TWI500627B - Phenol-containing multifunctional epoxy curing agents and their derivatives, preparation and use - Google Patents

Description

Phenolic-based 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 processes for their preparation. 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 or a cyanate ester.

Since ancient times, fires have always been one of the biggest accidents that endanger human life and property. Therefore, fireproof materials required for different types of sites and public buildings are also different. Conventional fire-retardant materials are mostly added with a halogen-containing compound to form a composition having high heat resistance. Although it has a considerable effect on fire suppression, it will produce corrosive and toxic substances, such as Dioxin, which may cause abnormalities in the body's metabolism and cause tension, sleep disorders, headache, eye diseases, arteriosclerosis and liver tumors. Animals The experiment was found to cause cancer.

In recent years, organophosphorus compounds have been studied to have good flame retardant properties for high molecular polymers, and organophosphorus compounds do not produce smoke and toxic gases, and have good processability compared with halogen-containing flame retardants. The advantages of low addition amount and low smoke generation, especially the introduction of the organophosphorus reactive group into the main structure of the polymer, make the polymer more flame retardant.

a phosphorus-containing compound such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), which has Active hydrogen reacted by electron-deficient compounds, and electron-deficient compounds such as benzoquinone, oxirane, maleic acid, bismaleimide, diamine The reaction of diaminobenzophenone and terephthaldicarboxaldehyde has attracted much attention from the academic community and the industry.

DOPOBQ [1] is synthesized from DOPO and phenylenedione, which has the following structure:

DOPOBQ is a pioneer in phosphorus-based bisphenol monomers, but its high raw material cost, coupled with poor solubility and reactivity, limits its industrial application.

In 2005, Lin et al. used DOPO and rosolic acid to synthesize a trifunctional dopotriol [2] with the following structure:

Dopotriol is an epoxy resin hardener with good glass transition temperature and flame retardant properties. However, the raw material rose acid is expensive and expensive, and is not economically viable in industrial applications. In 2008, Lin et al. developed a second synthetic route: successfully synthesized at a lower cost of 4,4'-dihydroxy benzophenone (DHBP), DOPO and phenol. The same structure of dopotriol [3]. Due to the low cost of this method, dopotriol has industrial applicability, but even so, DHBP is still a relatively expensive material. The present invention successfully synthesizes a phosphorus-containing polyfunctional compound which can be used as an epoxy resin hardener by using a cheaper raw material.

references

[1] Wang, CS; Shieh, JY Polymer 1998, 39, 5819.

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

[3] Lin, CH; Lin, TL; Chang, SL; Dai, SHA; Cheng, RJ; Hwang, KY; Tu, AP; Su, WC J. Polym. Sci. Part A: Polym. Chem. 2008, 46 ,7898.

SUMMARY OF THE INVENTION An 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 or a cyanate ester.

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 -OH, -OCH ₃ , -OCN 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 (wherein R is a C ₁ -C ₆ alkyl group); and R ₅ is selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ naphthenes group, a phenyl group and Suo group consisting of -CF _3.

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

Wherein two specific embodiments of the formula (MP ₃ ) are the formula (A) or the formula (D):

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

Where the two specific embodiments of the formula (MPA ₂ ) are of the formula (B) or the formula (E):

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

Where the two specific embodiments of the formula (MP ₂ A) are the formula (C) or the formula (F):

When R ₁ to R _{4 of} the compound of the above formula (1) 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 (1) may be

The two specific embodiments of the formula (MP ₃ -EP) are of the formula (A-ep) or the formula (D-ep):

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

The two specific embodiments of the formula (MP ₃ -CY) are of the formula (A-cy) or the formula (D-cy):

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

Where the two specific embodiments of the formula (HP ₃ ) are of the formula (G) or the formula (J):

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

Where the two specific embodiments of the formula (HPA ₂ ) are of the formula (H) or the formula (K):

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

Where the two specific embodiments of the formula (HP ₂ A) are of formula (I) or formula (L):

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

The two specific embodiments of the formula (HP ₃ -EP) are of the formula (G-ep) or the formula (J-ep):

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

The two specific embodiments of the formula (HP ₃ -CY) are of the formula (G-cy) or (J-cy):

Preparation

The present invention provides a process for preparing a compound of the above formula (1), which comprises reacting an organophosphorus compound of the formula (2), a compound of the formula (3), a compound of the formula (4) and an acidic catalyst to form a formula (1). 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 -OH, the formula (2) 9, 10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) catechol and acid catalyst to form compound of formula (A) , or the formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), the formula (3) 4-hydroxyacetophenone, the formula (4) meta-phenylene The phenol and the acidic catalyst form a compound of the formula (D).

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, A is -OH, and B and C' are simultaneously -NH ₂ , the formula (2) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) o-phenylenediamine and acid catalyst formation (B) a compound, or a formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), a formula (3) 4-hydroxyacetophenone, a formula (4) The m-phenylenediamine and the acidic catalyst form a compound of the formula (E).

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, A is -OH, and B and C' are -OH and -NH ₂ respectively, (2) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) 2-aminophenol and acidity Catalyst to form compound of formula (C), or formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone Formula (4) 3-Aminophenol and an acidic catalyst form a compound of formula (F).

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 hydrogen atom, and A, B and C' are simultaneously -OH, the formula (2) 9, 10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4) catechol and an acidic catalyst to form a compound of formula (G), Or the formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), the formula (3) 4-hydroxybenzaldehyde, the formula (4) resorcinol and An acidic catalyst produces a compound of formula (J).

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 hydrogen atom, A is -OH, and B and C' are simultaneously -NH ₂ , the formula (2) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4) o-phenylenediamine and acid catalyst formation formula ( H) a compound, or a formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), a formula (3) 4-hydroxybenzaldehyde, and a formula (4) The phenylenediamine and the acidic catalyst form a compound of the formula (K).

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 hydrogen atom, A is -OH, and B and C' are -OH and -NH ₂ , respectively, (2) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4) 2-aminophenol and acid touch Forming a compound of formula (I), or formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4) 3-Aminophenol and an acidic catalyst to form a compound of the formula (L).

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 or cyanate esterified to a material such as cyanate.

In some specific embodiments of the present invention, four phosphorus compounds such as formula (A), formula (D), formula (G) and formula (J) are synthesized into an epoxy group-containing compound formula by epoxidation reaction ( A-ep), formula (D-ep), formula (G-ep) and formula (J-ep); cyanate esterification reaction can also be used to synthesize the above four phosphorus compounds to form cyanate (A-cy) , formula (D-cy), formula (G-cy) and formula (J-cy).

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 the formula (A-ep), or the compound of the formula (A) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (A) - cy) 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 the formula (D-ep), or the compound of the formula (D) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (D) - cy) compound.

According to the above method, in a further embodiment of the present invention, the compound of the formula (G) can be prepared first, and the compound of the formula (G) is reacted with epichlorohydrin in a solvent to form A, B and C'. The product of the formula (G-ep), or the compound of the formula (G) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (G) - cy) compound.

According to the above method, in a further embodiment of the present invention, the compound of the formula (J) can be prepared first, and the compound of the formula (J) is reacted with epichlorohydrin in a solvent to form A, B and C'. The product of the formula (J-ep), or the compound of the formula (J) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (J) - cy) 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 (1) or a mixture thereof, wherein A of the compound is -OH or -OCH ₃ , and B and C' are each selected from -OH, -NH ₂ , - A group consisting of OR, -NHR and -NR ₂ wherein R is a C ₁ -C ₆ alkyl group.

The invention also discloses a flame retardant resin (including an epoxy resin and a cyanate ester), which comprises a compound of the formula (1) as described above, wherein the compound of the formula (1) A is -OCN or , B and C' are each -OCN or .

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)

Using organic cyclic phosphorus compounds DOPO, catechol, 4-hydroxyacetophenone and acid catalyst, R ₅ is synthesized as methyl group, and A, B and C' are both -OH. Phosphorus compound (A). The synthesis steps are as follows:

The organic cyclic phosphorus compound DOPO 5.405 g (0.025 mol), catechol 14 g (0.125 mol), 4-hydroxyacetophenone 3.405 g (0.025 mol) and oxalic acid 0.216 g (4 wt% of DOPO) Place 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 ₂₁ O ₅ P 444.1127; anal., 445.1134, C26, H22, O5, P.

Fig. 1 is a ¹ H NMR spectrum of a phosphorus compound (A).

Synthesis Example 2: Synthesis of Compound (B)

Using organic cyclic phosphorus compound DOPO, o-phenylenediamine, 4-hydroxyacetophenone and acid catalyst, R ₅ is synthesized as methyl group, A is -OH, and B and C' are both -NH ₂ Phosphorus compound (B). The synthesis steps are as follows: 6.825 g (0.03 mol) of organic cyclic phosphorus compound DOPO, 16 g (0.15 mol) of o-phenylenediamine, 4.09 g (0.04 mol) of 4-hydroxyacetophenone, 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 ₂₃ N ₂ O ₃ P 442.1446; anal., 443.1476, C26, H24, N2, O3, P.

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

Synthesis Example 3: Synthesis of Compound (C)

Using organic cyclic phosphorus compound DOPO, 2-aminophenol, 4-hydroxyacetophenone and acid catalyst, R ₅ is synthesized as methyl group, A is -OH, and B and C' are -OH, respectively. Phosphorus complex (C) with -NH ₂ . The synthesis steps are as follows: 9.45 g (0.0435 mol) of organic cyclic phosphorus compound DOPO, 23.7 g (0.225 mol) of 2-aminophenol, 5.955 g (0.0435 mol) of 4-hydroxyacetophenone, and 0.378 g of oxalic acid. (4% by weight of DOPO), placed in a 250 ml three-necked reaction crying.

Next, the reaction temperature was raised to 180 ° 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 product (C) in a yield of about 92%. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₂ NO ₄ P 443.1286;anal.,444.1345,C26,H23,N,O4,P.

Synthesis Example 4: Synthesis of Compound (D)

A phosphorus-based compound in which R ₅ is a methyl group, and A, B and C' are both -OH, using an organic cyclic phosphorus compound DOPO, resorcinol, 4-hydroxyacetophenone, and an acid catalyst. ). The synthesis steps are as follows: 10.81 g (0.05 mol) of organic cyclic phosphorus compound DOP, 27.53 g (0.25 mol) of resorcinol, 6.81 g (0.05 mol) of 4-hydroxyacetophenone, and 0.432 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 added dropwise to water to precipitate, filtered and dried to obtain a yellow powder of the product (D) in a yield of about 95% and a melting point of 163 °C. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₁ O ₅ P 444.1127; anal., 445.1107, C26, H22, O5, P.

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

Synthesis Example 5: Synthesis of Compound (E)

Using organic cyclic phosphorus compounds DOPO, m-phenylenediamine, 4-hydroxyacetophenone and an acidic catalyst, R ₅ is synthesized as methyl, A is -OH, and B and C' are both -NH ₂ Phosphorus compound (E). The synthesis steps are as follows: 8.65 g (0.04 mol) of organic cyclic phosphorus compound DOPO, 21.63 g (0.2 mol) of m-phenylenediamine, 5.45 g (0.04 mol) of 4-hydroxyacetophenone and 0.346 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 added dropwise to water to precipitate, filtered and dried to obtain a brown powder of the product (E) in a yield of about 89%. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₃ N ₂ O ₃ P 442.1446; anal., 443.1453, C26, H24, N2, O3, P.

Synthesis Example 6: Synthesis of Compound (F)

Using organic cyclic phosphorus compound DOPO, 3-aminophenol, 4-hydroxyacetophenone and acid catalyst, R ₅ is synthesized as methyl group, A is -OH, and B and C' are -OH, respectively. Phosphorus compound (F) with -NH ₂ . The synthesis steps are as follows: organic cyclic phosphorus compound DOPO 6.3 g (0.029 mol), 3-amine phenol 15.8 g (0.15 mol), 4-hydroxyacetophenone 3.97 g (0.029 mol) and oxalic acid 0.252 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 white powder of the product (F) in a yield of about 89%. HR-MS(FAB+)m/z:calcd. for C ₂₆ H ₂₂ NO ₄ P 443.1286;anal.,444.1273,C26,H23,N,O4,P.

4 is a ¹ H NMR spectrum of a phosphorus compound (F).

Synthesis Example 7: Synthesis of Compound (G)

Phosphorus compounds in which R ₅ is hydrogen and A, B and C' are -OH are synthesized by organic cyclic phosphorus compounds DOPO, catechol, 4-hydroxybenzaldehyde and acidic catalysts. ). The synthesis steps are as follows: organic cyclic phosphorus compound DOPO 7.99 g (0.037 mol), catechol 21 g (0.185 mol), 4-hydroxybenzaldehyde 4.52 g (0.05 mol) and oxalic acid 0.32 g (DOPO) 4 wt%), 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, added with a small amount of methanol, and then added dropwise to water to precipitate, filtered and dried to give the product (G), yield 75%, melting point 173 °C. HR-MS(FAB+)m/z:calcd. for C ₂₅ H ₁₉ O ₅ P 430.097;anal.,431.0982,C25,H20,O5,P.

Fig. 5 is a ¹ H NMR spectrum of the phosphorus compound (G).

Synthesis Example 8: Synthesis of Compound (H)

A phosphorus-based compound (H) in which R ₅ is hydrogen, A is -OH, and B and C' are both -NH ₂ using an organic cyclic phosphorus compound DOPO, o-phenylenediamine, 4-hydroxybenzaldehyde and an acid catalyst. . The synthesis steps are as follows: organic cyclic phosphorus compound DOPO 9.05 g (0.042 mol), o-phenylenediamine 22.7 g (0.21 mol), 4-hydroxybenzaldehyde 5.124 g (0.04 mol) and oxalic acid 0.362 g (DOPO) 4 wt%), 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 methanol, and then dropped into water to precipitate, filtered and dried to give the product (H), yield 74%. HR-MS(FAB+)m/z:calcd. for C ₂₅ H ₂₁ N ₂ O ₃ P 428.129;anal.,429.1281,C25,H22,N2,O3,P.

Synthesis Example 9: Synthesis of Compound (I)

The organic cyclic phosphorus compound DOPO, 2-aminophenol, 4-hydroxybenzaldehyde and acid catalyst are used to synthesize R ₅ as hydrogen, A is -OH, and B and C' are phosphorus systems of -OH and -NH ₂ , respectively. Compound (I). The synthesis steps are as follows: 7.56 g (0.0348 mol) of organic cyclic phosphorus compound DOPO, 18.96 g (0.18 mol) of 2-aminophenol, 4.248 g (0.0348 mol) of 4-hydroxybenzaldehyde and 0.3024 g of oxalic acid ( 4 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, the reaction temperature was raised to 180 ° 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 methanol, and then added dropwise to water to precipitate, filtered and dried to give the product (I), yield 73%. HR-MS(FAB+)m/z:calcd. for C ₂₅ H ₂₀ NO ₄ P 429.1130; anal., 430.1234, C25, H21, N, O4, P.

Synthesis Example 10: Synthesis of Compound (J)

A phosphorus-based compound (J) in which R ₅ is hydrogen and A, B and C' are both -OH is synthesized using an organic cyclic phosphorus compound DOPO, resorcin, 4-hydroxybenzaldehyde and an acid catalyst. The synthesis steps are as follows: 10.81 g (0.05 mol) of organic cyclic phosphorus compound DOP, 27.53 g (0.25 mol) of resorcinol, 6.11 g (0.05 mol) of 4-hydroxybenzaldehyde and 0.432 g of oxalic acid (DOPO) 4 wt%), 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 methanol, and then added dropwise to water to precipitate, filtered and dried to give the product (J), yield 76%, melting point 168 °C. HR-MS(FAB+)m/z:calcd. for C ₂₅ H ₁₉ O ₅ P 430.097;anal.,431.0911,C25,H20,O5,P.

Fig. 6 is a ¹ H NMR spectrum of the phosphorus compound (J).

Synthesis Example 11: Synthesis of Compound (K)

A phosphorus-based compound (K) in which R ₅ is hydrogen, A is -OH, and B and C' are both -NH ₂ using an organic cyclic phosphorus compound DOPO, m-phenylenediamine, 4-hydroxybenzaldehyde and an acid catalyst. . The synthesis steps are as follows: 8.65 g (0.04 mol) of organic cyclic phosphorus compound DOP, 21.63 g (0.2 mol) of m-phenylenediamine, 4.88 g (0.04 mol) of 4-hydroxybenzaldehyde and 0.346 g of oxalic acid (DOPO) 4 wt%), 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 methanol, and then dropped into water to precipitate, filtered and dried to give the product (K), yield 78%. HR-MS(FAB+)m/z:calcd. for C ₂₅ H ₂₁ N ₂ O ₃ P 428.129;anal.,429.1271,C25,H22,N2,O3,P.

Synthesis Example 12: Synthesis of Compound (L)

The organic cyclic phosphorus compound DOPO, 3-aminophenol, 4-hydroxybenzaldehyde and acid catalyst are used to synthesize R ₅ as hydrogen, A is -OH, and B and C' are -OH and -NH ₂ respectively. Compound (L). The synthesis steps are as follows: 6.3 g (0.029 mol) of organic cyclic phosphorus compound DOC, 15.8 g (0.15 mol) of 3-aminophenol, 3.54 g (0.029 mol) of 4-hydroxybenzaldehyde and 0.252 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 methanol, and then added dropwise to water to precipitate, filtered and dried to give the product (L), yield 78%. HR-MS(FAB+)m/z:calcd. for C ₂₅ H ₂₀ NO ₄ P 429.1130; anal., 430.1159, C25, H21, N, O4, P.

Synthesis Example 13: Synthesis of Compound A-ep

Compound A-ep was synthesized from phosphorus compound (A). The synthesis steps are as follows: 178 g of the phosphorus compound (A) and 740 g of epichlorohydrin are added to a 3 liter reactor, and the mixture is stirred under normal pressure to form a homogeneous mixed solution, and then the reaction temperature is raised to 190 mmHg absolute pressure. At 70 ° C and 200 g of 20% sodium hydroxide solution were added in portions over 4 hours, and simultaneously, the water in the reactor was azeotropically distilled off. After the reaction, the cyclochloropropane 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 a white color. The epoxy group has an A-ep having an epoxy equivalent of 204 g/eq.

Synthesis Example 14: Synthesis of Compound A-cy

The compound A-cy was synthesized using the phosphorus compound (A). The synthesis procedure was as follows: Anhydrous acetone (70 g) was added to a three-neck reactor. After the reactor was cooled to -15 ° C, 10.804 g (0.102 mol) of cyanogen bromide (BrCN) was added and stirred while the temperature was lowered to below -25 °C. Further, 13.3 g (0.03 mol) of the phosphorus compound (A) and triethylamine (Triethylamine, Et ₃ N) 9.198 g (0.0909 mol) were thoroughly mixed and dissolved in anhydrous acetone (100 g), followed by a feed funnel. The solution was slowly dropped into the reactor, and the temperature was maintained at -30 ° C, and the reaction was maintained for 2 hours. When the reaction temperature returned to -30 ° C, the reaction was dropped into deionized water to wash to remove the ammonium bromide salt. After filtration, the resulting precipitate was extracted with CH ₂ Cl ₂ /H ₂ O. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH ₂ Cl _{2 was} removed using a rotary evaporator at room temperature to give a cyanate ester solid.

Synthesis Example 15: Synthesis of Compound D-ep

The compound D-ep was synthesized from the phosphorus compound (D). The synthesis steps are as follows: 222 g of the phosphorus compound (D) and 925 g of epichlorohydrin are added to a 3 liter reactor, and after stirring under normal pressure to form a homogeneous mixed solution, the reaction temperature is raised at an absolute pressure of 190 mmHg until At 70 ° C and 200 g of 20% sodium hydroxide solution were added in portions over 4 hours, and simultaneously, the water in the reactor was azeotropically distilled off. After the reaction, the cyclochloropropane 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 a white color. The epoxy group had D-ep with an epoxy equivalent of 204 g/eq.

Synthesis Example 16: Synthesis of Compound D-cy

The compound D-cy was synthesized using the phosphorus compound (D). The synthesis procedure was as follows: Anhydrous acetone (70 g) was added to a three-neck reactor. After cooling the reactor to -15 ° C, BrCN 7.2027 g (0.068 mol) was added and stirred while the temperature was lowered to below -25 °C. Further, 8.89 g (0.02 mol) of the phosphorus compound (D) and Et ₃ N 6.1321 g (0.0606 mol) were thoroughly mixed and dissolved in anhydrous acetone (100 g), and then slowly dropped into the reactor through a feed funnel. The temperature was maintained at -30 ° C and the reaction was maintained for 2 hours. When the reaction temperature returned to -30 ° C, the reaction was dropped into deionized water to wash to remove the ammonium bromide salt. After filtration, the resulting precipitate was extracted with CH ₂ Cl ₂ /H ₂ O. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH ₂ Cl _{2 was} removed using a rotary evaporator at room temperature to give a cyanate ester solid.

Synthesis Example 17: Synthesis of Compound G-ep

The compound G-ep was synthesized from the phosphorus compound (G). The synthesis steps are as follows: 194 g of the phosphorus compound (G) and 833 g of epichlorohydrin are added to a 3 liter reactor, and after stirring at a normal pressure to form a homogeneous mixed solution, the reaction temperature is raised at an absolute pressure of 190 mmHg until At 70 ° C and 200 g of 20% sodium hydroxide solution were added in portions over 4 hours, and simultaneously, the water in the reactor was azeotropically distilled off. After the reaction, the cyclochloropropane 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 a white color. G-ep of epoxy group with an epoxy equivalent of 200 g/eq.

Synthesis Example 18: Synthesis of Compound G-cy

The compound G-cy is synthesized using a phosphorus compound (G). The synthesis procedure was as follows: Anhydrous acetone (70 g) was added to a three-neck reactor. After cooling the reactor to -15 ° C, 5.402 g (0.051 mol) of BrCN was added and stirred while the temperature was lowered to below -25 °C. Further, 6.455 g (0.015 mol) of the phosphorus compound (G) and Et ₃ N 4.604 g (0.0455 mol) were thoroughly mixed and dissolved in anhydrous acetone (100 g), and then slowly dropped into the reactor through a feed funnel. The temperature was maintained at -30 ° C and the reaction was maintained for 2 hours. When the reaction temperature returned to -30 ° C, the reaction was dropped into deionized water to wash to remove the ammonium bromide salt. After filtration, the resulting precipitate was extracted with CH ₂ Cl ₂ /H ₂ O. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH ₂ Cl _{2 was} removed using a rotary evaporator at room temperature to give a cyanate ester solid.

Synthesis Example 19: Synthesis of Compound J-ep

Compound J-ep was synthesized from phosphorus compound (J). The synthesis step is as follows: 215 g of the phosphorus compound (J) and 925 g of epichlorohydrin are added to a 3 liter reactor, and after stirring at a normal pressure to form a homogeneous mixed solution, the reaction temperature is raised at an absolute pressure of 190 mmHg until At 70 ° C and 200 g of 20% sodium hydroxide solution were added in portions over 4 hours, and simultaneously, the water in the reactor was azeotropically distilled off. After the reaction, the cyclochloropropane 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 a white color. The epoxy group has a J-ep having an epoxy equivalent of 200 g/eq.

Synthesis Example 20: Synthesis of Compound J-cy

The compound J-cy was synthesized using the phosphorus compound (J). The synthesis procedure was as follows: Anhydrous acetone (70 g) was added to a three-neck reactor. After cooling the reactor to -15 ° C, BrCN 7.2027 g (0.068 mol) was added and stirred while the temperature was lowered to below -25 °C. Further, 8.606 g (0.02 mol) of the phosphorus compound (J) and Et ₃ N 6.1321 g (0.0606 mol) were thoroughly mixed and dissolved in anhydrous acetone (100 g), and then slowly dropped into the reactor through a feed funnel. The temperature was maintained at -30 ° C and the reaction was maintained for 2 hours. When the reaction temperature returned to -30 ° C, the reaction was dropped into deionized water to wash to remove the ammonium bromide salt. After filtration, the resulting precipitate was extracted with CH ₂ Cl ₂ /H ₂ O. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH ₂ Cl _{2 was} removed using a rotary evaporator at room temperature to give a cyanate ester solid.

Figure 1 is a ¹ H NMR spectrum of the compound of formula (A).

Figure 2 is a ¹ H NMR spectrum of the compound of formula (B).

Figure 3 is a ¹ H NMR spectrum of the compound of formula (D).

Figure 4 is a ¹ H NMR spectrum of the compound of formula (F).

Figure 5 is a ¹ H NMR spectrum of the compound of formula (G).

Figure 6 is a ¹ H NMR spectrum of the compound of formula (J).

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 (11)

a phosphorus compound of the formula (1), Wherein R ₁ to R ₄ are each hydrogen; and A is selected from the group consisting of -OH, -OCH ₃ , -OCN 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 (wherein R is a C ₁ -C ₆ alkyl group); and R ₅ is selected from the group consisting of hydrogen and a C ₁ -C ₆ alkyl group. The compound of claim 1, wherein R ₅ is methyl, (a) when A, B and C' are simultaneously -OH, the compound of formula (1) is of formula (MP ₃ ); (b) when A is -OH, B and C' are simultaneously -NH ₂ , and the compound of formula (1) is of the formula (MPA ₂ ); (c) when A is -OH, B and C' are -OH and -NH ₂ , respectively, and the compound of formula (1) is of the formula (MP ₂ A); (d) when A, B and C' are simultaneously , the compound of the formula (1) is of the formula (MP ₃ -EP); (e) When A, B and C' are simultaneously -OCN, the compound of formula (1) is of the formula (MP ₃ -CY) The compound of claim 2, wherein R ₅ is methyl, (a) when A, B and C' are simultaneously -OH, the compound of formula (MP ₃ ) may be a compound of formula (A) or a compound of formula (D); or (b) when A is -OH, B and C' are simultaneously -NH ₂ , the compound of formula (MPA ₂ ) may be a compound of formula (B) or a compound of formula (E); (c) when A is -OH, B and C' are -OH and -NH ₂ , respectively, and the compound of formula (MP ₂ A) 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 (MP ₃ -EP) may be a compound of the formula (A-ep) or a compound of the formula (D-ep); (e) When A, B and C' are simultaneously -OCN, the compound of the formula (MP ₃ -CY) may be a compound of the formula (A-cy) or a compound of the formula (D-cy) The compound of claim 1, wherein R ₅ is a hydrogen atom, (a) when A, B and C' are simultaneously -OH, the compound of formula (1) is of formula (HP ₃ ); (b) when A is -OH, B and C' are simultaneously -NH ₂ , and the compound of formula (1) is of the formula (HPA ₂ ); (c) when A is -OH, B and C' are -OH and -NH ₂ , respectively, and the compound of formula (1) is of the formula (HP ₂ A); (d) when A, B and C' are simultaneously , the compound of formula (1) is of the formula (HP ₃ -EP); or (e) When A, B and C' are both -OCN, the compound of formula (1) is of the formula (HP ₃ -CY) The compound of claim 4, wherein R ₅ is a hydrogen atom, when A is -OH, and B and C' are simultaneously -NH ₂ , the compound of formula (HPA ₂ ) may be a compound of formula (H) or a compound of formula (K) ;or (b) when A is -OH, B and C' are -OH and -NH ₂ , respectively, and the compound of formula (HP ₂ A) may be a compound of formula (I) or a compound of formula (L); (c) When A, B and C' are simultaneously , the compound of the formula (HP ₃ -EP) may be a compound of the formula (G-ep) or a compound of the formula (J-ep); (d) When A, B and C' are simultaneously -OCN, the compound of the formula (HP ₃ -CY) may be a compound of the formula (G-cy) or a compound of the formula (J-cy) A process for preparing a compound of the formula (1) according to claim 1, which comprises reacting an organophosphorus compound of the formula (2), a compound of the formula (3), a compound of the formula (4) and an acidic catalyst to form a formula (1). Compound Wherein R ₁ to R ₄ , A, B, C′ and R ₅ are defined in claim 1. The method of claim 6, 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 -OH, the formula (2) 9, 10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) catechol and acid catalyst to form formula (A) a compound, or a formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), a formula (3) 4-hydroxyacetophenone, a formula (4) meta-benzene Diphenol and an acidic catalyst to form a compound of formula (D); or (b) when R ₅ is a methyl group, A is -OH, and B and C' are simultaneously -NH ₂ , the formula (2) 9, 10 - two Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) o-phenylenediamine and an acidic catalyst to form a compound of formula (B), Or the formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), the formula (3) 4-hydroxyacetophenone, the formula (4) m-phenylenediamine Forming a compound of formula (E) with an acidic catalyst; or (c) when R ₅ is a methyl group, A is -OH, and B and C' are -OH and -NH ₂ respectively, formula (2) 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) 2-aminophenol and acid catalyst (C) a compound, or a compound of formula (2) 9,10-dihydro-9-oxygen -10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxyacetophenone, formula (4) 3-aminophenol and an acidic catalyst to form a compound of formula (F); or (d) R ₅ is a hydrogen atom, and when A, B and C' are simultaneously -OH, the formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula ( 3) 4-hydroxybenzaldehyde, formula (4) catechol and acid catalyst to form compound of formula (G), or formula (2) 9,10-dihydro-9-oxa-10-phosphanthene- 10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4) resorcinol and an acidic catalyst to form a compound of formula (J); or (e) when R ₅ is a hydrogen atom, A is -OH, B and C' are -NH ₂ at the same time, the formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4- Hydroxybenzaldehyde, (4) o-phenylenediamine and an acidic catalyst to form a compound of formula (H), or a compound of formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4) m-phenylenediamine and an acidic catalyst to form a compound of formula (K); or (f) when R ₅ is a hydrogen atom, A is -OH, B When C' is -OH and -NH ₂ respectively, the formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), the formula (3) 4-hydroxyl group Benzaldehyde, formula (4) 2-aminophenol and acid Catalyst to form a compound of formula (I), or formula (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4-hydroxybenzaldehyde Formula (4) 3-Aminophenol and an acidic catalyst form a compound of formula (L). The method of claim 7, which further comprises (g) 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 The product of the formula (A-ep), or the compound of the formula (A) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (A) - cy) compound; or (h) 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' The product of the formula (D-ep), or the compound of the formula (D) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (D) - cy) compound; or (i) repeating step (d), first preparing a compound of formula (G), and reacting the compound of formula (G) with epichlorohydrin in a solvent to form A, B and C' The product of the formula (G-ep), or the compound of the formula (G) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (G) - cy) compound; or (j) repeating step (d), first preparing a compound of formula (J), and reacting the compound of formula (J) with epichlorohydrin in a solvent to form A, B and C' The product of the formula (J-ep), or the compound of the formula (J) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form a product of A, B and C' as -OCN (J) - cy) compound. The method of claim 6 or 7, 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 ). A phosphorus-based compound of the formula (1) of claim 1, or a mixture thereof, which is a hardener, wherein A of the compound is -OH or -OCH ₃ , and B and C' are each selected from -OH, -NH _a group consisting of -OR, -NHR and -NR ₂ wherein R is a C ₁ -C ₆ alkyl group. A phosphorus-based compound of the formula (1) of claim 1, which is a flame retardant resin, wherein A of the compound of the formula (1) is -OCN or , B and C' are each -OCN or .