TWI465457B - Amino-containing multifunctional epoxy curing agents and their derivatives, preparation and use - Google Patents

Description

Amine-containing polyfunctional epoxy resin hardener, derivative thereof, and production method and use thereof

The present invention relates to a series of phosphorus-based polyfunctional compounds and a process for their production. In addition to being an epoxy resin hardener, the phosphorus-containing compound can also be used to prepare a flame retardant resin such as an epoxy resin.

Halogen-containing epoxy resins are widely used on printed circuit boards because of their flame retardant properties. However, halogen-containing epoxy resins produce toxic and corrosive substances such as diphenyl dioxin. -p-dioxin) and toxic substances such as dibenzo-furan. Therefore, the EU has now completely banned halogen-containing products from entering the European market. In addition to halogen-containing compounds, organophosphorus compounds also have flame retardant properties. Since the protective layer of polyphosphoric acid can be formed when the organic phosphorus atom is burned, the organophosphorus compound has a flame retardant property. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce smoke and toxic gases when burned, and also have the advantages of good processability and low addition.

a phosphorus-containing compound such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), which has The active hydrogen atom reacted by electron-deficient compounds can be associated with electron-deficient compounds such as benzoquinone [1], oxirane, maleic acid, bismaleimide. , diaminobenzophenone (diaminobenzophenone) and terephthalic acid (terephthaldicarboxaldehyde) reaction, its derivatives have attracted the attention of the academic community and the industry.

Since the amine compound has many advantages as an epoxy resin hardener, for example, the epoxy resin hardened material prepared thereof has a relatively high crosslinking density, good mechanical properties and thermal properties, and thus is an epoxy resin hardener. Among the types, amine hardeners are the most important. Due to the electronics industry's requirements for the flame retardancy of materials, many scientists have invested in the study of upgrading amine hardeners, such as the introduction of phosphorus-containing groups into the structure of amine compounds. By introducing a phosphorus-containing group, the amine compound can be used not only as an epoxy resin hardener but also as a flame retardant for epoxy resins.

In 2005, Lin C. H. et al. used DOPO and pararosaniline chloride to synthesize a hexafunctional amine compound dopo-ta [2]. Has the following structure:

Dopo-ta is an epoxy resin hardener with good glass transition temperature and flame retardant properties. However, raw rose aniline is expensive and expensive, and it is not economically viable in industrial applications. This patent therefore focuses on the synthesis of phosphorus-containing polyfunctional epoxy resin hardeners from inexpensive raw materials.

references

[1] Wang, CS; Lin, CH Polymer 1999 , 40, 747.

[2] Lin, CH; Cai, SX; Lin, CH J Polym. Sci. Part A: Polym. Chem . 2005 , 43, 5971.

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel phosphorus-based compound which can be used as an epoxy resin hardener and can be further used for preparing a resin having flame retardancy characteristics, such as an epoxy resin.

Compound

The present invention discloses a phosphorus-based compound having the following chemical formula:

Wherein R ₁ to R ₄ are each selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, nitro, amine and halogen atoms; A is selected from -NH ₂ , -NHR, -NR ₂ and a group consisting of; B and C' are each selected from -OH, -NH ₂ , -OCN, , a group consisting of -OR, -NHR and -NR ₂ ; R ₅ is selected from the group consisting of C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, phenyl and -CF ₃ ; It is a C ₁ -C ₆ alkyl group.

When R ₁ to R _{4 of} the compound of the above formula (I) are each a hydrogen atom, R ₅ is a methyl group, and A, B and C′ are simultaneously -NH ₂ , the structural formula of the compound of the formula (I) may be

Where the two specific embodiments of the formula (II) are the formula (A) or the formula (D):

When R ₁ to R _{4 of} the compound of the above formula (I) are each a hydrogen atom, R ₅ is a methyl group, A is -NH ₂ , and B and C′ are simultaneously -OH, the structural formula of the compound of the formula (I) may be for

Where the two specific embodiments of the formula (III) are the formula (B) or the formula (E):

When R ₁ to R _{4 of} the above compound of the formula (I) are each a hydrogen atom, R ₅ is a methyl group, A is -NH ₂ , and B and C' are -OH and -NH ₂ , respectively, the compound of the formula (I) The structural formula can be

Where the two specific embodiments of the formula (IV) are the formula (C) or the formula (F):

When R ₁ to R _{4 of} the compound of the above formula (I) are each a hydrogen atom, R ₅ is a methyl group, and A, B and C' are simultaneously The structural formula of the compound of the formula (I) may be

Where the two specific embodiments of the formula (V) are of the formula (A-ep) or the formula (D-ep):

Preparation

The present invention provides a process for the preparation of a compound of the above formula (I) which comprises reacting an organophosphorus compound of the formula (VI), a compound of the formula (VII), a compound of the formula (VIII) and an acidic catalyst to form a formula (I). a compound wherein R ₁ to R ₄ , A, B, C′ and R ₅ are as defined above;

According to the above method, in the specific embodiment of the present invention, when R ₁ to R ₄ are a hydrogen atom, R ₅ is a methyl group, and A, B and C' are simultaneously -NH ₂ , the formula (VI) 9, 10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-aminoacetophenone of formula (VII), o-phenylenediamine of formula (VIII) and acidic catalyst-forming formula (A a compound, or a compound of formula (VI) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, formula (VIII) The m-phenylenediamine and the acidic catalyst form a compound of the formula (D).

According to the above method, in a specific embodiment of the present invention, when R ₁ to R ₄ are a hydrogen atom, R ₅ is a methyl group, A is -NH ₂ , and B and C' are simultaneously -OH, formula (VI) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, formula (VIII) catechol and acid catalyst formation a compound of formula (B), or a compound of formula (VI) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, (VIII) Resorcinol and an acidic catalyst form a compound of formula (E).

According to the above method, in a specific embodiment of the present invention, when R ₁ to R ₄ are a hydrogen atom, R ₅ is a methyl group, A is -NH ₂ , and B and C' are -OH and -NH ₂ respectively, Formula (VI) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-aminoacetophenone of formula (VII), 2-aminophenol of formula (VIII) Forming a compound of formula (C) with an acidic catalyst, or a compound of formula (VI) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-amino group of formula (VII) Acetophenone, a compound of formula (VIII) 3-aminophenol and an acidic catalyst form a compound of formula (F).

From the above, it is understood that the phosphorus-based compound of the present invention has a reactive phenol and an amine functional group at the terminal, and thus can be used as a curing agent for an epoxy resin. It can also be further epoxidized to epoxy resin.

In some specific embodiments of the present invention, two kinds of phosphorus compounds such as formula (A) and formula (D) are synthesized into an epoxy group-containing compound (A-ep) and a formula (D-ep) by an epoxidation reaction. ).

According to the above method, in a further embodiment of the present invention, the compound of formula (A) can be prepared first, and then the compound of formula (A) can be reacted with epichlorohydrin in a solvent to form A, B and C'. The product of formula (A-ep) is a compound.

According to the above method, in a further embodiment of the present invention, the compound of formula (D) can be prepared first, and then the compound of formula (D) can be reacted with epichlorohydrin in a solvent to form A, B and C'. The product of formula (D-ep) is a compound.

The acidic catalyst used in the above method is selected from the group consisting of oxalic acid, p-Toluenesulfonic acid (pTSA), acetic acid, methanesulfonic acid, and trifluorobenzene. Trifluoromethane sulfonic acid, sulfuric acid, halogenated acid (HX), trifluoroactic acid (CF ₃ COOH), nitric acid (HNO ₃ ) and phosphoric acid (H _{3 )} PO ₄ ) The group consisting of.

Hardener and flame retardant resin

The present invention discloses a hardener comprising a compound of the above formula (I) or a mixture thereof, wherein A of the compound is -NH ₂ , -NHR or -NR ₂ , and B and C' are each selected from -OH, - a group consisting of NH ₂ , -OR, -NHR and -NR ₂ wherein R is a C ₁ -C ₆ alkyl group.

The present invention also discloses a flame retardant resin comprising a compound of the formula (I) as defined above, wherein the compound A of the formula (I) is , B and C' are

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be obtained without departing from the spirit of the invention are range.

Example

The implementation of the above related inventions can be expressed in the following flow, and we will explain in the following specific embodiments.

Synthesis Example 1: Synthesis of Compound (A)

Synthesis of R ₁ to R ₄ as a hydrogen atom and R ₅ as a methyl group using an organic cyclic phosphorus compound DOPO, o-phenylenediamine, 4-aminoacetophenone and an acidic catalyst. A, B and C' are each a phosphorus compound (A) of -NH ₂ . The synthesis steps are as follows: organic cyclic phosphorus compound DOPO 5.405 g (0.025 mol), 4-aminoacetophenone 3.379 g (0.025 mol), o-phenylenediamine 13.5 g (0.125 mol) and oxalic acid 0.216 g (4 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 130 ° C, and stirring was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into water to precipitate, filtered and dried to obtain a brown powder of the product (A) in a yield of about 91%, which was recrystallized from ethanol/water. . HR-MS (FAB +) m / z:.. Calcd for C 26 H 24 N 3 O 2 P 441.1606; anal, 442.1634, C26, H25, N3, O2, P in FIG. 1 is a phosphorus-based compound (A) ¹ H NMR spectrum, a characteristic peak of a group of methyl groups at 1.3 ppm can be observed in the spectrum, and split into two peaks due to the influence of phosphorus coupling; the chemical shift is between 4.2 ppm and 5.0 ppm, and an amine can be observed. The characteristic peak of the base. This shows that we have successfully synthesized the phosphorus compound (A) and the product has good purity.

Synthesis Example 2: Synthesis of Compound (B)

The organic cyclic phosphorus compound DOPO, 4-aminoacetophenone, catechol and acid catalyst are used to synthesize R ₁ to R ₄ as a hydrogen atom, R ₅ is a methyl group, and A is -NH ₂ . A phosphorus compound (B) in which both B and C' are -OH. The synthesis steps are as follows: 6.825 g (0.03 mol) of organic cyclic phosphorus compound DOPO, 4.05 g (0.03 mol) of 4-aminoacetophenone, 16.5 g (0.15 mol) of catechol and 0.259 g of oxalic acid. (4 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 130 ° C, and stirring was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into water to precipitate, filtered and dried to obtain a dark purple powder of the product (B) in a yield of about 88%. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₂ NO ₄ P 443.1286;anal.,444.1250,C26,H23,N,O4,P.

Synthesis Example 3: Synthesis of Compound (C)

The organic cyclic phosphorus compound DOPO, 4-aminoacetophenone, 2-aminophenol and acid catalyst are used to synthesize R ₁ to R ₄ as a hydrogen atom, R ₅ is a methyl group, and A is - NH ₂ , B and C' are a phosphorus-based compound (C) of -OH and -NH ₂ , respectively. The synthesis steps are as follows: 12.97 g (0.06 mol) of organic cyclic phosphorus compound DOPO, 8.11 g (0.06 mol) of 4-aminoacetophenone, 32.7 g (0.30 mol) of 2-aminophenol and 0.259 oxalic acid. Gram (4 wt% of DOPO) was placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 130 ° C, and stirring was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into water to precipitate, filtered and dried to obtain a dark purple powder of the product (C) in a yield of about 88%. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₃ N ₂ O ₃ P 442.1446; anal., 443.1476, C26, H24, N2, O3, P. Since the starting material of the reaction is 2-aminophenol There are two reaction sites on the ring, which are the para position of the phenol group and the amino group. Therefore, when the aromatic electrophilic substitution reaction is carried out, two different compounds are finally formed (as shown in the flow chart). ).

Synthesis Example 4: Synthesis of Compound (D)

The organic cyclic phosphorus compound DOPO, 4-aminoacetophenone, m-phenylenediamine and acidic catalyst are used to synthesize R ₁ ~ R ₄ as a hydrogen atom, R ₅ as a methyl group, A, B and C' is a phosphorus-based compound (D) of -NH ₂ . The synthesis steps are as follows: 4.32 g (0.02 mol) of organic cyclic phosphorus compound DOPO, 2.7 g (0.02 mol) of 4-aminoacetophenone, 10.8 g (0.10 mol) of m-phenylenediamine and 0.173 g of oxalic acid. (4 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 130 ° C, and stirring was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into water to precipitate, filtered and dried to obtain a dark purple powder of the product (D) in a yield of about 88%. . HR-MS (FAB +) m / z:.. Calcd for C 26 H 24 N 3 O 2 P 441.1606; anal, 442.1676, C26, H25, N3, O2, P in FIG. 2 is a phosphorus-based compound (D) is ¹ H-NMR spectrum, a characteristic peak of a group of methyl groups at 1.3 ppm can be observed in the spectrum, and split into two peaks due to the influence of phosphorus coupling; the chemical shift is between 4.5 ppm and 5.0 ppm, which can be observed. Characteristic peaks to three amine groups. From the above analysis, it was revealed that the phosphorus compound (D) has been successfully synthesized and has good purity.

Synthesis Example 5: Synthesis of Compound (E)

The organic cyclic phosphorus compound DOPO, 4-aminoacetophenone, resorcinol and acidic catalyst are used to synthesize R ₁ to R ₄ as a hydrogen atom, R ₅ is a methyl group, and A is -NH ₂ . A phosphorus compound (E) in which both B and C' are -OH. The synthesis steps are as follows: 6.825 g (0.03 mol) of organic cyclic phosphorus compound DOPO, 4.055 g (0.03 mol) of 4-aminoacetophenone, 16.5 g (0.15 mol) of resorcinol and 0.259 g of oxalic acid. (4 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 130 ° C, and stirring was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into water to precipitate, filtered and dried to obtain a dark purple powder of the product (E) in a yield of about 88%. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₂ NO ₄ P 443.1286;anal.,444.1276,C26,H23,N,O4,P.

Synthesis Example 6: Synthesis of Compound (F)

The organic cyclic phosphorus compound DOPO, 4-aminoacetophenone, 3-aminophenol and acid catalyst are used to synthesize R ₁ to R ₄ as a hydrogen atom, R ₅ is a methyl group, and A is - NH ₂ , B and C' are a phosphorus-based compound (F) of -OH and -NH ₂ , respectively. The synthesis steps are as follows: 8.457 g (0.04 mol) of organic cyclic phosphorus compound DOO, 5.40 g (0.04 mol) of 4-aminoacetophenone, 21.8 g (0.20 mol) of 3-aminophenol and 0.346 of oxalic acid. Gram (4 wt% of DOPO) was placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 130 ° C, and stirring was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into water to precipitate, filtered and dried to obtain a dark purple powder of the product (F) in a yield of about 88%. . HR-MS (FAB +) m / z:.. Calcd for C 26 H 23 N 2 O 3 P 442.1446; anal, 443.1455, C26, H24, N2, O3, P 3 is a phosphorus-based compound (F) ¹ On the H-NMR spectrum, two sets of methyl characteristic peaks between 1.2 ppm and 1.6 ppm were observed in the spectrum, and characteristic peaks of the two groups of amine groups and phenol groups were observed at 5.0 ppm and 8.8 ppm, respectively. From the above analysis, the product is a mixture, because the starting material of the reaction, 3-aminophenol, has two reaction sites on the benzene ring, which are the para position of the phenol group and the alignment of the amine group, respectively. When an aromatic electrophilic substitution reaction is carried out, two different compounds are eventually produced (as shown in the scheme).

Synthesis Example 7: Synthesis of Compound A-ep

A-ep was synthesized from the phosphorus compound (A), and the synthesis procedure was as follows: 178 g of the phosphorus compound (A) and 740 g of epichlorohydrin were added to a 3 liter reactor, and stirred at a normal pressure to form a homogeneous mixed solution. Thereafter, the reaction temperature was raised to 70 ° C under an absolute pressure of 190 mmHg, and 200 g of a 20% sodium hydroxide solution was added in portions over 4 hours, and simultaneously, the water in the reactor was azeotropically distilled off. After the reaction, the epichlorohydrin and the solvent are distilled off by vacuum distillation, the product is dissolved in methyl ethyl ketone and deionized water, the sodium chloride in the resin is washed, and the solvent is distilled off under reduced pressure to obtain white. The epoxy group-containing A-ep has an epoxy equivalent of 140 g/eq.

Synthesis Example 8: Synthesis of Compound D-ep

D-ep was synthesized from the phosphorus compound (D), and the synthesis procedure was as follows: 222 g of the phosphorus compound (D) and 925 g of epichlorohydrin were added to a 3 liter reactor, and stirred at a normal pressure to form a homogeneous mixed solution. Thereafter, the reaction temperature was raised to 70 ° C under an absolute pressure of 190 mmHg, and 200 g of a 20% sodium hydroxide solution was added in portions over 4 hours, and simultaneously, the water in the reactor was azeotropically distilled off. After the reaction, the epichlorohydrin and the solvent are distilled off by vacuum distillation, the product is dissolved in methyl ethyl ketone and deionized water, the sodium chloride in the resin is washed, and the solvent is distilled off under reduced pressure to obtain white. The epoxy group-containing D-ep has an epoxy equivalent of 138 g/eq.

Fig. ^{1 is a 1} H NMR spectrum chart of the phosphorus compound (A).

Fig. 2 is a ¹ H NMR spectrum chart of the phosphorus compound (D).

Fig. 3 is a ¹ H NMR spectrum chart of the phosphorus compound (F).

The following patent claims are intended to define the scope of the invention. It should be understood that the obvious modifications that can be made by the skilled person based on the disclosure of the present invention are also within the scope of the present invention.

(no component symbol description)

Claims (9)

a phosphorus compound of the formula (I), Wherein R ₁ to R ₄ are each selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, nitro, amine and halogen atoms; A is selected from -NH ₂ , -NHR, -NR ₂ and a group consisting of; B and C' are each selected from -OH, -NH ₂ , a group consisting of -OR, -NHR and -NR ₂ ; R _{5 is} selected from the group consisting of C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl and -CF ₃ ; and R is C ₁ ~ C ₆ alkyl. The compound of claim 1, wherein R ₁ to R _{4 are} each a hydrogen atom, R ₅ is a methyl group, (a) when A, B and C' are simultaneously -NH ₂ , the compound of the formula (I) is a formula (II) );or (b) when A is -NH ₂ , B and C' are simultaneously -OH, the compound of formula (I) is of formula (III); (c) when A is -NH ₂ , B and C' are -OH and -NH ₂ , respectively, and the compound of formula (I) is formula (IV); (d) when A, B and C' are simultaneously , the compound of formula (I) is formula (V) The compound of claim 2, wherein R ₁ to R _{4 are} each a hydrogen atom, and R ₅ is a methyl group, (a) when A, B and C' are simultaneously -NH ₂ , the compound of the formula (II) may be a formula ( A) a compound or a compound of formula (D); or (b) when A is -NH ₂ and B and C' are simultaneously -OH, the compound of formula (III) may be a compound of formula (B) or a compound of formula (E); (c) when A is -NH ₂ , B and C' are -OH and -NH ₂ , respectively, and the compound of formula (IV) may be a compound of formula (C) or a compound of formula (F); (d) when A, B and C' are simultaneously The compound of the formula (V) may be a compound of the formula (A-ep) or a compound of the formula (D-ep) A process for the preparation of a compound of formula (I) according to claim 1 which comprises reacting an organophosphorus compound of formula (VI), a compound of formula (VII), a compound of formula (VIII) and an acidic catalyst to form formula (I) Compound Wherein R ₁ to R ₄ , A, B, C′ and R ₅ are defined in claim 1. The method of claim 4, wherein R ₁ to R ₄ are a hydrogen atom, which comprises (a) when R ₅ is a methyl group, and A, B and C' are simultaneously -NH ₂ , the formula (VI) 9 is 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, formula (VIII) o-phenylenediamine and acid catalyst formation formula ( A) a compound, or a compound of formula (VI) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-aminoacetophenone of formula (VII), formula (VIII) M-phenylenediamine and an acidic catalyst to form a compound of formula (D); or (b) when R ₅ is a methyl group, A is -NH ₂ , and B and C' are simultaneously -OH, formula (VI) 9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, formula (VIII) catechol and acid catalyst formation formula ( B) a compound, or a compound of formula (VI) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-aminoacetophenone of formula (VII), formula (VIII) Resorcinol and an acidic catalyst form a compound of formula (E). (c) When R ₅ is a methyl group, A is -NH ₂ , and B and C' are -OH and -NH ₂ , respectively, the formula (VI) 9,10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, formula (VIII) 2-aminophenol and an acidic catalyst to form a compound of formula (C), or formula (VI) 9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (VII) 4-aminoacetophenone, formula (VIII) 3-aminophenol and acid catalyst formation (F) a compound. The method of claim 5, further comprising, (c) repeating step (a), first preparing a compound of formula (A), and reacting the compound of formula (A) with epichlorohydrin in a solvent to form A, B and C. 'for a product of the formula (A-eP); or (d) repeating step (a), first preparing a compound of formula (D), and reacting the compound of formula (D) with epichlorohydrin in a solvent to form A, B and C 'for The product of formula (D-ep) is a compound. The method of claim 4 or 5, wherein the acidic catalyst is selected from the group consisting of oxalic acid, p-Toluenesulfonic acid (pTSA), acetic acid, and methanesulfonic acid ( Methanesulfonic acid), trifluoromethane sulfonic acid, sulfuric acid, halogenated acid (HX), trifluoroacetic acid (CF ₃ COOH), nitric acid (HNO ₃ ) and phosphoric acid a group consisting of (phosphoric acid, H ₃ PO ₄ ). The compound of claim 1, which is a hardener, wherein A of the compound is -NH ₂ , -NHR or -NR ₂ , and B and C' are each selected from -OH, -NH ₂ , -OR, -NHR And a group consisting of -NR ₂ wherein R is a C ₁ -C ₆ alkyl group. The compound of claim 1, which is a resin flame retardant, wherein the compounds A, B, and C' are