TW201100444A - Phenol-containing multifunctional epoxy curing agents and their derivatives, preparation and use - Google Patents

Abstract

A series of phosphorus-containing compounds having the following formula are disclosed: wherein R1 to R4 are independently selected from the group consisting of H, C1 to C6 alkyl, nitro, amino, and halogen; A is selected from the group consisting of -OH, -OCH3, -OCN, and; B and C' are independently selected from the group consisting of -OH, -NH2, -OCN, -OR, -NHR, and -NR2 (wherein R is C1 to C6 alkyl); and R5 is selected from the group consisting of H, C1 to C6 alkyl, C3 to C6 cyclic alkyl, phenyl, and -CF3. The present invention provides a process for the preparation of the compound of formula (1). The present invention also provides a curing agent and a flame resistant resin.

Description

201100444 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a series of phosphorus-based polyfunctional compounds and a method for producing the same. The dish-containing compound can be used as a hard-and-burn resin such as a resin and a cyanate ester in addition to an epoxy resin. [Prior Art] Since ancient times, fires have always been one of the greatest contrived to human life and property, so the fire materials required for different types of sites and public buildings are also different. Conventional fire-resistant materials are mostly added with dentate-containing compounds to form a highly heat-rich composition. Although there is a considerable political effect on fire suppression, it will produce corrosive and toxic substances such as Dioxin, which may cause abnormal metabolism, cause nervousness, sleep disorders, headache, eye diseases, arteriosclerosis and liver tumors. Animals The experiment was found to cause cancer. In recent years, organophosphorus compounds have been developed to have good flame retardant properties for high molecular polymers' and compared with the inclusion of flame retardants, organophosphorus compounds do not produce smoke and toxic gases, and are processable. Good, low addition and low smoke generation, especially the main structure of the organic phosphorus reactive group introduced into the polymer will make the polymer more flame retardant. A lining compound such as 9,10-dihydro-9-oxa-10-phosphonium-10-oxide (9,1 O-dihydro-9-oxa-1O-phosphaphenanthrene- 10-oxide, DOPO) has Active hydrogen reactive with electron-deficient compounds, and electron-deficient compounds such as benzoquinone, oxirane, maleic acid, bismaleimide, Amine 140534.doc 201100444 Diphenylbenzophenone and terephthaldicarboxaldehyde, the derivatives of which are well received by the academic community and the industry. DOPOBQ [l] is synthesized from DOPO and benzodiatone, 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:

OH dopotriol uses dopotriol as 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: successful synthesis at a lower cost of 4,4'-dihydroxy benzophenone (DHBP), DOPO and benzene. The same structure of dopotriol [3]. Due to the low cost of this method, dopotriol has industrial applicability, but even so, DHBP still belongs to the material of 140534.doc 201100444. The present invention can be used as an epoxy resin hardener. References Wang] Wang, c. s.; shieh, The present invention successfully synthesizes a phosphorus-containing polyfunctional compound of a hardener using a cheaper raw material. [2] Lin, C. H.; Cai, S. 儿户〇/少衍·C/iem. 2005,43 [3] Lin, C. ^ Cheng, R. j.;

Shieh, J. Y. Polymer 1998, 39, 5819. ai, S. X.; Lin, C. H. J. P〇iym_ Sci Part 〇5, 43, 5971. S. X.; Lin

Sci. Part A: Polym. Chem. 2008, 46, 7898. 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 retardant properties. Such as epoxy resin or cyanate ester. Compounds The present invention discloses scaly compounds having the following chemical formula:

Ri~R4 are each selected from the group consisting of hydrogen, Ci~C6 alkyl, nitro, amine and halogen atoms; A is selected from the group consisting of -〇H, _OCH3, _OCN and the group; 140534.doc 201100444 Β And the C series are each selected from the group consisting of: 〇Η, Ν Ν 2、 2, 〇 〇 CN, 〇 〇, -OR, -NHR, and _NR2 (wherein R is a Cl~c6 alkyl group); and R5 is selected from the group consisting of hydrogen, Ci a group consisting of ~C6 alkyl, c3~C6 cycloalkyl, phenyl and 〇]p:. When Rr5 of the compound of the above formula (1) is each a hydrogen atom, R5 is a fluorenyl group, and A, B and C' are both _〇h, the structural formula of the compound of the formula (1) may be

Ο (MP3), wherein the two embodiments of the formula (MP3) are of the formula (A) or the day (D):

Ο (D). When R of the compound of the above formula (1) is each a hydrogen atom, 1 is a methyl group, and 7 is -OH' B and C' is simultaneously _NH2, the structure 3 of the compound of the formula (1) may be

(MPA) 140534.doc 201100444 The two embodiments of the formula (MPA2) are of the formula (B) or (E):

When R^R4 of the compound of the above formula (1) is each a hydrogen atom, & is a methyl group, A is -OH, and B and C are -OH and -NH2, respectively, and the structure of the compound of the formula (1) may be

(MP2A), wherein the two specific embodiments of the formula (MPZA) are of the formula (c) or < (F):

When the RrR4 of the compound of the above formula (1) is a mouse atom, R_5 is a methyl group, and A, B and C' are simultaneously a ruthenium, and the structural formula of the compound of the formula (1) can be 140534.doc 201100444

(MPs-EP), wherein the two specific embodiments of the formula (MPs-EP) are of the formula (A-print) or

(D-ep) (D-ep):

When the thiol groups A, B and C' are simultaneously -〇CN, the structural formula of the compound of the formula (1) can be

N

CN (mp3-cy) 5 wherein the two specific embodiments of the formula (MP^CY) are of the formula (A_c force or formula (D-cy): 140534.doc -9- 201100444

Tian A

(D-cy) wherein each of the compounds of the formula (1) is a hydrogen atom, r5 is a hydrogen atom, and 8: (: ' is simultaneously -OH, the structural formula of the compound of the formula (1) may be

(HP3) wherein the two specific embodiments of the formula (HP3) are of the formula (G) or the formula (J):

S The compound of the above formula (1), 2Ri to R4, each of which is a hydrogen atom, & is a hydrogen atom, and A is -OH, B and C, and at the same time, the structure of the compound of the formula (1) may be

140534.doc 201100444 Two of the formulas (HPA2) (K):

The aspect of the specific embodiment is a formula (Η) or a formula

When R1 to R4 of the compound of the above formula (1) are each a hydrogen atom, and I is a hydrogen atom,

A is -〇H, B and C. are respectively, and the structure of the compound of the formula (1) can be

(HP2A), wherein the two specific embodiments of the formula (HPM) are of the formula (1) or the formula (L):

When the RrR4 of the compound of the above formula (1) is a ruthenium atom, & is a ruthenium atom, and A, B and C' are simultaneously, the structural formula of the compound of the formula (1) may be 140534.doc • 11 · 201100444

〇 ) Λ 4 (ΗΡ3-ΕΡ) , where the two specific embodiments of the formula (ΗΡ3_ΕΡ) are of the formula (G_ep) or (J-ep):

(G-ep)

〇 ‘ When RrR4 of the above formula (1) is a hydrogen atom and Rs is a chlorine atom, and A, B and C1 are simultaneously -OCN, the structural formula of the compound of the formula (1) can be

N

CN (HP3-CY) is a form of two specific embodiments of the formula (G-cy) or of the formula (HPs-CY) (j-cy): 140534.doc -12- 201100444

The present invention provides a process for producing 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) The compounds Β, C' and R_5 are as defined above; wherein R][~R4, A,

B

0-P-0

I Η (2) (7) (4) According to the above method, in the specific embodiment of the present invention, when R1 to h are chlorine atoms '1 is a methyl group, and A, B and C' are simultaneously -OH,

(2) 9,1〇_Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), formula (3) 4_ hydroxybenketone, formula (4) catechol and acid touch The product of formula (A) or formula (7) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (〇) formula (3) 4-hydroxyacetophenone, between formula (4) Hydroquinone and an acidic catalyst form a compound of formula (D). Red According to the above method, in the specific embodiment of the present invention, when the hydrogen atom R5 is a methyl group, A is -OH, and B and C' are simultaneously -NH2, the formula (), hydrazine oxa-10- Phosphenephenanthrene-10-oxide (d〇p〇), formula (3) 4-p-phenylene, 4 γu. Formula (4) o-phenylenediamine and acid catalyst to form formula (B) 140534.doc •13· 201100444 or formula (2) 9,10-dihydro-9-oxa-10-fluorene-10-oxide (:2), formula (3) 4-hydroxyacetophenone, 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 U4 is ^ atomic to methyl, W, B and C are respectively _0H and the mother will be (2) 9,10-dihydro·9-oxygen a compound of the formula (C), which is a compound of the formula (3), a compound of the formula (3), a phenyl group, and an acid catalyst, Or the formula (7) 9,1G-dihydro·9-oxa. linofene _ oxide (D〇P〇), formula (7) 4 _ acetophenone, formula (4) 3-aminobenzene and acid catalyst A compound of formula (F) is produced. According to the above method, in the specific embodiment of the present invention, when & is a hydrogen atom 'Π5 is a hydrogen atom, A, B and c, and at the same time, the formula (2) 9,10-dihydro_9_ Oxygen 〇 〇 菲 〇 〇 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 9,10-Dihydro-9-oxa-10-phosphonium phenanthrene oxide (DOPO), formula (3) 4_ thiophene formaldehyde, formula (4) resorcinol and acid catalyst generation (J) Compound According to the above method, in the specific embodiment of the present invention, when Ri~heart is a hydrogen atom 'Rs is a hydrogen atom, and A is -〇H, B and C, and is _Nh2, the formula (2) 9,10--hydrogen-9-oxa-10-phenanthrene-10-oxide (DOPO), formula (3) 4-pyrimidine formaldehyde, formula (4) o-phenylene diamine and acid catalyst阳)) compound ' or formula (2) 9,10-dihydro-9-oxa-10-phosphaphenidinium oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, formula (4 The stupid diamine and the acidic catalyst form a formula (K) > f complex. 140534.doc -14· 201100444 According to the above method, in the specific embodiment of the present invention, when R is ~ a nitrogen atom, R5 is a hydrogen atom 'A is · 〇Η, Β and C, respectively, rhyme and solitude, The formula (2) 9,10-dihydro-9-oxa-1〇_phosphaphenanthene oxide (D〇P〇), the formula (3) 4_ via the base benzophenone, the formula (4) 2 _ Aminobenzene is expected to form a compound of the formula (1) with an acid catalyst, or a compound of the formula (7), 9,1 〇-diaza·9-oxa-1〇_filling phenanthrene 〇 1 〇·oxide (D0P0), formula (3) 4 _ The compound of the formula (L) is formed by a benzyl group, a compound of the formula (4), and an acidic catalyst. From the above, it is understood that the ruthenium compound of the present invention has reactivity at the terminal (4) and an amine functional group', and thus can be used as a curing agent for an epoxy resin. It can also be further oxidized to epoxy resin or cyanate esterified to cyanate ester and other materials. In some specific embodiments of the present invention, four phosphorus compounds such as formula (A), formula (D), formula (G) and formula (7) are synthesized into an epoxy group-containing compound by an epoxidation reaction (A. Ep), formula (D_ep), formula (G_ep) and formula (~); can also synthesize the above four phosphorus compounds by the cyanide sensation reaction to synthesize cyanate (A_Cy), formula (D-cy), formula ( G-cy) and formula (J-Cy). Q, according to the above method, in a further embodiment of the present invention, the compound of the formula (A) can be prepared first, and the compound of the formula (A) is reacted with an epoxy propylene in a solvent to form A, B and C'. The compound 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 compound of the formula (A-cy) wherein A, 8 and hydrazine are -OCN. . According to the above method, in a further embodiment of the present invention, the compound of the formula (D) can be prepared first, and then the compound of the formula (D) can be reacted with epoxidized propane in a solvent to form A, B and C. The product of formula (D_ep), or the compound of formula (D) is reacted with cyanogen bromide and triethylamine in a solvent to form cyanate 140534.doc -15- 201100444 to form A, B and C' -OCN product of formula (D-cy). 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) can be reacted with epichlorohydrin in a solvent to form a product of A, B and C'. a compound of the formula (G-ep), or a cyanate esterification reaction of a compound of the formula (G) 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) may be first prepared, and the compound of the formula (J) is reacted with epichlorohydrin in a solvent to form a product of A, B and C'. A compound of the formula (J-ep), or a 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, trifluoroethylene. 1 Trifluoromethane sulfonic acid, sulfuric acid, halogenated acid (HX), trifluoroacetic acid (CF3COOH), nitric acid (HNO3) and phosphoric acid (H3P04) ) The group formed. Hardener and flame retardant resin The present invention discloses a hardener comprising a compound of the formula (1) as described above or a mixture thereof, wherein A of the compound is -OH or -OCH3, and B and C' are each selected from -OH, a group consisting of -NH2, -OR, -NHR and -NR2, wherein R is a CfCe alkyl group. The invention also discloses a flame retardant resin (including an epoxy resin and a cyanate ester), 140534.doc -16- 201100444, which comprises a former test [> 4 λ Λ 〇 cn ^ 〇 2 〇 (5), wherein The compound A of the formula (1) is: N or -. The following is a description of the present invention, and is not intended to limit the scope of the invention. Modifications and variations are within the scope of the invention. "Examples Ο The implementation of the above related inventions can be illustrated by the following specific examples in the following flow charts. Show and we

140534.doc 17- 201100444

140534.doc 18· 201100444 Synthesis Example 1: Synthesis of Compound (A) Synthesis of organic cyclic compound DOPO, catechol, 4-hydroxyacetophenone and acid catalyst A phosphorus-based compound (A) wherein R5 is a methyl group and A, B and C' are both -OH. The synthesis steps are as follows: 5.405 g (0.025 mol) of organic cyclic phosphorus compound D0P0, 14 g (0.125 mol) of catechol, 3.405 g (0.025 mol) of 4-hydroxyacetophenone and 0.216 g of oxalic acid ( 4 wt% of DOPO), placed in a 250 ml three-neck reactor. 〇 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 added dropwise to 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. 1111-]^8 (corpse 8+) 111/^:〇&1〇〇1· for C26H2i〇5P 444.1127; anal., 445.1134, C26, H22, 05, P. Figure 1 is a phosphorus compound (A 1H NMR spectrum. Synthesis Example 2: Synthesis of Compound (B) The organic cyclic phosphorus compound D0P0, o-phenylenediamine, 4-pyridylbenzene-glycol and acid catalyst were synthesized, and R5 was synthesized into a methyl group, and A was -OH, B and C' are each a phosphorus compound (B) of -NH2. The synthesis steps are as follows: 6.45 g (0.03 mol) of organic cyclic phosphorus compound D0P0, 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 D0P0), placed in a 250 ml three-neck reactor. Next, the reaction temperature was raised to 130 ° C, and after stirring for 24 hours, the stirring was stopped: mixing. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then dropped into 140534.doc -19- 201100444

It was precipitated in water, filtered and dried to give a dark purple powder of product (B) with a yield of about 88 %. HR-MS (FAB+) m/z: calcd. for C26H23N2O3P 442.1446; anal., 443.1476, C26, H24, N2, 03, P. Fig. 2 is a 1H NMR spectrum of the phosphorus compound (B). Synthesis Example 3: Synthesis of Compound (C) Using an organic cyclic phosphorus compound D0P0, 2-aminophenol, 4-p-acetophenone and an acidic catalyst, R5 is synthesized as a methyl group, and A is - OH, B and C' are a phosphorus-based compound (C) of -OH and -NH2, respectively. 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. (DOP 4 wt. /.), placed in a 250 ml three-neck reactor. Subsequently, 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 added dropwise to water to precipitate, filtered and dried to give the product (C) in a yield of about 92%. 1^11-MS(FAB + ) m/z: calcd· for C26H22NO4P 443.1286; anal., 444.1345, C26, H23, N, 04, P. Synthesis Example 4: Synthesis of compound (D) with organic cyclic compound DOPO, resorcinol, 4-hydroxyacetophenone and an acid catalyst, a phosphorus compound (D) in which R5 is a methyl group and A, B and C' are both -OH. 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 grass 140534.doc -20- 201100444 0.432 g of acid (4 wt% of DOPO), placed in a 250 ml three-neck reactor. Subsequently, the reaction temperature was raised to 130 ° C, and the reaction 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 poured out in human water, 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 C26H2105P 444.1127; anal·, 445.1107, C26, H22, 05, P, Fig. 3 is a 1H NMR spectrum of the phosphorus compound (D). Synthesis Example 5: Synthesis of Compound (E) The organic cyclic phosphorus compound DOPO, m-phenylenediamine, 4-hydroxyacetophenone, and an acid catalyst were used, and the synthetic ruler 5 was a methyl group, and A was - OH, B and C' are each a phosphorus compound (E) of -NH2. The synthesis steps are as follows: 8.85 g (0.04 mol) of organic cyclic phosphorus compound DOPO, 1.63 g (0.2 mol) of m-phenylenediamine 2, 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 the reaction was stopped for 24 hours, and then the stirring was stopped. The reactor was cooled to room temperature, dissolved in a small amount of ethanol, and then added dropwise.

It was precipitated in water, filtered and dried to give a brown powder of product (E) with a yield of about 89 %. HR-MS(FAB+) m/z: calcd. for C26H23N2O3P 442.1446; anal., 443.1453, C26, H24, N2, 03, P. Synthesis Example 6: Synthesis of Compound (F) with Organic Cyclic Phosphorus Compound DOPO, 3 -Aminophenol, 4-hydroxyacetophenone and an acidic catalyst, synthesizing a phosphorus compound in which r5 is a methyl group, A is -OH, and B and C' are -OH and -NH2, respectively (F) . 140534.doc -21- 201100444 The synthesis steps are as follows: 6.3 g (0.029 mol) of organic cyclic phosphorus compound DOPO, 15.8 g (0.15 mol) of 3-amine benzene, 3.97 g of 4-phenylacetophenone (0.029 mol) and 0.252 g of oxalic acid (4 wt% of DOPO) were placed in a 250 ml three-neck reactor. Subsequently, 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 added dropwise to water to precipitate a white powder of the product (F), which was about 89%. HR-MS (FAB+) m/z: calcd. for C26H22N04P 443.1286; anal., 444.1273, C26, H23, N, 04, P. Fig. 4 is a 1H NMR spectrum of the phosphorus compound (F). Synthesis Example 7: Synthesis of Compound (G) Organic cyclic phosphorus compound DOPO, catechol, 4-hydroxybenzoic acid

(4-hydroxybenzaldehyde) and an acidic catalyst, a phosphorus compound (G) in which R5 is hydrogen and a, B and C' are both -OH. 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. Then, the reaction temperature is raised to 13 (TC, the reaction is stopped after 24 hours of maintaining the reaction. The reactor is cooled to room temperature, dissolved in a small amount of methanol, and then dropped into water to precipitate, filtered and dried to obtain a product (G). , yield 75%, melting point 173 ° C. HR-MS (FAB+) m / z: calcd · for C25H1905P 430.097; anal., 431.0982, C25, H20, 05, P_ Figure 5 is a phosphorus compound (G) 1H NMR spectrum. Synthesis Example 8: Synthesis of Compound (H) 140534.doc -22- 201100444 Synthesis of <Hydrogen, A, with organic cyclic phosphorus compound DOPO, o-phenylenediamine, 4-hydroxybenzaldehyde and ruthenium catalyst The phosphorus compound (H) which is -OH, B and C' are both -NH2. The synthesis procedure is as follows: 9.05 g (0.042 mol) of organic cyclic phosphorus compound DOPO and 22.7 g of o-phenylenediamine (〇·21) Mohr), 4-hydroxybenzaldehyde 5.124 g (〇.〇4 mol) and oxalic acid 0.362 g (4 wt% of DOPO) were placed in a 250 ml three-neck reactor. Next, the temperature of the sublimation reaction reached 13 ° ° C, after the reaction is maintained for 24 hours, the mixing is stopped. The reactor is cooled to room temperature, dissolved in a small amount of methanol, and then dropped into water to precipitate, filtered and dried to produce (H), Yield 74 % ^ HR_ MS (FAB+) m/z: calcd. for C25H21N2 〇3P 428.129; anal., 429.1281, C25, H22, N2, 03, P. Synthesis Example 9: Compound (I) Synthetic with organic cyclic phosphorus compound DOPO, 2-aminophenol, 4_ thiophene oxime and acid catalyst, synthesize R5 as hydrogen, A is -OH, B and C' are the scales of -OH and _NH2, respectively. The compound (1) is synthesized as follows: · The organic cyclic compound DOPO 7·56 g (〇.〇348 mol), 2-aminobenzene, 18.96 g (0.18 mol), 4-hydroxybenzaldehyde 4.248 G (0.03 48 mol) and 0.3024 g of oxalic acid (4 wt% of DOPO) were placed in a 250 ml three-neck reactor. Next, the reaction temperature was raised to 180 ° C. The reaction was stopped after 24 hours of maintaining the reaction. Cool to room temperature, add a small amount of methanol to dissolve, and then drip into water to precipitate, filter and dry to obtain product (I), yield 73%. HR-MS (FAB+) m/z: calcd. for C25H2〇N04p 429.1130; anal., 430.1234, C25, H21, N, 04, P. 140534.doc -23· 201100444 Synthesis Example ίο: Synthesis of Compound (J) with Organic Cyclic Phosphorus Compound DOPO, Resorcinol, 4-Hydroxyl Benzaldehyde and acidity As the catalyst, a phosphorus-based compound (J) in which R5 is hydrogen and A, B and C' are both -OH is synthesized. 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 streptophenol, 6.11 g (0.05 mol) of 4-hydroxybenzaldehyde and 0.432 g of oxalic acid. (4 wt% of DOPO), placed in a 250 ml three-neck reactor. Then, the reaction temperature was raised to 130 ° C, and the reaction was stopped after the reaction was maintained for 24 hours. The reactor was cooled to room temperature, added with a small amount of decyl alcohol, 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 C25H1905P 430.097. anal., 431.0911, C25, H20, 05, P. Fig. 6 is a 1H NMR spectrum of the phosphorus compound (J). Synthesis Example 11: Synthesis of Compound (K) The organic cyclic compound DOPO, m-phenylenediamine, 4-perbenzylbenzene and acid catalyst 'synthesized Rs to hydrogen, A was -OH, B and C, both Is a dish compound (K) of -NH2. The synthesis steps are as follows: 8.85 g of organic cyclic lining compound DOPO, 21..〇4 mol, m-phenylenediamine 21.63 g (0.2 mol), 4-hydroxybenzaldehyde 4.88 g (0.04 mol) and oxalic acid 0.346 g (4 wt% of DOPO) was placed in a 250 ml three-neck reactor. Then 'increasing the reaction temperature to 13 (TC, stirring was stopped after 24 hours of maintaining the reaction. 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 obtain a product, yield 78 140534.doc 201100444 MS(FAB+) m/z: caicd. for C25H21N203P 428.129; anal., 429.1271, C25, H22, N2, 03, P. Synthesis Example 12: Synthesis of Compound (L) with Organic Cyclic Phosphorus The compound DOPO, 3-aminophenol, 4-hydroxybenzene disk and acid catalyst 'synthesize R_5 as hydrogen, A is -OH, B and C are phosphorus compounds (L) of -OH and -NH2, respectively. The synthesis procedure is as follows: 6.3 g (0.029 mol) of organic cyclic compound DOPO, 15-8 g (0.15 mol) of 3-aminophenol, 3.54 g (0.029 mol) of 4-hydroxybenzaldehyde and bismuth oxalate. 252 g (4 wt% of D〇p〇) was placed in a 250 ml three-neck reactor. Then 'the reaction temperature was raised to 13 ° C, and the reaction was stopped for 24 hours. The reactor was cooled to room temperature. , adding a small amount of methanol to dissolve, and then dropping into water to precipitate, filtering and drying to obtain the product (L), the yield of 78% 〇 1 ^ _ MS (FAB +) m / z; caicd. f〇r c25H20NO4P 429.1130; anal., 430.1159, C25, H21, N, 04, P. Synthesis Example 13: Synthesis of Compound A_ep q The compound A-ep was synthesized from the phosphorus compound (A). The synthesis procedure was as follows: 178 g of phosphorus was taken. The compound (A) and 74 g of epichlorohydrin are added to the ^ liter reactor, and after stirring under normal pressure to form a homogeneous mixed solution, the reaction temperature is raised to (10) under an absolute pressure of 19 〇 mmHg and is divided into 々 hours. 200 grams of 20% sodium hydroxide solution was added in batches, and the water in the reactor was azeotroped simultaneously. After the reaction, the cyclopropane and the solvent were distilled to reduce the net by vacuum distillation. The base network and deionized water are dissolved, the sodium chloride in the resin is washed, and the solvent is distilled off under reduced pressure to obtain a white epoxy-containing A-ep having an epoxy equivalent of 2〇4 g/eq. -25- 201100444 Synthesis Example 14: Synthesis of Compound A-cy Spear] Compound A-cy was synthesized using the compound (A). The synthesis procedure was as follows: Anhydrous propylene (70 g) was added to a three-neck reactor. After the reactor was cooled to _15 ° C, add cyanogen bromide (BrCN) 10.804 g (0.102 mol) and stir At the same time, the temperature is lowered to _25. 〇. In addition, 133 g (〇〇3 mol) of the lanthanide compound (A) and triethylamine (Triethylamine, Et3N) 9.198 g (0.0909 mol) are thoroughly mixed and dissolved. After a dry acetone (100 g), the reactor was slowly dripped into the reactor, and the temperature was maintained at _ 3 〇 C ' for 2 hours. When the reaction temperature returns to _3 〇. In the case of hydrazine, 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 . The organic phase was collected and dried over anhydrous magnesium sulfate. After removing magnesium sulfate, CH 2 CI 2 was removed by a rotary evaporator at room temperature to obtain cyanate vinegar (Cyanate is called a solid. Synthesis Example 15: Synthesis of Compound D-ep Synthesis of Compound D by Phosphorus Compound (D) Ep. The synthesis steps are as follows: Take 222 grams of phosphorus compound (D), 925 grams of epigas oxide into a 3 liter reactor, stir to a homogeneous mixed solution under normal pressure, and then raise at 19 〇mmHg absolute pressure. The reaction temperature is up to 7〇t and 200g of 20% sodium hydroxide solution is added in batches within 4 hours, and the water in the reactor is simultaneously azeotropically distilled out after the reaction. After the reaction, the cyclopropane and the solvent are distilled by vacuum distillation. The steaming hall is clean. The product is dissolved in methyl ethyl ketone and deionized water, the sodium vaporized in the resin is washed, and the solvent is distilled off under reduced pressure to obtain a white epoxy-containing D-ep. The epoxy equivalent is 204 g/eq. 140534.doc •26- 201100444 Synthesis Example 16: Synthesis of Compound D-cy Compound D-cy was synthesized using phosphorus compound (D). The synthesis procedure was as follows: Add anhydrous acetone (70 g) to three necks In the reactor. After cooling the reactor to -15 ° C, add BrCN 7.2027 g (0.068 mol) and stir while reducing the temperature to below -25 ° C. Another 8.89 g (0.02 mol) of phosphorus compound (D) and Et N N 6.1321 g (0.0606 mol) After thoroughly mixing and dissolving in anhydrous acetone (100 g), slowly drip into the reactor 以 with a feed funnel and the temperature was maintained at -3 ° C, and the reaction was maintained for 2 hours. When the reaction temperature returned to -30 C, The reaction liquid is washed into deionized water to remove the brominated sulphate salt. After filtration, the obtained precipitate is extracted with CH2C12/H20. The organic phase is collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the chamber is removed. The CHWh was removed by a rotary evaporator under temperature to obtain 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 procedure was as follows: 194 g of the phosphorus-based compound (G) and 833 g of epichlorohydrin were placed in a 3 liter reactor, and after stirring under normal pressure to form a homogenous mixed solution, the reaction temperature was raised to 7 Torr under an absolute pressure of 19 〇 mmHg. 〇 and add 200 grams of 20% sodium hydroxide in batches within 4 hours The liquid is added simultaneously and the water in the reactor is azeotropically distilled off. After the reaction, the chloropropanol is burned and the solvent is distilled off by vacuum distillation. The product is dissolved in methyl ethyl ketone and silk water, and the resin is washed with water. The sodium chloride was distilled off by distillation under reduced pressure to obtain a white epoxy group-containing G-ep having an epoxy equivalent of 200 g/eq [140534.doc •27·201100444 Synthesis Example 18: Compound G- The synthesis of cy uses the compound (G) to synthesize the compound G-cy. The synthesis procedure was as follows: Anhydrous acetone (70 g) was added to a three-neck reactor. The reactor was cooled to -15. After C, add 5.402 g (0.051 mol) of BrCN and mix it while reducing the temperature to -25. 〇The following. Further, 6.455 g (〇_〇15 mol) of the phosphorus compound (G) and EtaN 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 -3 0 C, the reaction was dropped into deionized water to wash to remove the brominated salt. After filtration, the resulting precipitate was extracted with CH 2 Cl 2 /H 2 . The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, c^c!2 was removed by a rotary evaporator at room temperature to obtain a cyanate ester solid. Synthesis Example 19 Synthesis of Compound j_ep The compound j_ep was synthesized from the phosphorus compound (j). The synthesis steps are as follows: 215 g of phosphorus compound (J) and 925 g of epigas oxide are added to a 3 liter reactor, stirred at a normal pressure to form a homogeneous mixed solution, and then the reaction temperature is raised at an absolute pressure of 19 〇 mmHg. To 7 Torr, 200 g of 20% sodium hydroxide solution was added in portions over 4 hours, and the water in the reactor was simultaneously azeotropically distilled off. After the reaction, the cyclopropane and the solvent are distilled off by vacuum distillation. The product is dissolved in methyl ethyl ketone and silk water, the sodium carbonate in the resin is washed, and the solvent is distilled off under reduced pressure to obtain a white color. The epoxy group-containing J-ep' epoxy equivalent is 200 g/eq. 140534.doc -28- 201100444 Synthesis Example 20: Synthesis of Compound J-cy Compound J-cy was synthesized using a 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. In addition, 8.606 g (0.02 mol) of phosphorus compound (J) and Et3N 6.1321 g (〇·〇6〇6 mol) were thoroughly mixed and dissolved in anhydrous acetone (100 g), and then slowly dropped into the feed funnel. In the reactor 'and the temperature was maintained at -30 ° C, the reaction was maintained for 2 hours. When the reaction temperature was returned to -30 ° C, the reaction was dropped into deionized water for washing to remove the bromine I salt. After the transition, the resulting sediment was extracted with CH2Cl2/H2. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH2C12 was removed by a rotary evaporator at room temperature to obtain a cyanate ester solid. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1H NMR spectrum of the compound of the formula (A). Figure 2 is a 1H NMR spectrum of the compound of the formula (Β).

Q Figure 3 is a 1H NMR spectrum of the compound of formula (D). Figure 4 is a 1H NMR spectrum of the compound of formula (F). Fig. 5 is a chart of the H NMR spectrum of the compound of the formula (G). Figure 6 is an iHNMR 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 those skilled in the art based on the present disclosure are also intended to be within the scope of the present invention. 140534.doc -29-

Claims (1)

201100444 VII. Patent application scope: i· A phosphorus compound such as general formula (1), (1) R!~I are each selected from the group consisting of hydrogen, Ci~C0 alkyl, nitro, amine and halogen atoms; A is selected from -OH, -〇ch3, -OCN and -0 a group of 6 and <:: each selected from the group consisting of -OH, -NH2, -OCN, -, 0R, -NHR, and -NR_2 (wherein r is Cl~C:6 alkyl); and Rs It is selected from the group consisting of hydrogen, c丨~Ce alkyl, C3~Ce cycloalkyl, phenyl and/or fluorene. 3. The compound of claim 1, wherein R and R4 are each a hydrogen atom, & is a methyl group, (), A, B and C1 are simultaneously _OH, and the compound of formula (1) is a formula (μι) ; Η (μρ3) 140534.doc 201100444 (b) When A is -〇H, B disk c丨 rsi ni xttt ” L gate is ·ΝΗ2, the compound of formula (1) is of formula (ΜΡΑ2); or (4) When Α is -〇Η' Β and C, respectively, rhyme and _丽2, the compound of formula (1) is formula (MP2A); or (MP2A) (4) When A, B and c are simultaneously, the compound of the formula (1) is of the formula (MP3-EP); (MP3-EP) (e) When A, B and C are simultaneously _〇cn, the compound of formula (1) is of formula (mP3-CY) 140534.doc 201100444 (MP3-CY) ο3. The compound of claim 2, wherein Ri~R4 are each a hydrogen atom, ι is a methyl group, and, (a) when A, B and C are simultaneously _0H, the formula (Μ) 3) the compound may be a compound of formula or a compound of formula (D); or Can be a compound of formula (B) or a compound of formula (E); or The compound may be a compound of formula (C) or a compound of formula (F); or 140534.doc 201100444 OH (4) when A, B and C are simultaneously an o-c2", the compound of the formula (MP3-EP) may be a compound of the formula (A-ep) or a compound of the formula (D-ep); 〇 (e) When A, Β and C· are simultaneously -OCN, the compound of the formula (MP3-CY) may be a compound of the formula (A-cy) or a compound of the formula (D-cy). (A-cy) (D-cy) A compound as claimed in claim 1, wherein R1 to R4 are each a hydrogen atom, & is a hydrogen atom, (4) when A, B and C are simultaneously -0H, and the compound of the formula (1) is a formula (3) ; or 140534.doc -4- 201100444 (b) when A is -OH, B and C1 are simultaneously captured 2, and the compound of formula (1) is of formula (ΗΡΑ)); or 〇 (ΗΡΑ2) (C) Α is -OH, Β and C' are _〇Η and _ΝΗ2, respectively, and the compound of formula (1) is of the formula (ΗΡ2Α); or Η (HP2a), the compound of formula (i) is of formula (d) when A, B and C' are simultaneously (HP3-EP); (ηρ3-ερ) 140534.doc 201100444 is a formula (HP3-(e) W A 'B and C' are simultaneously -OCN, the compound of formula (1) CY) Ocn H 〇CN (HP3-CY) 5. The compound of claim 4, wherein R and R4 are each a hydrogen atom, and R<subunit is a hydrogen source (4), although VIII and b' are simultaneously _〇h, the formula (d) The compound may be a compound of formula (6) or a compound of formula (J); or Compound (H) or formula (κ) OH Compound; or The NH 2 compound may be a compound of the formula (1) or a compound of the formula (L); 140534.doc 201100444 OH is a compound of the formula (G-ep) or a compound of the formula (j_ep); or 〇 (G-cy) compound or formula (j_cy) compound 〇 6. A process for preparing a compound of the formula (1) according to claim 1, which comprises reacting an organic scale 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; > R3 〇=Ρ-ο I Η (2) (3) (4) 140534.doc 201100444 Its "1~R4, A, B, C, and R5 are defined in the request item: month 6: The method of item 6 where R1 to R4 are argon atoms, Including, 5 is methyl, A, B and c, and when it is _OH, the formula (7) 9, 1 〇 _ 2 9-oxa-10-phosphaphenanthrene-10-oxide (D0P0), formula (3) 4. The compound of formula (4) or the formula (2) 9,1 〇-dihydro -9-oxa-1 〇 _ phenanthrene phenanthrene can be formed by the acetophenone ketone, the formula (4) phthalic acid and the acidic catalyst. 〇_Oxide (PO) Formula (3) 4·Hydroxyacetophenone 'Formula (4) Resorcinol and Acid Catalyst to form compound of formula (D); or, (8) When K is sulfhydryl, #_〇H , B and c, at the same time _ 丽 2, will be the formula (2) 9, 10 - dihydro _9_ oxa-10-10 phenanthrene-10-oxide (DOPO), formula (3) 4-hydroxy stupid Ethyl ketone, formula (4) o-phenylenediamine and acidic catalyst to form compound of formula (B), or formula (2) 9,1 〇_dihydro·9_oxa-1〇_phosphine _ι〇_ Oxide (D〇P〇), formula (3) 4-hydroxyphenylacetamidine, m-phenylenediamine and an acid catalyst to form a compound of the formula (或); or (4) when the ruler 5 is a methyl group, ΑΛ_〇Η, 3 and <:' are ^^ and ... respectively, when the formula (2) 9 , 1〇-dihydro_9_oxa_10_phosphaphenanthene oxide (DOPO), formula (3) 4-hydroxy acetophenone, formula (4) 2-aminophenol and acid catalyst Producing a compound of the formula (C), or a formula (2) 9, an oxime-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (D0p0), a formula (3) 4-hydroxyacetophenone, Formula (4) 3-aminophenol and an acidic catalyst to form a compound of formula (F); or (4) when & is a hydrogen atom, Α, Β and c, and _〇η, formula (2) 9,10 - Diterpenoid-9-oxa-10-phenanthrene-10-oxide (D〇p〇), formula (3) 4-hydroxybenzaldehyde, formula (4) catechol and acid catalyst formation formula ( G) a compound, or a compound of the formula (2) 9,10-difluoren-9-oxa-ίο·phosphphenyridin-1-140534.doc 201100444 oxide (DOPO), formula (3) 4-hydroxybenzaldehyde, Formula (4) Resorcinol and an acidic catalyst to form a compound of formula (J); or 0) when & is a hydrogen atom, A is -〇H, B and c, and at the same time _Nh2, formula (2) 9,1〇-dihydro_9_oxa-1〇_phosphaphenanthene·1〇_oxide (D〇p〇), formula (3) 4-hydroxybenzaldehyde, formula (4) o-phenylenediamine and Acidic catalyst to form compound of formula (H), or formula (2) 9,1 〇_dihydrogen _9_oxax〇-phosphonium _ 10-oxide (DOPO), formula (3) 4-hydroxybenzofural, formula (4) m-phenylenediamine and acidic catalyst-forming compound; or (0 R5 is a hydrogen atom 'Α is -OH, Β and c' are respectively %, and the formula (2) 9,10-dihydro-9-oxa-10-10 phenanthrene quinone oxide (DOPO), (3) 4-hydroxybenzaldehyde, a compound of the formula (4) 2-aminophenol and an acidic catalyst to form a compound of the formula (I), or a compound of the formula (2) 9, 1 quinone dihydro-9_oxa-10-phosphine Phenanthrene-10-oxide (D0P0), formula (3) 4-hydroxybenzaldehyde, formula (sentence 3-aminophenol and acid catalyst formation formula (1〇 compound). 8. The method of claim 7, further comprising, (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 The product of formula (A-ep) with C' is -〇-c2i\, or the compound of formula (A) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form A, B and C. 'A-cy compound as -OCN; or (h) repeating step (a), first preparing a compound of the formula, and then reacting the compound of formula (D) with epoxy chloropropane to form A, B The product of formula (D-ep) with C' is -〇-, or the compound of the formula is cyanate-esterified with cyanogen bromide and triethylamine to form 140534.doc 201100444 A, B and C' a compound of the formula (D-cy) of -OCN; or (i) repeating the step (d), first preparing a compound of the formula (G), and then reacting the compound of the formula (G) with an epoxidized solvent to form A, a compound of formula (G-ep) wherein B and C' are - or a compound of formula (G) is cyanate-esterified with cyanogen bromide and triethylamine in a solvent to form A, B and C'- OCN product (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 as one 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·-OCN (J- Cy) compound. 9. 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 sulfhydryl yellow. Methanesulfonic acid, trifluoromethane sulfonic acid, sulfuric acid, halogenated acid (HX), trifluoroactic acid (CF3COOH), nitric acid (HN〇3) And a group of phosphoric acid (H3PO4). 10. A hardener comprising a compound of formula (1) according to claim 1 or a mixture thereof, wherein A of the compound is -OH or -OCH3, and B and C' are each selected from -OH, -NH2, - a group consisting of OR, -NHR and -NR2, wherein R is an alkyl group. A flame retardant resin comprising the compound of the formula (1) according to claim 1, wherein A of the compound of the formula (1) is -OCN or one, and B and C' are each -00 Å. 140534.doc -10-