embodiment of the cyclic phosphazene compound of the present invention, n in formula (1) is 3 or 4.

[0022] Another embodiment of the cyclic phosphazene compound of the present invention is that in formula (1), n is 3 and a and b are 0. One example of the cyclic phosphazene compound of the present invention involved in this embodiment is a mixture of diastereomers. In addition, another example of the cyclic phosphazene compound of the present invention involved in this embodiment is that the stereo configuration of the adjacent oxygen-containing heterophosphaphenanthrene ring structures is cis-cis-cis. Another example of the cyclic phosphazene compound of the present invention involved in this embodiment is that the stereo configuration of the adjacent oxygen-containing heterophosphaphenanthrene ring structures is trans-cis-trans.

[0023] The present invention according to another aspect relates to a mixture of cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure, wherein the mixture contains two or more cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure according to the present invention.

[0024] The novel cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure and a mixture of the cyclic phosphazene compounds according to the present invention are useful as flame retardants for resin materials.

[0025] The present invention according to another aspect relates to a method for producing a cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure according to the present invention. The method comprises the following steps: Step 1, using an azidating agent to derive a chlorodibenzooxaphosphaphenanthrene compound represented by the following formula (2) into an azidation intermediate; and Step 2, subjecting the azidation intermediate obtained in the previous step to a cyclization reaction.

[0026] [Chemical Formula 2]

[0027]

[0028] In formula (2), R 1 and R 2 The following are: (i) each independently represents any one of a nitro group, an alkyl group or alkoxy group having 1 to 8 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group, and an aryl group or aryloxy group having 6 to 20 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group, or (ii) each independently represents a saturated or unsaturated cyclic structure which may be substituted with an alkyl group having 1 to 6 carbon atoms or a carbonyl group. In addition, a and b each independently represent an integer from 0 to 4.

[0029] In one embodiment of this production method, the azidation intermediate used in step 2 is a mixture of two or more azidation intermediates. In this embodiment, the mixture of azidation intermediates is obtained by using two or more chlorodibenzoxaphosphaphenanthrene compounds in step 1.

[0030] According to the production method of the present invention, the novel cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure of the present invention can be produced.

[0031] The present invention according to another aspect relates to a resin composition comprising a resin component and one or more cyclic phosphazene compounds having an oxaphosphaphenanthrene ring structure according to the present invention.

[0032] In the resin composition of the present invention, the resin component is selected from at least one of the following: epoxy resin, phenolic resin, unsaturated polyester resin, diallyl phthalate resin, maleimide resin, polyimide resin, benzophenone resin, Oxazine resin, benzocyclobutene resin, polyolefin resin, styrene resin, polyester resin, aliphatic polyamide resin, semi-aromatic polyamide resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin and modified resins thereof.

[0033] Since the resin composition of the present invention contains one or more novel cyclic phosphazene compounds of the present invention, it is possible to improve flame retardancy while suppressing degradation of the physical properties of the resin material and achieve a low Dk / Df.

[0034] The present invention according to another aspect relates to a resin molded (shaped) body comprising the resin composition of the present invention.

[0035] Since the resin molded article according to the present invention is composed of the resin composition of the present invention, it is possible to improve flame retardancy while suppressing degradation of physical properties of the resin material and achieve a low Dk / Df.

[0036] The present invention according to another aspect relates to an electric / electronic component including the resin molded article of the present invention.

[0037] Since the electric / electronic component according to the present invention includes the resin molded article according to the present invention, it is possible to improve flame retardancy while suppressing degradation of physical properties of the resin material and achieve low Dk / Df. DETAILED DESCRIPTION

[0038] <Cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure>

[0039] The cyclic phosphazene compound of the present invention has an oxygen-containing phosphaphenanthrene ring structure and is represented by the following formula (1).

[0040] [Chemical Formula 3]

[0041]

[0042] In formula (1), n represents an integer from 3 to 8. Therefore, the cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure represented by formula (1) is: a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure (trimer) in which n is 3, a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure (tetramer) in which n is 4, a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure (pentamer) in which n is 5, a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure (hexamer) in which n is 6, a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure (heptamer) in which n is 7, or a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure (octamer) in which n is 8.

[0043] When the cyclic phosphazene compound of the present invention is used as a component of a resin composition for producing a resin molded body for an electrical / electronic component, for example, a compound with a small n tends to achieve a resin molded body with excellent dielectric properties. Therefore, when the cyclic phosphazene compound of the present invention is used as a material for producing a resin molded body for an electrical / electronic component, it is preferred that n in formula (1) is an integer of 3 to 4, and particularly preferably n is 3. In addition, when the cyclic phosphazene compound of the present invention is a mixture of two or more compounds with different n, the greater the content of the compound with a small n, the easier it is to achieve a resin molded body with excellent dielectric properties. Therefore, when the cyclic phosphazene compound of the present invention is a mixture of compounds with different n and is used as a material for producing a resin molded body for an electrical / electronic component, it is preferred that the mixture contains 95% or more of compounds with n of 3 to 4 by mass, and particularly preferably the mixture contains 95% or more of compounds with n of 3 by mass.

[0044] R in formula (1) 1 and R 2 Each independently represents a nitro group, the following R-1 or the following R-2, or the following R-3. 1 and R 2 The numbers a and b are each independently an integer from 0 to 4.

[0045] R-1:

[0046] An alkyl group or alkoxy group having 1 to 8 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group.

[0047] Examples of corresponding alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, 2-ethylhexyl, benzyl, and 2-phenylethyl. In addition, examples of corresponding alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, 2-ethylhexyloxy, benzyl, and 2-phenylethoxy.

[0048] When the cyclic phosphazene compound of the present invention is used as a material for producing a resin molded body for electric / electronic components, R-1 is preferably a methyl group, an ethyl group, an n-propyl group, a benzyl group, or a methoxy group, and particularly preferably a methyl group or an ethyl group.

[0049] R-2:

[0050] An aryl group or aryloxy group having 6 to 20 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group.

[0051] Examples of corresponding aryl groups include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, n-propylphenyl, isopropylphenyl, isopropylmethylphenyl, isopropylethylphenyl, diisopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, n-hexylphenyl, phenylphenyl, naphthyl, anthracenyl, and phenanthryl. Examples of corresponding aryloxy groups include phenoxy, methylphenoxy, dimethylphenoxy, ethylphenoxy, ethylmethylphenoxy, diethylphenoxy, n-propylphenoxy, isopropylphenoxy, isopropylmethylphenoxy, isopropylethylphenoxy, diisopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-pentylphenoxy, n-hexylphenoxy, phenylphenoxy, naphthyloxy, anthracenyloxy, and phenanthryloxy.

[0052] When the cyclic phosphazene compound of the present invention is used as a material for producing a resin molded body for electric / electronic components, R-2 is preferably phenyl, methylphenyl, dimethylphenyl, diethylphenyl, phenylphenyl, naphthyl or phenoxy, and particularly preferably phenyl or methylphenyl.

[0053] R-3:

[0054] It is in R 1 With R 2 The saturated or unsaturated cyclic structure formed by each other may be substituted by an alkyl group or a carbonyl group having 1 to 6 carbon atoms.

[0055] Examples of the corresponding repeating unit of formula (1) having an oxaphosphaphenanthrene ring structure having a saturated ring structure include units represented by the following formulae (3) and (4).

[0056] [Chemical Formula 4]

[0057]

[0058] Furthermore, examples of the corresponding repeating unit of formula (1) having an oxaphosphaphenanthrene ring structure having an unsaturated ring structure include units represented by the following formula (5).

[0059] [Chemical Formula 5]

[0060]

[0061] The types of the oxygen-containing phosphaphenanthrene ring structures in each repeating unit of the cyclic phosphazene compound of the present invention are independent. Therefore, the cyclic phosphazene compound of the present invention may be a compound in which all oxygen-containing phosphaphenanthrene ring structures are the same, or a compound having two or more oxygen-containing phosphaphenanthrene ring structures.

[0062] Specific examples of the cyclic phosphazene compound of the present invention represented by formula (1) include any one of a cyclotriphosphazene compound having an oxygen-containing phosphaphenanthrene ring structure in which n is 3 in formula (1), a cyclotetraphosphazene compound having an oxygen-containing phosphaphenanthrene ring structure in which n is 4 in formula (1), a cyclopentaphosphazene compound having an oxygen-containing phosphaphenanthrene ring structure in which n is 5 in formula (1), a cyclohexaphosphazene compound having an oxygen-containing phosphaphenanthrene ring structure in which n is 6 in formula (1), a cycloheptaphosphazene compound having an oxygen-containing phosphaphenanthrene ring structure in which n is 7 in formula (1), or a cyclooctaphosphazene compound having an oxygen-containing phosphaphenanthrene ring structure in which n is 8 in formula (1), wherein a, b, and R 1 and R 2 The combinations are shown in Table 1 below.

[0063] [Table 1]

[0064] Table 1

[0065]

[0066]

[0067] When the cyclic phosphazene compound of the present invention is used as a material for producing a resin molded body for electrical / electronic components, among the above examples, a cyclotriphosphazene compound wherein n is 3 in formula (1) or a cyclotetraphosphazene compound wherein n is 4 in formula (1), i.e., the compound of combination example 1, 2 or 3, is preferred, and a cyclotriphosphazene compound wherein n is 3 in formula (1), i.e., the compound of combination example 1 or 2, is particularly preferred.

[0068] In the above examples, the compound of the cyclotriphosphazene compound in which n is 3 in the formula (1), ie, the compound of Combination Example 1, has a structure represented by the following formula (6).

[0069] [Chemical Formula 6]

[0070]

[0071] The cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure represented by formula (6) is generally obtained as a mixture of diastereomers when produced by the following production method. That is, in the stereo configuration of the adjacent oxygen-containing phosphaphenanthrene ring structure, it is obtained as a mixture of a cis-cis-cis compound represented by formula (7) below (hereinafter referred to as "cis type") and a trans-cis-trans compound represented by formula (8) below (hereinafter referred to as "trans type").

[0072] [Chemical Formula 7]

[0073]

[0074] [Chemical Formula 8]

[0075]

[0076] Such a mixture of diastereomers can be used as a mixture, but the cis- and trans-type compounds can also be separated and used as a single compound of each type. As a separation method, for example, a combination of separation and filtration using solubility in a solvent such as toluene, solvent extraction, recrystallization, or separation by column chromatography can be used.

[0077] <Mixture of cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure>

[0078] The mixture of cyclic phosphazene compounds of the present invention contains two or more cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure according to the present invention. Examples of such a mixture include any mixture of the compounds listed as specific examples of the cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure according to the present invention. When the cyclic phosphazene compound of the present invention is used as a material for producing a resin molded article for an electric / electronic component, a mixture of a cyclotriphosphazene compound having n of 3 in formula (1) and a cyclotetraphosphazene compound having n of 4 in formula (2), i.e., any combination selected from Combination Examples 1, 2, and 3, is preferred.

[0079] It should be noted that the mixture of cyclic phosphazene compounds involved in the present invention may be a mixture of isomers such as the diastereoisomer mixture of the above-mentioned cyclotriphosphazene compound. The cyclic phosphazene compound involved in the present invention, wherein n in formula (1) is 4 or greater, is usually obtained as a mixture of stereoisomers having a plurality of diastereomers and enantiomers when produced by the following production method.

[0080] <Method for producing a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure>

[0081] The cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure according to the present invention can be produced, for example, by any of the following production methods 1 to 4, which uses a chlorodibenzooxaphosphaphenanthrene compound as a starting material and intermolecularly cyclizes an intermediate derived from the starting material.

[0082] Manufacturing method 1

[0083] This production method is carried out, for example, according to the production method of a cyclic phosphazene compound described in the following non-patent document 1 or 2, that is, the production method comprises the following steps: step 1, azidating a chlorine-containing dibenzoxaphosphaphenanthrene compound; and step 2, cyclizing the azidated intermediate obtained in step 1.

[0084] [Non-Patent Document 1]

[0085] G.Tesi,CPHaber,CMDouglas,Proc.Chem.Soc.,London,1960,p.219.

[0086] [Non-Patent Document 2]

[0087] RHKratzer,KLPaciorek,Inorg.Chem.,1965,Vol.4,p.1767.

[0088] Chlorodibenzoxaphosphaphenanthrene compounds:

[0089] In this production method, first, a chlorodibenzoxaphosphaphenanthrene-based compound represented by the following formula (2) is prepared as a raw material.

[0090] [Chemical Formula 9]

[0091]

[0092] R in formula (2) 1 and R 2 Each independently represents a nitro group or the following R-1, R-2 or R-3.1 and R 2 The numbers a and b are each independently an integer from 0 to 4.

[0093] R-1:

[0094] The same as R-1 in formula (1).

[0095] R-2:

[0096] The same as R-2 in formula (1).

[0097] R-3:

[0098] In R 1 With R 2 The saturated or unsaturated cyclic structure formed by each other may be substituted by an alkyl group or a carbonyl group having 1 to 6 carbon atoms.

[0099] Examples of the corresponding chlorodibenzoxaphosphaphenanthrene-based compound represented by formula (2) having an oxaphosphaphenanthrene ring structure having a saturated ring structure include compounds represented by the following formulas (9) and (10).

[0100] [Chemical Formula 10]

[0101]

[0102] Furthermore, examples of the corresponding chlorodibenzoxaphosphaphenanthrene-based compound represented by formula (2) having an oxaphosphaphenanthrene ring structure having an unsaturated ring structure include compounds represented by the following formula (11).

[0103] [Chemical Formula 11]

[0104]

[0105] In the case of producing the compound involved in the above specific example of the cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure involved in the present invention, the chlorodibenzooxaphosphaphenanthrene compound as a raw material is selected from a, b, R 1 and R 2 Compounds corresponding to the combinations in Table 1 above.

[0106] The chlorodibenzoxaphosphaphenanthrene-based compound represented by formula (2) can be produced by reacting a phenol represented by the following formula (12) with phosphorus trichloride and then adding a catalyst such as zinc chloride to carry out a cyclization reaction.

[0107] [Chemical Formula 12]

[0108]

[0109] R in formula (12)1 and R 2 And a and b are the same as in formula (2).

[0110] Methods for producing such chlorodibenzoxaphosphaphenanthrene-based compounds are described in documents such as Patent Documents 8 and 9 and Non-Patent Documents 3 and 4 listed below.

[0111] [Patent Document 8]

[0112] U.S. Patent No. 3,702,878

[0113] [Patent Document 9]

[0114] U.S. Patent No. 5,391,798

[0115] [Non-Patent Document 3]

[0116] Stephen D. Pastor, John D. Spivack, Leander P. Steinhuebel, Phosphorus and Sulfur, 1987, Vol.31, p.71.

[0117] [Non-Patent Document 4]

[0118] Asfia Qureshi,Allan S.Hay,J.Chem.Res(M),1998,p.1601.

[0119] As the phenols represented by the formula (12), R-containing cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure can be used. 1 and R 2 and R corresponding to a and b 1 and R 2As well as the phenols of a and b. Examples of the corresponding phenols include 2-phenylphenol, 2-methyl-6-phenylphenol, 3-methyl-6-phenylphenol, 3-methyl-2-phenylphenol, 4-methyl-2-phenylphenol, 2-(2-methylphenyl)phenol, 2-(3-methylphenyl)phenol, 2-(4-methylphenyl)phenol, 2,3-dimethyl-6-phenylphenol, 2,5-dimethyl-6-phenylphenol, 3,5-dimethyl-2-phenylphenol, Phenol, 4,5-dimethyl-2-phenylphenol, 2-(2,3-dimethylphenyl)phenol, 2-(2,4-dimethylphenyl)phenol, 2-(2,5-dimethylphenyl)phenol, 2-(3,5-dimethylphenyl)phenol, 2'-hydroxy-2,3'-dimethyl-biphenyl, 2'-hydroxy-2,5'-dimethyl-biphenyl, 2'-hydroxy-3,5'-dimethyl-biphenyl, 2'-hydroxy-4,5'-dimethyl phenylphenol, 2-tert-butyl-6-phenylphenol, 4-tert-butyl-2-phenylphenol, 2-tert-butyl-4-methyl-6-phenylphenol, 5-benzyl-2-phenylphenol, 2-(2-methoxyphenyl)phenol, 2-(3-methyl-6-phenylphenol), 2-(2-methoxyphenyl)phenol, 2-(2-methyl-2-phenylphenol), 2-(2-methyl-6-phenylphenol), 2-(2-methyl-2 ... phenol, 2-(4-methoxyphenyl)phenol, 2-(2-methoxy-5-methylphenyl)phenol, 2-(4-methoxy-2-methylphenyl)phenol, 2-(4-methoxy-3-methylphenyl)phenol, 2-(4-ethoxy-2-methylphenyl)phenol, 2,3-diphenylphenol, 2,6-diphenylphenol, 4-nitro-2-phenylphenol, 4-hydroxyfluorene, 4-hydroxyfluorenone and 4-phenanthrol, etc.

[0120] When the target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure has one type of oxygen-containing phosphaphenanthrene ring structure, one type of phenol corresponding to the target oxygen-containing phosphaphenanthrene ring structure can be used as the above-mentioned phenol. When the target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure has two or more types of oxygen-containing phosphaphenanthrene ring structures, two or more types of phenol corresponding to the target oxygen-containing phosphaphenanthrene ring structure can be mixed and used as the above-mentioned phenol.

[0121] In addition to the method using the above-mentioned phenols, the chlorodibenzoxaphosphaphenanthrene-based compound represented by formula (2) can also be produced by chlorinating dibenzoxaphosphaphenanthrene oxide with phosphorus trichloride as described in Non-Patent Document 5.

[0122] [Non-Patent Document 5]

[0123] P.Abranyi-Balogha,G.Keglevich,Synthetic Communications,2011,vol.41,p.1421.

[0124] Step 1:

[0125] Depending on the type of the target cyclic phosphazene compound containing an oxaphosphaphenanthrene ring structure, a single chlorodibenzooxaphosphaphenanthrene compound represented by formula (2) as the azidation target in this step may be used, or a mixture of two or more of these compounds may be used. The mixture of two or more compounds may be a mixture prepared by mixing two or more chlorodibenzooxaphosphaphenanthrene compounds represented by formula (2) prepared separately, or a mixture obtained by mixing two or more phenols when preparing the chlorodibenzooxaphosphaphenanthrene compound represented by formula (2).

[0126] Various known azidating agents can be used for the azidation of chlorodibenzoxaphosphaphenanthrene compounds. Examples of usable azidating agents include metal azides such as lithium azide, sodium azide, and potassium azide; organic azide compounds such as trimethylsilyl azide, p-toluenesulfonyl azide, and tosyl azide (TsN3); and phosphoryl azide compounds such as diphenylphosphoryl azide (DPPA). Among these azidating agents, sodium azide, trimethylsilyl azide, or DPPA are preferred from the perspective of versatility, with sodium azide being particularly preferred. Two or more azidating agents can also be used in combination, for example by mixing them.

[0127] From the viewpoint of sufficient progress of the azidation reaction, the amount of the azidating agent used is preferably about 1 to 2 equivalents, more preferably about 1.1 to 1.3 equivalents, relative to the chlorodibenzoxaphosphaphenanthrene compound represented by formula (2).

[0128] In this process, a chlorodibenzoxazolidinone compound represented by formula (2) and an azidating agent are usually added to a solvent to carry out an azidation reaction. At this time, the temperature can be heated to about 40 to 250°C. There is no particular limitation on the type of solvent used here, but an aprotic polar solvent is preferred. Examples of aprotic polar solvents include organic solvents such as acetone, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide. Among such aprotic polar solvents, N,N-dimethylformamide or dimethyl sulfoxide, which have a particularly high relative dielectric constant and can be obtained at a low cost, are preferably used. The solvents can be used in combination by mixing two or more solvents.

[0129] By the azidation reaction of this step, the chlorodibenzoxaphosphaphenanthrene compound represented by formula (2) is derived into an azidation intermediate.

[0130] When a mixture of chlorodibenzoxaphosphaphenanthrene compounds represented by formula (2) is used in this step, a mixture of azidation intermediates corresponding to the mixture of chlorodibenzoxaphosphaphenanthrene compounds represented by formula (2) is obtained in this step.

[0131] Step 2:

[0132] The azidation intermediate obtained in step 1 is subjected to a cyclization reaction to derive the target cyclic phosphazene compound having an oxaphosphaphenanthrene ring. Depending on the type of oxaphosphaphenanthrene ring structure possessed by the target cyclic phosphazene compound, a single azidation intermediate or a mixture of two or more intermediates can be used as the subject of the cyclization reaction in this step. The mixture of two or more intermediates can be a mixture prepared by mixing two or more azidation intermediates prepared separately in step 1, or a mixture obtained by using a mixture of two or more chlorodibenzooxaphosphaphenanthrene-based compounds represented by formula (2) in step 1.

[0133] In this step, the cyclization reaction can be basically carried out by stirring or allowing the reaction solution obtained in step 1 to stand. At this time, the reaction system may be heated. The heating temperature of the reaction system is generally preferably set to 40 to 100°C. The degree of progress of the cyclization reaction (i.e., the formation of n-mers such as trimers and tetramers of the azidation intermediate) can be controlled within a certain range by selecting the type of solvent that can be used in this step and adjusting the reaction temperature.

[0134] The cyclization reaction can be carried out in the absence of a solvent or in a solvent. The type of solvent that can be used is not particularly limited as long as it does not adversely affect the cyclization reaction, but aprotic polar solvents are generally preferred. Examples of preferred aprotic polar solvents include organic solvents such as acetone, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide, but N,N-dimethylformamide or dimethyl sulfoxide, which have a particularly high relative dielectric constant and can be obtained cheaply, are preferred. It can be carried out and used in combination by mixing two or more solvents. When a solvent is used, the heating temperature for the cyclization reaction is controlled within a range not exceeding the boiling point of the solvent.

[0135] The target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure obtained in this step is usually obtained as a mixture of a plurality of compounds having different numbers of repeating units of formula (1). Furthermore, when a single azidation intermediate is used in this step, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is the same. Furthermore, when two or more azidation intermediates are used in this step, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is two or more.

[0136] The target cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure obtained in this step can be usually isolated and purified from the reaction system by a common method such as filtration, solvent extraction, separation by column chromatography, or recrystallization.

[0137] Manufacturing method 2

[0138] In this production method, the target cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure is produced according to the following steps, which include: step 1, chlorinating a chlorodibenzooxaphosphaphenanthrene compound to derive a trichloro-dibenzoxyphosphorane compound; and step 2, cyclizing the trichloro-dibenzoxyphosphorane compound obtained in step 1.

[0139] Step 1:

[0140] Depending on the type of oxaphosphaphenanthrene ring structure possessed by the target cyclic phosphazene compound, the chlorodibenzoxaphosphaphenanthrene compound used in this step may be a compound represented by formula (2) used in Production Method 1, or a mixture of two or more of these compounds. The mixture of two or more compounds may be a mixture prepared by mixing two or more chlorodibenzoxaphosphaphenanthrene compounds prepared separately, or a mixture obtained by mixing two or more phenols when preparing the chlorodibenzoxaphosphaphenanthrene compound.

[0141] In this step, for example, referring to the description in the following Non-Patent Document 6, a chlorodibenzoxaphosphaphenanthrene compound is reacted with a chlorinating agent to be chlorinated and thereby derived into a trichloro-dibenzoxyphosphorane compound.

[0142] [Non-Patent Document 6]

[0143] J.Gloede,U.Piepera,B.Costisella,RP.Kruger,Z.Anorg.Allg.Chem.2003,Vol.629,p.998.

[0144] Various known chlorinating agents can be used in the chlorination step of this step. A preferred example of a chlorinating agent is chlorine gas. To ensure sufficient chlorination while preventing excessive chlorination, the amount of the chlorinating agent used is preferably 1 to 1.1 equivalents, more preferably 1.01 to 1.05 equivalents, relative to the chlorodibenzoxaphosphaphenanthrene compound.

[0145] In this step, a chlorinating agent is typically added to a chlorodibenzoxaphosphaphenanthrene compound, either in the absence of a solvent or in the presence of a solvent, to carry out a chlorination reaction. The temperature can be heated to approximately 40 to 150°C. When a solvent is used, the type of solvent that can be used is not particularly limited, but aprotic solvents are preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among these aprotic solvents, chlorobenzene or dichlorobenzene is preferred because the solvent itself is difficult to chlorinate. Combination use of two or more solvents is also possible, for example by mixing them.

[0146] In this step, the trichloro-dibenzoxaphosphaphenanthrene compound derived by chlorinating the chlorodibenzoxaphosphaphenanthrene compound is represented by the following formula (13). 1 and R 2 And a and b are the same as in formula (2).

[0147] [Chemical Formula 13]

[0148]

[0149] When a mixture of chlorodibenzoxaphosphaphenanthrene compounds is used in this step, a mixture of trichloro-dibenzooxyphosphacyclopentane compounds represented by formula (13) corresponding to the mixture of chlorodibenzoxaphosphaphenanthrene compounds is obtained in this step.

[0150] Step 2:

[0151] In this step, the trichloro-dibenzooxyphospholane compound obtained in step 1 is subjected to a cyclization reaction to derive a cyclic phosphazene compound having the target oxaphosphaphenanthrene ring. Depending on the type of oxaphosphaphenanthrene ring structure possessed by the target cyclic phosphazene compound, a single trichloro-dibenzooxyphospholane compound or a mixture of two or more such compounds may be used in this step. The mixture of two or more compounds may be a mixture prepared by mixing two or more trichloro-dibenzooxyphospholane compounds prepared separately in step 1, or a mixture obtained by using a mixture of two or more chlorodibenzooxaphosphaphenanthrene compounds in step 1.

[0152] The trichloro-dibenzooxyphospholane compound obtained in step 1 is cyclized by reacting with ammonia or ammonium chloride according to the description of, for example, Patent Document 10 or Non-Patent Document 7 or 8 listed below.

[0153] [Patent Document 10]

[0154] U.S. Patent No. 2,853,517

[0155] [Non-Patent Document 7]

[0156] CPHaber,DLHerring,EALawton,J.Am.Chem.Sci.,1958,Vol.80,p.2116.

[0157] [Non-Patent Document 8]

[0158] M.Taillefer,F.Plenat,C.Chamalet-Combes,V.Vicente,HJCristau,Phosphorus Res.Bull.,1999,Vol.10,p.696.

[0159] The cyclization reaction of trichloro-dibenzoylphosphacyclopentane compounds using ammonia or ammonium chloride can be carried out in the absence of a solvent or in a solvent. When a solvent is used, the type of solvent that can be used is not particularly limited as long as it does not adversely affect the cyclization reaction, but aprotic solvents are generally preferred. Examples of preferred aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene, but chlorobenzene or toluene, which are available at low cost, are preferred. The reaction can be carried out in combination by mixing two or more solvents.

[0160] The reaction system may be heated during the cyclization reaction. The heating temperature of the reaction system is preferably set to 40 to 170°C. However, when a solvent is used, the heating temperature is controlled within a range not exceeding the boiling point of the solvent.

[0161] The degree of cyclization (i.e., trimerization, tetramerization, etc. of the trichloro-dibenzooxyphospholane compound) can be controlled within a certain range by selecting the type of solvent used in this step or adjusting the reaction temperature.

[0162] The target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure obtained in this step is usually obtained as a mixture of a plurality of compounds having different numbers of repeating units of formula (1). Furthermore, when a single trichloro-dibenzooxyphosphacyclopentane compound is used in this step, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is the same. Furthermore, when two or more trichloro-dibenzooxyphosphacyclopentane compounds are used in this step, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is two or more.

[0163] Manufacturing method 3

[0164] In this production method, according to the description of the following Non-Patent Document 9, a chlorodibenzooxaphosphaphenanthrene compound is reacted with chloramine, and the intermediate product is cyclized to produce the target cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure.

[0165] [Non-Patent Document 9]

[0166] ITGilson,HHSisler,Inorg.Chem.,1965,Vol.4,p.273.

[0167] The chlorodibenzoxaphosphaphenanthrene compound used in this production method is the compound represented by formula (2) used in Production Method 1. Depending on the type of the oxaphosphaphenanthrene ring structure possessed by the target cyclic phosphazene compound, a single compound or a mixture of two or more compounds may be used. The mixture of two or more compounds may be a mixture prepared by mixing two or more chlorodibenzoxaphosphaphenanthrene compounds prepared separately, or a mixture obtained by mixing two or more phenols when preparing the chlorodibenzoxaphosphaphenanthrene compound.

[0168] From the viewpoint of allowing the chloramination (chloroamination) reaction of the chlorodibenzoxaphosphaphenanthrene-based compound to proceed sufficiently while suppressing excessive chloramination reaction, the amount of chloramine used is preferably set to about 1 to 1.1 equivalents, more preferably about 1.01 to 1.05 equivalents, relative to the chlorodibenzoxaphosphaphenanthrene-based compound.

[0169] The reaction of the chlorodibenzoxaphosphaphenanthrene compound with chloramine can be carried out in the absence of a solvent or in the presence of a solvent. When a solvent is used, the type of solvent that can be used is not particularly limited as long as it does not adversely affect the cyclization reaction, but aprotic solvents are preferred. Preferred examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene, with chlorobenzene and toluene being preferred due to their low cost. Two or more solvents can be mixed and used in combination.

[0170] During the reaction of the chlorodibenzoxaphosphaphenanthrene compound and chloramine, the reaction system may be heated. The heating temperature of the reaction system is preferably set to 40 to 170°C. However, when a solvent is used, the heating temperature is controlled within a range not exceeding the boiling point of the solvent.

[0171] In the reaction between a chlorodibenzoxaphosphaphenanthrene compound and chloramine, chloramine is added to the chlorodibenzoxaphosphaphenanthrene compound. This addition product (i.e., the intermediate product) is then subjected to a dehydrochlorination step for condensation to undergo a cyclization reaction, thereby obtaining the target cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure.

[0172] The degree of the cyclization reaction (i.e., the trimerization, tetramerization, or other n-merization of the chlorodibenzoxaphosphaphenanthrene compound) can be controlled within a certain range by selecting the type of solvent used or adjusting the reaction temperature.

[0173] The target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure obtained by this production method is usually obtained as a mixture of a plurality of compounds having different numbers of repeating units of formula (1). Furthermore, when a single chlorodibenzooxaphosphaphenanthrene-based compound is used, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is the same. When two or more chlorodibenzooxaphosphaphenanthrene-based compounds are used, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is two or more.

[0174] Manufacturing Method 4

[0175] In this production method, the target cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure is produced according to the following steps, which include: step 1, preparing a phosphonamidate compound represented by the following formula (14) from a chlorodibenzooxaphosphaphenanthrene compound; and step 2, deriving the phosphonamidate compound obtained in step 1 into a cyclic phosphazene compound.

[0176] [Chemical Formula 14]

[0177]

[0178] R in formula (14) 1 and R 2 And a and b are the same as in formula (2).

[0179] Step 1:

[0180] This process includes the following steps: step 1A, deriving a chlorodibenzoxaphosphine-phenanthrene compound into a dibenzoxaphosphine-oxide compound represented by the following formula (15); step 1B, deriving the dibenzoxaphosphine-oxide compound obtained in step 1A into a chloro-dibenzoxaphosphine-oxide compound represented by the following formula (16); and step 1C, deriving the chloro-dibenzoxaphosphine-oxide compound obtained in step 1B into a target phosphonamide ester compound.

[0181] Process 1A

[0182] The chlorodibenzoxaphosphaphenanthrene compound used in this step is the compound represented by formula (2) used in Production Method 1. Depending on the type of the oxaphosphaphenanthrene ring structure possessed by the target cyclic phosphazene compound, a single compound or a mixture of two or more compounds may be used. The mixture of two or more compounds may be a mixture prepared by mixing two or more chlorodibenzoxaphosphaphenanthrene compounds prepared separately, or a mixture obtained by mixing two or more phenols when preparing the chlorodibenzoxaphosphaphenanthrene compound.

[0183] In this step, for example, according to the description of Patent Document 11 or 12 listed below, a chlorodibenzoxaphosphophananthrene compound is hydrolyzed to induce a dibenzoxaphosphine-oxide compound represented by the following formula (15).

[0184] [Patent Document 11]

[0185] U.S. Patent No. 5,481,017

[0186] [Patent Document 12]

[0187] U.S. Patent No. 5,821,376

[0188] [Chemical Formula 15]

[0189]

[0190] R in formula (15) 1 and R 2 And a and b are the same as in formula (2).

[0191] Various known hydrolyzing agents can be used for the hydrolysis of chlorodibenzoxaphosphaphenanthrene compounds. Examples of usable hydrolyzing agents include water, ice, and steam.

[0192] From the viewpoint of allowing the hydrolysis reaction to proceed sufficiently while suppressing excessive hydrolysis, the amount of the hydrolyzing agent used is preferably 1 to 100 equivalents, more preferably 10 to 50 equivalents, relative to the chlorodibenzoxaphosphaphenanthrene compound.

[0193] In this step, a hydrolysis agent is usually added to the chlorodibenzoxaphosphaphenanthrene compound in the absence of a solvent or in a solvent to allow the hydrolysis reaction to proceed. At this time, the reaction system can be heated to about 40 to 150°C. When a solvent is used, the solvent that can be used is not particularly limited as long as it does not hinder the hydrolysis reaction, but an aprotic solvent is preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, mesitylene, acetone, tetrahydrofuran, and acetonitrile. Among such aprotic solvents, chlorobenzene or toluene is preferably used because they are easily separated from the hydrolysis agent. The solvents can be used in combination by mixing two or more solvents.

[0194] When a mixture of chlorodibenzoxaphosphophanate-based compounds is used in this step, a mixture of dibenzoxaphosphine-oxide-based compounds represented by formula (15) corresponding to the mixture of chlorodibenzoxaphosphophanate-based compounds is obtained in this step.

[0195] Process 1B

[0196] In this step, for example, according to the description in the following Non-Patent Document 10, the dibenzooxaphosphine-oxide compound obtained in step 1A is chlorinated to induce a chloro-dibenzooxaphosphine-oxide compound represented by the following formula (16).

[0197] [Non-Patent Document 10]

[0198] A.Salmeia,G.Baumgartner,M.Jovic,A.Gossi,W.Riedl,T.Zich,S.Gann,Org.Process Res.Dev.,2018,Vol.22,p.1570-1577.

[0199] [Chemical Formula 16]

[0200]

[0201] R in formula (16) 1 and R 2 And a and b are the same as in formula (2).

[0202] In this step, a single dibenzooxaphosphine-oxide compound obtained in step 1A or a mixture of two or more dibenzooxaphosphine-oxide compounds may be used, depending on the type of the target chlorodibenzoxaphosphine-oxide compound. The mixture of two or more compounds may be a mixture prepared by mixing two or more dibenzooxaphosphine-oxide compounds prepared separately in step 1A, or a mixture obtained by using a mixture of two or more chlorodibenzoxaphosphine-phenanthren-based compounds in step 1A.

[0203] In this step, the dibenzoxazine-oxide compound obtained in step 1A is basically chlorinated by reacting it with a chlorinating agent. As the chlorinating agent, various known chlorinating agents can be used. For example, carbon tetrachloride, chlorine gas, sulfuryl chloride, trichloroisocyanuric acid (TCCA), or N-chlorosuccinimide (NCS) described in Non-Patent Document 10 can be used.

[0204] The chlorination reaction can be carried out in the absence of a solvent or in a solvent. When a solvent is used, the solvent is not particularly limited as long as it is unlikely to hinder the chlorination reaction, but an aprotic solvent is preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among such aprotic solvents, chlorobenzene or toluene, which are available at low cost, are preferred. The reaction can be carried out in combination by mixing two or more solvents.

[0205] During the chlorination reaction, the reaction system may be heated. In this case, the heating temperature is generally preferably set to 40-100°C. However, when a solvent is used, the heating temperature is controlled within a range not exceeding the boiling point of the solvent. The extent of the chlorination reaction (i.e., the chlorination of the dibenzoxazine-oxide compound) can be controlled within a certain range by selecting the type of solvent or adjusting the reaction temperature.

[0206] When a mixture of dibenzoxazine-oxide compounds is used in this step, a mixture of chloro-dibenzoxazine-oxide compounds represented by formula (16) corresponding to the mixture of dibenzoxazine-oxide compounds is obtained in this step.

[0207] Process 1C

[0208] In this step, for example, according to the description in Non-Patent Document 11 below, the chloro-dibenzoxaphosphine-oxide compound obtained in Step 1B is reacted with an aminating agent to induce a target phosphonamide ester compound.

[0209] [Non-Patent Document 11]

[0210] N.Kreutzkamp,H.Schindler,Arch.Pharm.(Weiheim),1960,Vol.293,p.296-305.

[0211] In this step, a single chloro-dibenzoxazine-oxide compound obtained in step 1B or a mixture of two or more compounds may be used, depending on the type of the target phosphonamidate compound. The mixture of two or more compounds may be a mixture prepared by mixing two or more chloro-dibenzoxazine-oxide compounds prepared separately in step 1B, or a mixture obtained by using a mixture of two or more dibenzoxazine-oxide compounds in step 1B.

[0212] In this step, the chloro-dibenzoxaphosphine-oxide compound obtained in step 1B is basically reacted with an aminating agent to achieve amination. Various known aminating agents can be used as the aminating agent. For example, aqueous ammonia or ammonia gas described in Non-Patent Document 11 can be used.

[0213] The amination reaction can be carried out in the absence of a solvent or in the presence of a solvent. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit the amination reaction, but an aprotic solvent is preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among these aprotic solvents, chlorobenzene or toluene are preferred, as they are inexpensive. Two or more solvents can be mixed and used in combination.

[0214] During the amination reaction, the reaction system may be heated. In this case, the heating temperature is generally preferably set to 40-100°C. However, when a solvent is used, the heating temperature should be controlled within a range not exceeding the boiling point of the solvent. The degree of progress of the amination reaction (i.e., amination of the chloro-dibenzoxazine-oxide compound) can be controlled within a certain range by selecting the type of solvent or adjusting the reaction temperature.

[0215] When a mixture of chloro-dibenzoxazine-oxide compounds is used in this step, a mixture of phosphonamide ester compounds represented by formula (14) corresponding to the mixture of chloro-dibenzoxazine-oxide compounds is obtained in this step.

[0216] Step 2:

[0217] In this step, for example, according to the description in Non-Patent Document 12, the phosphonamidate compound obtained in Step 1 is cyclized by an Appel reaction to induce a target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure.

[0218] [Non-Patent Document 12]

[0219] Rolf Appel, Heinz Einig, Chem. Ber. 1975, Vol. 108, p. 914.

[0220] In this step, depending on the type of oxygen-containing phosphaphenanthrene ring structure possessed by the target cyclic phosphazene compound, a single compound or a mixture of two or more compounds of the phosphonamidate-based compound obtained in step 1 may be used. The mixture of two or more compounds may be a mixture prepared by mixing two or more phosphonamidate-based compounds prepared separately in step 1, or a mixture obtained by using a mixture of two or more chloro-dibenzoxaphosphine-oxide-based compounds in step 1C of step 1.

[0221] In this step, the phosphonamide compound obtained in step 1 is basically cyclized by subjecting it to an Appel reaction with a phosphine such as a triarylphosphine or a trialkylphosphine, carbon tetrachloride, and a tertiary amine such as triethylamine or diisopropylethylamine.

[0222] In this step, the cyclization reaction can be carried out in the absence of a solvent or in the presence of a solvent. When a solvent is used, the solvent is not particularly limited as long as it does not hinder the cyclization reaction, but an aprotic solvent is preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among such aprotic solvents, chlorobenzene or toluene, which are inexpensive to obtain, are preferred. The reaction can be carried out in combination by mixing two or more solvents.

[0223] During the cyclization reaction, the reaction system may be heated. In this case, the heating temperature is generally preferably set to 40-170°C. However, when a solvent is used, the heating temperature should be controlled within a range not exceeding the boiling point of the solvent. The degree of cyclization (i.e., the formation of n-mers such as trimerization and tetramerization of the phosphonamidate compound) can be controlled within a certain range by selecting the type of solvent or adjusting the reaction temperature.

[0224] The target cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure obtained in this step is usually obtained as a mixture of a plurality of compounds having different numbers of repeating units of formula (1). Furthermore, when a single phosphonamidate-based compound is used in this step, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is the same. Furthermore, when two or more phosphonamidate-based compounds are used in this step, the oxygen-containing phosphaphenanthrene ring structure of each repeating unit of formula (1) in the target cyclic phosphazene compound is two or more.

[0225] The target cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure obtained in this step can be usually isolated and purified from the reaction system by a common method such as filtration, solvent extraction, separation by column chromatography, or recrystallization.

[0226] <Resin Composition>

[0227] The resin composition of the present invention comprises the cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to the present invention and a resin component. Two or more cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure according to the present invention may be used in combination.

[0228] The resin component is not particularly limited, and various thermoplastic resins or thermosetting resins can be used. A thermosetting resin and a thermoplastic resin can be used in combination. Furthermore, the resin component can be natural or synthetic. It should be noted that the term "resin component" also includes rubber and elastomers.

[0229] Examples of thermosetting resins that can be used include epoxy resins, phenolic resins, melamine resins, urea resins, silicone resins, polyurethane resins, unsaturated polyester resins, diallyl phthalate resins, thermosetting acrylic resins, polyimide resins, polycarbodiimide resins, maleimide resins, maleimide-cyanate resins, cyanate resins, benzophenone resins, and the like. Azoline resin, polybenzimidazole resin, benzocyclobutene resin, natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, ethylene propylene diene rubber, acrylonitrile butadiene rubber, styrene isoprene butadiene rubber, and chloroprene rubber. Two or more thermosetting resins may be used in combination. Furthermore, in the above examples, polyimide resins such as polyimide resins, polycarbodiimide resins, maleimide resins, or maleimide-cyanate resins may be used in combination with thermoplastic or solvent-soluble resins to improve their processability and adhesiveness.

[0230] As the epoxy resins listed as examples of thermosetting resins, various epoxy resins can be used as long as they are compounds having two or more epoxy groups in one molecule. As specific examples, there can be listed novolac epoxy resins obtained by reacting phenols with aldehydes, such as phenol novolac epoxy resins, brominated phenol novolac epoxy resins, o-cresol novolac epoxy resins, biphenyl novolac epoxy resins, bisphenol-A novolac epoxy resins, and naphthol novolac epoxy resins; and novolac epoxy resins obtained by reacting phenols with aldehydes, such as bisphenol-A epoxy resins, brominated bisphenol-A epoxy resins, bisphenol-F epoxy resins, bisphenol-AD epoxy resins, bisphenol-S epoxy resins, bisphenol epoxy resins, naphthalene epoxy resins, cyclopentadiene epoxy resins, alkyl-substituted bisphenol epoxy resins, multifunctional phenol epoxy resins, and tris(hydroxyphenyl)methane epoxy resins. Phenol-type epoxy resins obtained by reaction; aliphatic epoxy resins obtained by reacting alcohols such as trimethylolpropane, oligopropylene glycol and hydrogenated bisphenol-A with epichlorohydrin; glycidyl ester epoxy resins obtained by reacting hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid with epichlorohydrin or 2-methylepichlorohydrin; glycidylamine epoxy resins obtained by reacting amines such as diaminodiphenylmethane or aminophenol with epichlorohydrin; heterocyclic epoxy resins obtained by reacting polyamines such as isocyanuric acid with epichlorohydrin; phosphazene compounds having a glycidyl group; epoxy-modified phosphazene resins; isocyanate-modified epoxy resins; cyclic aliphatic epoxy resins; and urethane-modified epoxy resins, etc. When the resin composition of the present invention is used as a material for manufacturing electric / electronic components, among the above-mentioned epoxy resins, phenol novolac epoxy resins, o-cresol novolac epoxy resins, bisphenol-A epoxy resins, bisphenol-type epoxy resins, biphenyl novolac epoxy resins, naphthalene-type epoxy resins, polyfunctional phenol-type epoxy resins, or phenol-type epoxy resins obtained by the reaction of tris(hydroxyphenyl)methane and epichlorohydrin are particularly preferably used. Two or more epoxy resins may be used in combination.

[0231] Examples of usable thermoplastic resins include polyolefin resins (e.g., polyethylene resins, polypropylene resins, polyisoprene resins, polybutene resins, cyclic polyolefin (COP) resins, and cyclic olefin copolymer (COC) resins), chlorinated polyolefin resins (e.g., polyvinyl chloride resins and polyvinylidene chloride resins), styrene resins (e.g., polystyrene resins, high impact polystyrene (HIPS) resins, syndiotactic polystyrene (SPS) resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene copolymers (AS resins), methacrylic resins, and the like. acrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin) and acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), etc.), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polyvinyl alcohol, polyester resins (such as polyethylene terephthalate resin, polypropylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polymethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polymethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin) polyamide resins (e.g., polyamide 6 resin, polyamide 66 resin, polyamide 11 resin, polyamide 12 resin, polyamide 46 resin, copolymers of polyamide 6 resin and polyamide 66 resin (polyamide 6 / 66 resin), and copolymers of polyamide 6 resin and polyamide 12 resin (polyamide 6 / 12 resin)), semi-aromatic polyamide resins (e.g., polyamide MXD6 resin, polyamide 6T resin, polyamide 9T resin, and polyamide 10T resin, which are composed of structural units having aromatic rings and structural units without aromatic rings). The present invention also includes but is not limited to resins such as polyimide (polyacrylate), polyimide (polyetherimide), polyether aromatic ketone (polyetherketone), polyetherketoneketone, polyetheretherketoneketone, and polyetheretherketone), thermoplastic polyimide (TPI), liquid crystal polymer (LCP) (liquid crystal polyester), polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polybenzimidazole resin. Two or more thermoplastic resins may be used in combination.

[0232] As examples of thermoplastic resins, polyphenylene ether resins may also be modified polyphenylene ether resins. Modified polyphenylene ether resins may be obtained, for example, by introducing one or more reactive functional groups such as acryloyloxy, methacryloyloxy, styryl, vinyl, carboxyl, epoxy, amino, hydroxyl, and anhydrous dicarboxyl groups into a portion or all of the polyphenylene ether resin by grafting, copolymerization, or other methods. They may also be resins that are terminally modified with substituents having carbon-carbon unsaturated double bonds. As substituents having carbon-carbon unsaturated double bonds for terminal modification, at least one substituent selected from vinylphenyl, vinylbenzyl, acryloyl, and methacryloyl groups may be cited. Modified polyphenylene ether resins that are terminally modified with substituents having carbon-carbon unsaturated double bonds may also be used by adding other compounds having carbon-carbon unsaturated double bonds in the molecule.

[0233] When the resin composition of the present invention is used for manufacturing materials for electric / electronic components, particularly for sealing materials for various IC elements, substrate materials for wiring boards, insulating materials such as interlayer insulating materials or insulating adhesives, insulating materials for Si substrates or SiC substrates, conductive materials or surface protective materials, or housings or parts for OA equipment, AV equipment, communication equipment or home appliances, epoxy resins, phenolic resins, unsaturated polyester resins, diallyl phthalate resins, maleimide resins, polyimide resins, benzophenone resins, and the like are preferably used as thermosetting resins or thermoplastic resins that can be used therefor. Oxazine resin, benzocyclobutene resin, polyolefin resin, styrene resin, polyester resin, aliphatic polyamide resin, semi-aromatic polyamide resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin or modified resins thereof. If necessary, two or more of these resin components may be used in combination.

[0234] In the resin composition of the present invention, the amount of the cyclic phosphazene compound having an oxophosphaphenanthrene ring structure can be appropriately set according to various conditions, such as the type of resin component or the intended use of the resin composition. However, it is generally preferably set to 0.1 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, per 100 parts by mass of the resin component calculated as solids. If the amount of the cyclic phosphazene compound having an oxophosphaphenanthrene ring structure is less than 0.1 parts by mass, the resin molded article formed from the resin composition may not exhibit sufficient flame retardancy. Conversely, if the amount exceeds 200 parts by mass, the inherent properties of the resin component may be impaired, and the desired properties may not be obtained.

[0235] In addition, the resin composition of the present invention may be blended with various additives within a range that does not impair the target physical properties, depending on the type of resin component or the application of the resin composition. Examples of available additives include natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, aluminum oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, titanium oxide, zinc oxide, molybdenum oxide, zinc molybdate, natural mica, synthetic mica, Aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, short glass fibers, glass micropowder, hollow glass, and potassium titanate fibers; surface treatment agents for fillers such as silane coupling agents; release agents such as waxes, fatty acids and their metal salts, acid amides, and paraffin waxes; phosphates, condensed phosphates, phosphoramides, phosphoramidates, phosphine oxides, bis(diphenylphosphine) oxides, phosphazenes, phosphinates, phosphinates, ammonium phosphates, and red phosphorus. Phosphorus-based flame retardants such as cyanurate (red phosphorus); nitrogen-based flame retardants such as melamine, melamine cyanurate, melam, melem, melon, and succinoguanamine; flame retardants such as chlorinated paraffin, silicone-based flame retardants, and brominated flame retardants; flame retardant additives such as antimony trioxide; anti-drip agents such as polytetrafluoroethylene (PTFE); UV absorbers such as benzotriazole; antioxidants such as hindered phenols and styrenated phenol; photopolymerization initiators such as thioxanthone; fluorescent brighteners such as stilbene derivatives; epoxy resins; phenolic resins; curing agents; dyes; pigments; colorants; light stabilizers; photosensitizers; thickeners; lubricants; defoamers; leveling agents; brighteners; polymerization inhibitors; thixotropy-imparting agents; plasticizers; and antistatic agents. Two or more additives may be used in combination as needed.

[0236] When a thermosetting resin is used as the resin component, the resin composition of the present invention is generally used in combination with a curing agent or curing accelerator. The type of curing agent or curing accelerator that can be used is not particularly limited, as long as it is a curing agent or curing accelerator commonly used for thermosetting resins. Representative examples include polyamine compounds such as aromatic polyamines, polyamide polyamines, and aliphatic polyamines; phenol compounds such as phenol novolacs and cresol novolacs; acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; phosphazene compounds having a hydroxyl group; Lewis acids such as boron trifluoride and their salts; imidazoles; dicyandiamides; and organic metal salts. These can also be used in combination of two or more.

[0237] When the resin composition of the present invention is used as a material for manufacturing electrical / electronic components, epoxy resin is typically used as the resin component. The amount of curing agent contained in the resin composition containing epoxy resin as the resin component (hereinafter referred to as "epoxy resin composition") is generally preferably set to 0.5 to 1.5 equivalents, and more preferably 0.6 to 1.2 equivalents, per 1 equivalent of epoxy groups in the epoxy resin.

[0238] Epoxy resin compositions generally preferably contain a curing accelerator in addition to the aforementioned curing agent or additive. Various known curing accelerators can be used as curing accelerators without particular limitation. For example, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2-(dimethylaminomethyl)phenol, or triphenylphosphine compounds can be used. The amount of curing accelerator used is generally preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the epoxy resin.

[0239] The epoxy resin composition may be blended with a known reactive diluent as needed. Various known reactive diluents can be used as reactive diluents without particular limitation. Examples include aliphatic alkyl glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether; alkyl glycidyl esters such as glycidyl methacrylate and tertiary carboxylic acid glycidyl ether; styrene oxide; and aromatic alkyl glycidyl ethers such as phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. Two or more of these reactive diluents may be used in combination.

[0240] The resin composition of the present invention, such as an epoxy resin composition, can be prepared by uniformly mixing the various components. A resin composition containing a thermosetting resin undergoes a sufficient curing reaction to form a cured product if it is placed at a temperature range of about 100 to 250° C. for 1 to 36 hours depending on the resin component. For example, an epoxy resin composition generally undergoes a sufficient curing reaction to form a cured product if it is placed at a temperature of 150 to 250° C. for 2 to 15 hours. The cyclic phosphazene compound having an oxygen-containing heterophosphaphenanthrene ring structure of the present invention has a high melting point and low solubility, and therefore can improve flame retardancy without compromising the mechanical properties (especially glass transition temperature) of the cured product based on the resin composition, and can achieve good dielectric properties, especially low Dk / Df. Therefore, the resin composition of the present invention can be widely used as a material for the manufacture of various resin molded bodies, coatings, adhesives, and other applications. In particular, the resin composition of the present invention is suitable as a material for the production of electrical / electronic components, such as a material for semiconductor sealing or for forming circuit substrates (particularly metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, insulating circuit protection films for printed wiring boards, conductive pastes for printed wiring boards, sealants for multilayer printed wiring boards, circuit protection agents, cover films, and cover inks).

[0241] Example

[0242] The following examples and comparative examples are provided to illustrate the present invention in detail, but the present invention is not limited thereto. In addition, hereinafter, unless otherwise specified, "%" and "parts" refer to "mass %" and "parts by mass" respectively.

[0243] based on 1 H-NMR spectrum and 31 The phosphazene compounds obtained in the Examples or Synthesis Examples were identified based on the results of P-NMR spectrum measurement, CHN elemental analysis, analysis of chlorine element (residual chlorine) by potentiometric titration using silver nitrate after alkali fusion, analysis of phosphorus element by ICP atomic emission spectrometry (ICP-AES) after microwave wet decomposition, and analysis using a high-resolution mass spectrometer (HRMS) using electrospray ionization (ESI).

[0244] In addition, the phosphorus-based flame retardants used in Examples and Comparative Examples are as follows.

[0245] Phosphorus flame retardant Y: Phosphate ester (trade name "CR-741" of Daihachi Chemical Industry Co., Ltd.)

[0246] Phosphorus flame retardant Z: phosphine oxide (trade name "PQ-60" manufactured by Taiwan Jinyi Chemical Co., Ltd.)

[0247] [Synthesis Example 1 (Synthesis of 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene)]

[0248] According to the method described in Stephen D. Pastor, John D. Spivack, Leander P. Steinhuebel, Phosphorus and Sulfur, 1987, Vol. 31, p. 71. (previously published non-patent document 3), the synthesis of 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene was attempted. 1 H-NMR spectrum and 31 The results of P-NMR spectrum measurement confirmed that the obtained compound was the target 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene (recovery rate: 85%).

[0249] [Synthesis Example 2 (Synthesis of 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene)]

[0250] According to the method described in Asfia Qureshi, Allan S. Hay, J. Chem. Res (M), 1998, p. 1601. (previously published non-patent document 4), the synthesis of 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene was attempted. 1 H-NMR spectrum and 31 The results of P-NMR spectrum measurement confirmed that the obtained compound was the target 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene (recovery rate: 81%).

[0251] [Example 1 (Production of a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure by production method 1)]

[0252] Into a 5,000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 234.6 g (1.0 mol) of 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene synthesized in Synthesis Example 1, 115.2 g (1.0 mol) of trimethylsilyl azide, and 2,000 mL of toluene were placed under a nitrogen stream and stirred at 50°C for 24 hours. After the reaction mixture was cooled to room temperature, 1,000 mL of ion-exchanged water was added and stirred at room temperature for 1 hour. The slurry thus obtained was filtered, and the filtrate was washed with toluene and ion-exchanged water. The resulting wet crystals were dried to obtain 177.8 g of a white powder (recovery rate: 83.4%). The analytical results of this white powder are as follows.

[0253] 1 H-NMR spectrum (in deuterated chloroform, δ, ppm):

[0254] 6.0~8.3(m)

[0255] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0256] -10~0(m), 1.8~3.5(m), 15.8(d), 17.5(s), 17.9(dd)

[0257] CHNP elemental analysis:

[0258] Theoretical values C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53%

[0259] Measured values: C: 67.49%, H: 3.79%, N: 6.55%, P: 14.49%

[0260] Residual chlorine analysis:

[0261] <0.01%

[0262] HRMS (ESI, m / z):

[0263] Theoretical value trimer: [C 36 H 24 N3O3P3+H] + : 640.1109, tetramer: [C 48 H 32 N4O4P4+H] + : 853.1452, pentamer: [C 60 H 40 N5O5P5+H] + :1066.1796 Measured values 640.1097, 853.1444, 1066.1797

[0264] From the above analysis results, it was confirmed that the obtained white powder was a mixture of N3P3(OC6H4-C6H4)3, N4P4(OC6H4-C6H4)4 and N5P5(OC6H4-C6H4)5, and its average composition was [NP(OC6H4-C6H4)] 3.6 A cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure.

[0265] [Example 2 (Separation of the trimer-cis isomer from the cyclic phosphazene compound obtained in Example 1)]

[0266] A 2,000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 150.0 g of the white powder obtained in Example 1 and 1,500 mL of toluene. The mixture was stirred under reflux for 3 hours, cooled to room temperature, and stirred for an additional 2 hours. The resulting slurry was filtered, and the filtrate was washed with toluene and dried to obtain 36.6 g of colorless crystals. The analysis results of these colorless crystals are as follows.

[0267] 1 H-NMR spectrum (in deuterated chloroform, δ, ppm):

[0268] 7.17(3H,td),7.35(3H,td),7.40(3H,dd),7.47(3H,t),7.61(3H,td),7.85(3H,dd),7.89(3H,m)

[0269] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0270] 17.5(s)

[0271] CHNP elemental analysis:

[0272] Theoretical values C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53%

[0273] Measured values: C: 67.59%, H: 3.80%, N: 6.61%, P: 14.55%

[0274] Residual chlorine analysis:

[0275] <0.01%

[0276] HRMS (ESI, m / z):

[0277] Theoretical value trimer: [C 36 H 24 N3O3P3+H] + :640.1109

[0278] Measured value 640.1097

[0279] From the above analysis results, it was confirmed that the obtained colorless crystals were cis-type N3P3(OC6H4-C6H4)3 cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure.

[0280] [Example 3 (Separation of trimer-trans isomer and tetramer from the cyclic phosphazene compound obtained in Example 1)]

[0281] The mother liquor obtained by filtering the slurry in Example 2 was concentrated using an evaporator, and the resulting solid was separated and purified using silica gel column chromatography (developing solvent: toluene / ethyl acetate = 9 / 1) to obtain fractions containing the trimer-trans isomer and tetramer of the cyclic phosphazene compound obtained in Example 1. Each fraction was concentrated under reduced pressure, and methanol was added and filtered. The crystals obtained by washing the filtrate with methanol were then dried. 86.7 g of colorless crystals of the trimer-trans isomer and 15.9 g of a white powder of the tetramer were obtained. The analytical results are shown below.

[0282] Trimer-trans isomer is colorless crystals:

[0283] 1 H-NMR spectrum (in deuterated chloroform, δ, ppm):

[0284] 7.18(3H,m),7.33(3H,m),7.52(2H,m),7.63(4H,m),7.88(6H,m),8.03(2H,m),8.25(1H,ddd)

[0285] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0286] 15.8(d),17.9(dd)

[0287] CHNP elemental analysis:

[0288] Theoretical values C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53%

[0289] Measured values: C: 67.51%, H: 3.81%, N: 6.54%, P: 14.48%

[0290] Residual chlorine analysis:

[0291] <0.01%

[0292] HRMS (ESI, m / z):

[0293] Theoretical value trimer: [C 36 H 24 N3O3P3+H] + :640.1109

[0294] Measured value 640.1097

[0295] From the above analysis results, it was confirmed that the obtained colorless crystals were trans-type N3P3(OC6H4-C6H4)3 cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure.

[0296] White powder of tetramer:

[0297] 1 H-NMR spectrum (in deuterated chloroform, δ, ppm):

[0298] 6.5~7.8(m)

[0299] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0300] 1.8~3.5(m)

[0301] CHNP elemental analysis:

[0302] Theoretical values C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53%

[0303] Measured values: C: 67.52%, H: 3.83%, N: 6.52%, P: 14.51%

[0304] Residual chlorine analysis:

[0305] <0.01%

[0306] HRMS (ESI, m / z):

[0307] Theoretical value of tetramer: [C 48 H 32 N4O4P4+H] + :853.1452

[0308] Measured value 853.1444

[0309] The above analysis results confirmed that the obtained white powder is a mixture of five isomers of a cyclic phosphazene compound having an oxaphosphaphenanthrene ring structure, N4P4(OC6H4-C6H4). The five isomers include cis, α-trans, β-trans, and γ-trans, as well as enantiomers. It should be noted that the names of the tetrameric stereoisomers are based on the nomenclature in the following non-patent document 13.

[0310] [Non-Patent Document 13]

[0311] Bernard Grushkin,Alvin J.Berlin,James L.McClanaham,Rip G.Rice,Inorg.Chem.,1966,Vol.5,p.172.

[0312] [Example 4 (Production of a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure by production method 1)]

[0313] The same procedures as in Example 1 were followed, except that 310.7 g (1.0 mol) of 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene synthesized in Synthesis Example 2 was used instead of the 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene synthesized in Synthesis Example 1. 274.2 g of a white powder was obtained (recovery rate: 94.8%). The analysis results of this white powder are as follows.

[0314] 1 H-NMR spectrum (in deuterated chloroform, δ, ppm):

[0315] 6.0~8.3(m)

[0316] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0317] -10~0(m),1.5~3.2(m),15.5(d),17.1(s),17.8(dd)

[0318] CHNP elemental analysis:

[0319] Theoretical values C: 74.74%, H: 4.18%, N: 4.84%, P: 10.71%

[0320] Measured values: C: 74.70%, H: 4.19%, N: 4.72%, P: 10.66%

[0321] Residual chlorine analysis:

[0322] <0.01%

[0323] HRMS (ESI, m / z):

[0324] Theoretical value trimer: [C 54 H 36 N3O3P3+H] + : 868.2048, tetramer: [C 72 H 48 N4O4P4+H] + :1157.2704,pentamer:[C 90 H 60 N5O5P5+H] + :1446.3361

[0325] Measured values: 868.2039, 1157.2712, 1146.3372

[0326] From the above analysis results, it was confirmed that the obtained white powder was a mixture of N3P3[OC6H3(C6H5)-C6H4]3, N4P4[OC6H3(C6H5)-C6H4]4 and N5P5[OC6H3(C6H5)-C6H4]5, and its average composition was {NP[OC6H3(C6H5)-C6H4]} 3.5 A cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure.

[0327] [Examples 5 to 10 and Comparative Examples 1 and 2 (Production of Resin Molded Articles)]

[0328] A polyphenylene ether oligomer modified with a vinyl group at the end (SABIC's trade name "SA-9000"), a styrene-butadiene copolymer (CRAY VALLEY's trade name "RICON184"), the phosphazene compound produced in Examples 1 to 4, a phosphorus-based flame retardant Y or Z, a polymerization initiator (Tokyo Chemical Industry Co., Ltd.'s reagent "t-Butyl Peroxide"), and methyl ethyl ketone (MEK) were mixed and stirred in the proportions shown in Table 2 to prepare a varnish. The varnish was applied to a polyethylene terephthalate resin film, allowed to stand at room temperature for 1 hour, and then dried at 90°C for 30 minutes. The dried coating was peeled off and placed in a separator made of polytetrafluoroethylene resin. The film was heated in stages under vacuum at 120°C for 30 minutes, 150°C for 30 minutes, and 180°C for 100 minutes, and then pressurized to cure. A molded body of a size suitable for the following evaluation was obtained.

[0329] [Examples 11 to 15 and Comparative Examples 3 and 4 (Production of Resin Molded Articles)]

[0330] To a mixture of 651 parts of a bisphenol A-type epoxy resin (trade name "Epikote 1001" manufactured by Japan Epoxy Resins Co., Ltd. / epoxy group equivalent weight 456 g / eq., resin solids content 70%), 300 parts of a cresol novolac epoxy resin (trade name "YDCN-704P" manufactured by Tohto Kasei Co., Ltd. / epoxy group equivalent weight 210 g / eq., resin solids content 70%), 303 parts of a novolac-type phenolic resin (trade name "BRG-558" manufactured by Showa High Molecular Co., Ltd. / hydroxyl group equivalent weight 106 g / eq., resin solids content 70%), 361 parts of aluminum hydroxide, and 0.9 part of 2-ethyl-4-methylimidazole, the phosphazene compounds produced in Examples 1 to 4 and the phosphorus-based flame retardant Y or Z were added in the proportions shown in Table 3. Propylene glycol monomethyl ether (PGM) was then added as a solvent to prepare an epoxy resin novolac having a resin solids content of 65%.

[0331] Next, the prepared epoxy resin varnish was applied to 180 μm glass woven fabric for impregnation and dried at 160°C to produce a prepreg. Eight of these prepregs were laminated, and the laminated body was heated and pressed at 170°C and 4 MPa for 100 minutes to obtain a molded body of a size suitable for the following evaluation.

[0332] [Examples 16 to 21 and Comparative Examples 5 and 6 (Production of Resin Molded Articles)]

[0333] A thermoplastic resin (polyphthalamide: SOLVAY trade name "Amodel AE-1133") previously dried at 100°C for 8 hours, the phosphazene compounds produced in Examples 1 to 4, and phosphorus-based flame retardants Y or Z were supplied to a twin-screw kneading extruder (manufactured by Toyo Seiki Co., Ltd.) in the ratios shown in Table 4 and kneaded at 310°C to obtain resin pellets. The resulting resin pellets were molded using an injection molding machine (manufactured by Digital Factory Co., Ltd.) at a resin temperature of 300°C and a mold temperature of 120°C to obtain molded articles of a size suitable for the following evaluations.

[0334] [evaluate]

[0335] The flame retardancy, dielectric properties, and heat resistance of the resin molded articles obtained in Examples 5 to 21 and Comparative Examples 1 to 6 were evaluated by the following evaluation methods. The results are shown in Tables 2 to 4.

[0336] <Flammability>

[0337] A resin molded body with a length of 125 mm, a width of 12.5 mm and a thickness of 1.5 mm was used as a test piece, and the flammability of the test piece was evaluated. Here, based on the UL-94 standard vertical combustion test of Underwriter's Laboratories Inc., the flammability is judged in four stages: V-0, V-1, V-2 and substandard (out of specification), according to the total burning time when 10 times of contact with the flame and whether the cotton is ignited by dripping during combustion. The evaluation of each stage is as follows. The level of flame retardancy is V-0, which is the highest, and decreases in the order of V-1, V-2, and substandard.

[0338] V-0: All of the following conditions are met.

[0339] (A) The total extinguishing time after 5 test pieces, each piece being exposed to flame twice, for a total of 10 times, is within 50 seconds.

[0340] (B) Five test pieces were exposed to flame twice, and the extinguishing time after the flame exposure was within 5 seconds.

[0341] (C) In all test pieces, there was no ignition of the absorbent cotton at a depth of 300 mm due to dripping.

[0342] (D) In all test pieces, the glow after the second exposure to flame was within 30 seconds.

[0343] (E) In all the test pieces, there was no burning up to the jig.

[0344] V-1: All of the following conditions are met.

[0345] (A) The total extinguishing time after 5 test pieces, each piece being exposed to flame twice, for a total of 10 times, is within 250 seconds.

[0346] (B) Five test pieces were exposed to flame twice, and the extinguishing time after the flame exposure was within 30 seconds.

[0347] (C) In all test pieces, the absorbent cotton at a depth of 300 mm was not ignited by the dripping matter.

[0348] (D) In all test pieces, the glow after the second exposure to flame was within 60 seconds.

[0349] (E) In all the test pieces, there was no burning up to the jig.

[0350] V-2: All of the following conditions are met.

[0351] (A) The total extinguishing time after 5 test pieces, each piece being exposed to flame twice, for a total of 10 times, is within 250 seconds.

[0352] (B) Five test pieces were exposed to flame twice, and the extinguishing time after the flame exposure was within 30 seconds.

[0353] (C) In at least one of the five test pieces, the absorbent cotton at a depth of 300 mm was ignited by dripping matter.

[0354] (D) In all test pieces, the glow after the second exposure to flame was within 60 seconds.

[0355] (E) In all the test pieces, there was no burning up to the jig.

[0356] <Dielectric Properties: Relative Permittivity and Dielectric Loss Tangent>

[0357] A resin molded article measuring 80 mm in length, 3 mm in width, and 1.0 mm in thickness was used as a test piece. The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were measured at 25°C and 10 GHz in accordance with JIS R1641, "Determination of microwave dielectric properties of fine ceramic substrates."

[0358] <Glass transition temperature (Tg)>

[0359] The dynamic viscoelasticity (DMA) of the resin molded article was measured, and the maximum value of tan δ (loss modulus / storage modulus) was defined as the glass transition temperature (Tg). The measurement was performed using a dynamic viscoelasticity measuring apparatus (Perkin Elmer Japan Co., Ltd. trade name "DMA8000") with a tensile module at a temperature increase of 5°C / minute.

[0360] <Heat resistance>

[0361] Test condition 1:

[0362] The resin molded article was heated at 160°C for 100 hours, and the oozing state on the surface of the resin molded article (the oozing state from the interior of the resin molded article) was evaluated by visual observation. The evaluation criteria are as follows: The less oozing is observed, the higher the heat resistance of the resin molded article.

[0363] AA: No exudation was observed at all.

[0364] A: Almost no exudation was observed.

[0365] B: Some exudation is visible.

[0366] C: Obvious exudation is visible.

[0367] Test condition 2:

[0368] After treating the resin molded article at 290° C. for 20 minutes, the presence or absence of changes in appearance due to bleed-out was observed. If there was no change in appearance, it was evaluated as having heat resistance; if there was a change in appearance, it was evaluated as not having heat resistance.

[0369] [Table 2]

[0370] Table 2

[0371]

[0372] *1: Trimer-trans isomer isolated from the cyclic phosphazene compound obtained in Example 1 *2: Tetramer isolated from the cyclic phosphazene compound obtained in Example 1

[0373] According to Table 2, the resin molded bodies of Examples 5 to 10 have higher flame retardancy, lower relative dielectric constant Dk and dielectric loss tangent Df, resulting in low Dk / Df, and excellent dielectric properties, compared to the resin molded bodies of Comparative Examples 1 and 2. In addition, since there is substantially no leakage of the cyclic phosphazene compound used in the heat resistance evaluation, the reliability at high temperatures is high.

[0374] [Table 3]

[0375] Table 3

[0376]

[0377] *1: Trimer-trans isomer isolated from the cyclic phosphazene compound obtained in Example 1 *2: Tetramer isolated from the cyclic phosphazene compound obtained in Example 1

[0378] According to Table 3, the resin molded bodies of Examples 11 to 15 have higher flame retardancy and higher glass transition temperatures than the resin molded bodies of Comparative Examples 3 and 4, and therefore also have good mechanical properties. Furthermore, since substantially no bleeding of the cyclic phosphazene compound, which is used for the evaluation of heat resistance, is observed, the resin molded bodies have high reliability at high temperatures.

[0379] [Table 4]

[0380] Table 4

[0381]

[0382] *: Tetramer isolated from the cyclic phosphazene compound obtained in Example 1

[0383] According to Table 4, the resin molded bodies of Examples 16 to 21 have higher flame retardancy, lower relative dielectric constant Dk and dielectric loss tangent Df, resulting in low Dk / Df, and excellent dielectric properties, compared to the resin molded bodies of Comparative Examples 5 and 6. In addition, since there is substantially no leakage of the cyclic phosphazene compound evaluated for heat resistance, the reliability at high temperatures is high.

[0384] [Example 22 (Production of a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure by production method 2)]

[0385] A toluene solution of 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene obtained in Synthesis Example 1 was prepared, and chlorine gas was introduced therein to react to synthesize 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxaphosphacyclopentane. 31 The following P-NMR spectrum analysis confirmed that 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene had been derived into the target 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxaphosphacyclopentane. The reaction solution was used directly in the next reaction. The chloride ion content in the reaction solution, as determined by silver nitrate titration, was 38.2%.

[0386] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0387] -25.3(s)

[0388] A 3,000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 58.8 g (1.1 mol) of ammonium chloride and 1,500 mL of toluene under a nitrogen stream to prepare a slurry solution, which was then heated. Subsequently, while the slurry solution was refluxed, 799.8 g (1.0 mol) of the reaction solution obtained in the above step, namely a toluene solution of 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxaphosphacyclopentane, was added dropwise over 18 hours. The toluene was then distilled off, and the reaction solution was concentrated until the final temperature reached 160°C, followed by stirring at the same temperature for 15 hours. Next, 500 mL of ion-exchanged water was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The crystals separated by filtering the slurry were washed with ion-exchanged water and dried to obtain 184.0 g of a white powder (recovery rate: 86.3%). As shown in the following analysis results, the white powder was confirmed to be a dibenzoxaphosphaphenanthrene ring-containing cyclic phosphazene compound represented by formula (1) (a mixture of compounds wherein a and b are 0 and n is an integer of 3 to 8).

[0389] 1 H-NMR spectrum (in deuterated chloroform, δ, ppm):

[0390] 6.0~8.3(m)

[0391] 31 P-NMR spectrum (in deuterated chloroform, δ, ppm):

[0392] -10~0(m),1.8~3.5(m),15.8(d),17.5(s),17.9(dd)

[0393] CHNP elemental analysis:

[0394] Theoretical values C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53%

[0395] Measured values: C: 67.55%, H: 3.81%, N: 6.53%, P: 14.48%

[0396] Residual chlorine analysis:

[0397] <0.01%

[0398] HRMS spectrum (ESI, m / z):

[0399] Theoretical value trimer: [C 36 H24 N3O3P3+H] + : 640.1109, tetramer: [C 48 H 32 N4O4P4+H] + : 853.1452, pentamer: [C 60 H 40 N5O5P5+H] + :1066.1796

[0400] Measured values: 640.1097, 853.1444, 1066.1797

[0401] [Example 23 (Production of a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure by production method 3)]

[0402] In a 3,000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 234.6 g (1.0 mol) of 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene obtained in Synthesis Example 1 and 1,500 mL of diethyl ether were placed under a nitrogen stream. Meanwhile, while cooling the reaction solution to keep it below 0°C, 183 mL of a pre-prepared 6M solution of chloramine in diethyl ether (chloramine amount: 1.1 mol) was added dropwise. The diethyl ether was then distilled off by heating the reaction solution, which was then concentrated until the temperature reached 160°C and stirred at the same temperature for 19 hours. 500 mL of ion-exchanged water was added to the reaction solution, which was stirred at room temperature for 1 hour. The resulting slurry was filtered to isolate the crystals. The isolated crystals were then washed with ion-exchanged water and dried to yield 158.8 g of a light brown powder (recovery rate: 74.5%). 1 H-NMR, 31 The analysis results of each spectrum of P-NMR and HRMS were consistent with the analysis results of the white powder obtained in Example 22, thus confirming that the light brown powder was a cyclic phosphazene compound containing a dibenzoxaphosphaphenanthrene ring represented by formula (1) (a mixture of compounds in which a and b are 0 and n is an integer of 3 to 8).

[0403] [Example 24 (Production of a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure by production method 4)]

[0404] The 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphaphenanthrene obtained in Synthesis Example 1 was hydrolyzed with reference to the descriptions of Patent Documents 11 and 12 to prepare 6H-dibenzo[c,e][1,2]oxaphosphacyclopentane-6-oxide. The obtained 6H-dibenzo[c,e][1,2]oxaphosphacyclopentane-6-oxide was then chlorinated according to the description of Non-Patent Document 10. 1H-NMR spectrum and 31 The results of P-NMR spectrum measurement confirmed that the thus obtained product was 6-chloro-6H-dibenzo[c,e][1,2]oxaphospholane-2-oxide (recovery rate: 94%).

[0405] Next, the obtained 6-chloro-6H-dibenzo[c,e][1,2]oxaphospholane-2-oxide was aminated using aqueous ammonia according to the method described in Non-Patent Document 11. 1 H-NMR spectrum and 31 The results of P-NMR spectrum measurement confirmed that the obtained product was 6-amino-6H-dibenzo[c,e][1,2]oxaphospholane-2-oxide (recovery rate 89%), which is a phosphonamidate-based compound.

[0406] Prepare a 10,000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and charge 231.2 g (1.0 mol) of the obtained 6-amino-6H-dibenzo[c,e][1,2]oxaphosphorane-2-oxide, 629.5 g (2.4 mol) of triphenylphosphine, 129.2 (1.0 mol) of N,N-diisopropylethylamine, and 4,500 mL of xylene therein under a nitrogen flow, and heat. While the solution in the flask is refluxed, 153.8 g (1.0 mol) of carbon tetrachloride is added dropwise over 2 hours, and stirring is continued for 4 hours. The solvent is distilled off from the reaction solution under reduced pressure, and the slurry obtained by adding 9,000 mL of methanol to the residue and stirring is filtered to separate the crystals. Then, the separated crystals are washed with methanol and dried to obtain 115.1 g of white powder (recovery rate: 54.0%). By 1 H-NMR and 31 The results of P-NMR spectrum analysis confirmed that the white powder was a dibenzoxaphosphaphenanthrene ring-containing cyclic phosphazene compound represented by formula (1) (a mixture of compounds wherein a and b are 0 and n is an integer of 3 to 8).

[0407] [Example 25 (Production of a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure by production method 4)]

[0408] The same operation as in Example 24 was carried out except that 73.9 g (0.2 mol) of tetrabutylammonium iodide was added to the four-necked flask prepared in Example 24 and 99.0 g (1.0 mol) of 1,2-dichloroethane was used instead of carbon tetrachloride to obtain 128.3 g of white powder (recovery rate: 60.2%). 1 H-NMR and 31The results of P-NMR spectrum analysis confirmed that the white powder was a dibenzoxaphosphaphenanthrene ring-containing cyclic phosphazene compound represented by formula (1) (a mixture of compounds wherein a and b are 0 and n is an integer of 3 to 8).

Claims

1. A cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure represented by the following formula (1), [Chemical Formula 1] In formula (1), n is an integer from 3 to 8, R 1 and R 2 (i) each independently represents any one of a nitro group, an alkyl group or an alkoxy group having 1 to 8 carbon atoms optionally substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group, and an aryl group or an aryloxy group having 6 to 20 carbon atoms optionally substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group, or (ii) each independently forms a saturated or unsaturated cyclic structure optionally substituted with an alkyl group having 1 to 6 carbon atoms or a carbonyl group, a and b are each independently an integer from 0 to 4, The type of the oxaphosphaphenanthrene ring structure in each repeating unit is independent.

2. The cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 1, wherein In formula (1), n is 3 or 4.

3. The cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 1, wherein In formula (1), n is 3 and a and b are 0.

4. The cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 3, which is a mixture of diastereomers.

5. The cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 3, wherein The stereo configuration of the adjacent oxygen-containing phosphaphenanthrene ring structures is cis-cis-cis.

6. The cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 3, wherein The stereo configuration of the adjacent oxygen-containing phosphaphenanthrene ring structures is trans-cis-trans. A mixture of cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure, comprising two or more cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure according to any one of claims 1 to 6.

8. A method for producing a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure, comprising the following steps: Step 1, using an azidating agent to derive a chlorodibenzoxaphosphaphenanthrene compound represented by the following formula (2) into an azidation intermediate; and Step 2, subjecting the aforementioned azidation intermediate to a cyclization reaction, [Chemical Formula 2] In formula (2), R 1 and R 2 (i) each independently represents any one of a nitro group, an alkyl group or an alkoxy group having 1 to 8 carbon atoms optionally substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group, and an aryl group or an aryloxy group having 6 to 20 carbon atoms optionally substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group, or (ii) each independently forms a saturated or unsaturated cyclic structure optionally substituted with an alkyl group having 1 to 6 carbon atoms or a carbonyl group, a and b are each independently an integer of 0-4.

9. The method for producing a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 8, wherein The aforementioned azidation intermediate used in step 2 is a mixture of two or more aforementioned azidation intermediates.

10. The method for producing a cyclic phosphazene compound having an oxygen-containing phosphaphenanthrene ring structure according to claim 9, wherein The mixture of the azidation intermediates is obtained by using two or more of the chlorodibenzoxaphosphaphenanthrene compounds in step 1. 11 . A resin composition comprising a resin component and one or more cyclic phosphazene compounds having an oxygen-containing phosphaphenanthrene ring structure according to claim 1 .

12. The resin composition according to claim 11, wherein The aforementioned resin component is at least one selected from the following: epoxy resin, phenolic resin, unsaturated polyester resin, diallyl phthalate resin, maleimide resin, polyimide resin, benzophenone resin, Oxazine resin, benzocyclobutene resin, polyolefin resin, styrene resin, polyester resin, aliphatic polyamide resin, semi-aromatic polyamide resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin and modified resins thereof.

13. A resin molded article composed of the resin composition according to claim 11.

14. An electric / electronic component comprising the resin molded article according to claim 13.

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