CN105295092B - A kind of phosphorous, nitrogen luxuriant molysite fire retardant and its preparation method and application - Google Patents

Abstract

The general structural formula of a class of ferrocene flame retardants containing phosphorus and nitrogen elements disclosed by the present invention is as follows: The invention also discloses the preparation method of the ferrocene salt flame retardant containing phosphorus and nitrogen elements, and the use of adding it to the light-curing epoxy resin system. The preparation process of the ferrocene salt of the present invention is simple, and the preparation process is based on the ferrocene salt containing chlorobenzene ligand as raw material, first synthesizing an imine intermediate and introducing a nitrogen-containing element group, and then combining with 9,10-dihydro-9- Oxa‑10‑phosphaphenanthrene‑10‑oxide reacts to introduce phosphorus-containing flame retardant groups. The ferrocene salt provided by the present invention not only solves the mobility of the aromatic hydrocarbon ligands removed during the photoinitiation process of the ferrocene salt as an initiator, but also serves as an additive flame retardant, and the ferrocene metal can be complexed with phosphorus and nitrogen elements. The compound has a synergistic flame retardant effect, which significantly improves the flame retardant performance of the resin added with this type of compound, and increases the amount of carbon residue.

Description

A class of ferrocene flame retardant containing phosphorus and nitrogen elements and its preparation method and use

technical field

The invention belongs to the technical field of functional metallocene compounds and their applications, and in particular relates to a class of ferrocene salts containing phosphorus and nitrogen elements, a preparation method thereof, and an application as a flame retardant for epoxy resins.

Background technique

Polymer materials are more and more widely used in daily life. However, the potential fire hazard of polymer materials cannot be ignored. Flame retardants can hinder flame combustion and reduce the generation of toxic gases and smoke. Although halogenated flame retardants have good flame retardant effects, they are gradually restricted in use due to high temperature decomposition and generation of toxic and corrosive gases such as hydrogen halides. Organic phosphorus-containing flame retardants have excellent flame retardant effects, are environmentally friendly and non-polluting, and are ideal choices for replacing halogenated flame retardants.

In the existing compound flame retardant system, intumescent flame retardant is currently recognized as an environmentally friendly and efficient flame retardant for high molecular polymers. Flame retardants containing phosphorus and nitrogen elements are a typical type of intumescent flame retardants. type flame retardant. Phosphorus and nitrogen elements have a synergistic flame retardant effect, and phosphorus and nitrogen synergistic flame retardants have better flame retardant effects than individual organic phosphorus-containing flame retardants (Polym. Degrad. Stab., 2008, 93:1037-1043; Polym. Degrad. Stab., 2011, 96:1118-1124). Phosphorus nitrogen system is flame retardant when decomposed at high temperature, non-toxic gas can dilute the surrounding oxygen and combustible gas, and in the presence of polyols, it is easy to form a high content of expanded carbon layer, which can isolate heat and oxygen and achieve flame retardant effect. Ammonium polyphosphate with high phosphorus and nitrogen content is widely used, but its water resistance, thermal stability and substrate compatibility are not good. An important means to solve the compatibility is to prepare organic phosphorus and nitrogen Elemental flame retardants, but the flame retardants developed generally have the problem of large usage.

As a halogen-free flame retardant, metal flame retardants have the advantages of non-toxicity, non-volatility, and low corrosion (Research Progress on Halogen-Free Flame Retardants. Plastic Industry, 2006, 34: 69-72.), but these inorganic flame retardants Moderate flame retardancy can only be obtained when the flame retardant is added in a relatively high amount, but the high added amount will definitely affect the processing performance and mechanical properties of the substrate, and the compatibility of the material will also be greatly reduced. It is reported in the literature that the polymer containing ferrocene structure is tested for LOI, and the LOI value of the polymer containing ferrocene structure is compared with that of the polymer not containing ferrocene structure. It is found that the LOI of the polymer containing ferrocene structure group The value is significantly improved, and the LOI value can be increased by about 5. And the TGA test of the polymer containing ferrocene structure found that the final carbon residue of the system can reach up to 72%, and the residue content is very high (React. Funct. Polym., 2007, 67, 883-892). There are also literature reports that ferrocene compounds can reduce flame propagation speed (Firesafety J., 2012, 51, 10–17; Prog. Energy Combust. Sci. 2008, 34, 288–329).

Ferrocene salt has a sandwich structure similar to ferrocene, and is a kind of ferrocene complex compound with simple synthesis method, which can be used as an initiator for thermal curing and photocuring of epoxy compounds. During the initiation process of ferrocene salts with a simple ligand structure, the removed ligands will remain in the resin and affect the performance of the resin. One of the directions to solve this problem is to endow the aromatic hydrocarbon ligands in ferrocene salts with synergistic properties with ferrocene. functionality, but there are few reports on this direction.

Contents of the invention

The invention provides a kind of ferrocene salt flame retardant of phosphorus and nitrogen elements and its preparation method, as well as the use as a flame retardant of epoxy resin. It not only provides a new way and new method for obtaining a flame retardant resin system with high flame retardancy and excellent performance, but also solves the influence of the aromatic hydrocarbon ligand of ferrocene salt on the performance of the resin.

Specifically, the present invention includes:

A class of ferrocene flame retardants containing phosphorus and nitrogen elements, characterized in that the general structural formula (I) or (II) of the ferrocene salts containing phosphorus and nitrogen elements is as follows:

wherein R ₁ , R ₂ , R ₃ are selected from: -H, -R´, phenyl, halogen, -OH, -OR´, halogenated R´, -R´COO- or -R´CONHR˝, where R´ is C1-12 alkyl or alkylene, R˝ is C1-12 alkyl;

Ar is selected from benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, carbazole or N-alkylcarbazole.

The synthesis method of the above-mentioned ferrocene salt flame retardant containing phosphorus and nitrogen elements with structural formula (I), the synthesis method is carried out as follows: react with chlorophenyl ferrocene salt and phenol with amino groups to generate structural formula (Ⅲ ) ferrocene salt; react ferrocene salt of structural formula (Ⅲ) with aryl aldehyde to generate ferrocene salt of structural formula (Ⅳ); combine ferrocene salt of structural formula (Ⅳ) with 9,10-dihydro-9-oxo Hetero-10-phosphaphenanthrene-10-oxide reacts to generate ferrocene salt containing phosphorus and nitrogen elements of structural formula (I);

wherein R ₁ , R ₃ and Ar are as defined above.

The synthesis method of the above-mentioned ferrocene salt flame retardant containing phosphorus and nitrogen elements with structural formula (II), the synthesis method is carried out according to the following steps: react with chlorophenylferrocene salt and arylboronic acid with aldehyde group to generate the structural formula (Ⅴ) ferrocene salt; react the ferrocene salt of structural formula (Ⅴ) with arylamine to generate the ferrocene salt of structural formula (Ⅵ); combine the ferrocene salt of structural formula (Ⅵ) with 9,10-dihydro-9 - Oxa-10-phosphaphenanthrene-10-oxide reacts to generate ferrocene salt containing phosphorus and nitrogen elements of structural formula (II);

wherein R ₁ , R ₃ and Ar are as defined above.

The ferrocene salts containing phosphorus and nitrogen elements of the structural formulas (I) and (II) can be used as flame retardants in epoxy resins, acrylate resins and methacrylate resins.

A light-curable epoxy resin system with flame retardancy, characterized in that the composition of the epoxy resin system in terms of mass percentage: ferrocene salt containing phosphorus and nitrogen elements with structural formula (I) or (II) : 0.5%-10%; cationic photoinitiator: 0%-5%; epoxy resin: 70-95%; reactive diluent: 4.5-30%.

The above-mentioned light-curable epoxy resin system with flame retardancy is characterized in that the epoxy resin used includes cycloaliphatic epoxy resin, bisphenol A epoxy resin and novolac epoxy resin; the reactive diluent used includes Alicyclic epoxy monomers and aliphatic epoxy monomers; cationic photoinitiators used include diaryl iodonium salts and triaryl sulfonium salts.

A light-curable acrylate resin system with flame retardancy, characterized in that the composition of the acrylate resin system in terms of mass percentage: ferrocene salt containing phosphorus and nitrogen elements with structural formula (I) or (II) : 0.5%-10%; Acrylic resin: 70-95%; N-methylpyrrolidone: 0.5%-5%; Reactive diluent: 4.5-30%.

The above flame-retardant acrylate resin system is characterized in that the acrylate resin used includes acrylate resin and methacrylate resin; the active diluent used includes acrylate monomer and methacrylate monomer.

The present invention has the following advantages:

1. Since the flame retardant provided by the invention has iron, phosphorus and nitrogen elements at the same time, it has a synergistic flame retardant function, which promotes the increase of flame retardancy and carbon residue, so that the addition amount is small and the flame retardant effect is good;

2. Since the preparation method provided by the present invention is mature and easy to operate, it is convenient for industrialized production;

3. When the ferrocene salt provided by the present invention is used for the flame retardant of epoxy resin and acrylic resin, it can not only be used as a flame retardant, but also as an initiator, which can reduce the cost and reduce the operation of adding the initiator , and improved flame retardancy

4. The ferrocene salt provided by the present invention solves the adverse effect of the aromatic hydrocarbon ligand of the ferrocene salt on the performance of the resin.

Description of drawings

Figure 1 is the H NMR spectrum of ( η ⁶ -4-(1-phenylamino-1-DOPO)methylbiphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCP).

Figure 2 is the NMR phosphorus spectrum of ( η ⁶ -4-(1-phenylamino-1-DOPO)methylbiphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCP).

Figure 3 is the H NMR spectrum of ( η ⁶ -4-(1-(4-hydroxyanilino)-1-DOPO) methylbiphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCPH) .

Figure 4 is the nuclear magnetic phosphorus spectrum of ( η ⁶ -4-(1-(4-hydroxyanilino)-1-DOPO) methylbiphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCPH) .

Figure 5 is the NMR of ( η ⁶ -4-(N-(1-phenyl-1-DOPO)methyl)aminophenoxybenzene)( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCOP) hydrogen spectrum.

Figure 6 is the NMR of ( η ⁶ -4-(N-(1-phenyl-1-DOPO)methyl)aminophenoxybenzene)( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCOP) Phosphorus Spectrum.

Figure 7 is ( η ⁶ -4-(N-(1-p-hydroxyphenyl-1-DOPO)methyl)aminophenoxybenzene)( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCOPH) NMR spectrum.

Figure 8 is ( η ⁶ -4-(N-(1-p-hydroxyphenyl-1-DOPO)methyl)aminophenoxybenzene)( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCOPH) NMR spectrum.

Synthetic example

Example 1 Flame retardant ( η ⁶ -4-(N-(1-p-hydroxyphenyl-1-DOPO) methyl) aminophenoxybenzene) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate Synthesis of FCOPH

The synthesis process is shown in the following formula:

Add ( η ⁶ -chlorobenzene) ( η 5 -cyclopentadiene) iron hexafluorophosphate (Fc-Cl) 20g (0.026mol), 4-aminophenol 7g (0.032mol), potassium carbonate in a 250ml round bottom flask 10g (0.036mmol), 120ml of N,N-dimethylformamide, react at room temperature (25°C) in the dark, and monitor the reaction by TLC until ( η ⁶ -chlorobenzene) ( η ⁵ -cyclopentadiene En) iron hexafluorophosphate reacted completely. Pour the reactant into cold water, a yellow solid precipitated out, let stand, filter under reduced pressure, rinse the filter cake with ethanol three times to obtain the target compound ( η ⁶ -aminodiphenyl ether) ( η ⁵ -cyclopentadiene) Iron hexafluorophosphate, yellow solid, yield: 72%.

Add 20g (0.044mol) of (η ⁶ -aminodiphenyl ether) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate, 5.4g of p-hydroxybenzaldehyde (0.044 mmol) and 100ml N,N-dimethylformamide, protected from light, stirred at 30°C for 5 hours, then added 9.6g (0.044mol) DOPO, monitored the reaction by TLC, and the reaction was completed in 13 hours. After the reaction was completed, the reaction solution was poured into cold water, a yellow solid was precipitated, left to stand, and filtered under reduced pressure to obtain the product (yield: 79%).

(KBr) ν max (cm ⁻¹ ): 844 (PF ₆ ^- ), 921 (POC), 1236 (P=O), 1456, 1503, 1608, 1656 (Ar ring), 3107 (Ar-H), 3280 (-NH), 3407 (-OH); ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ: 4.99 (m, 1H, PCH), 5.08 (s, 5H, Cp-H), 6.09 (m, 3H, Ar-H), 6.24 (t, 2H, Ar-H), 6.73 (d, 2H, Ar-H), 6.81 (d, 2H, Ar-H), 6.96 (d, 3H, Ar-H) , 7.09 (d, 1H, Ar-H), 7.24 (d, 2H, Ar-H), 7.35 (t, 1H, Ar-H), 7.49 (t, 1H, Ar-H), 7.61 (t, 1H , Ar-H), 7.81 (t, 1H, Ar-H), 8.04 (t, 1H, Ar-H), 8.21 (m, 2H, Ar-H), 9.47 (s, 1H, -OH); ³¹ P-NMR (400 MHz, DMSO- d ₆ ) δ _ppm : 28.59; MS: m/z=626 (M+1) ⁺ .

Example 2 flame retardant ( η ⁶ -4-(N-(1-phenyl-1-DOPO) methyl) aminophenoxybenzene) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCOP )Synthesis

The synthesis process is shown in the following formula:

Add 20g (0.044mol) of ( η ⁶ -aminodiphenyl ether) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (Fc-NH ₂ ), benzaldehyde 4.7g (0.044mol) and 100ml DMF, protected from light, stirred at 30°C for 5 hours, then added 9.6g (0.044mol) DOPO, monitored the reaction by TLC, and the reaction was completed in 13 hours. After the reaction was completed, the reaction solution was poured into cold water, a yellow solid was precipitated, left standing, and filtered to obtain the target product (yield: 82%).

(KBr) ν max (cm−1): 842 (PF ₆ ^- ), 929 (POC), 1237 (P=O), 1456, 1477, 1503, 1607 (Ar ring), 3090, (Ar-H); ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ: 5.08 (s, 5H, CP-H), 5.15 (m, 1H, PCH), 6.10 (m, 3H, Ar-H), 6.25 (t, 2H, Ar-H), 6.65 (m, 1H, Ar-H), 6.84 (m, 2H, Ar-H), 6.95 (m, 2H, Ar-H), 7.08 (m, 1H, Ar-H) , 7.36 (m, 4H, Ar-H), 7.45 (m, 3H, Ar-H), 7.63 (m, 1H, Ar-H), 7.83 (m, 1H, Ar-H), 8.05 (m, 1H , Ar-H), 8.22 (m, 2H, Ar-H); ³¹ P-NMR (400 MHz, DMSO- d ₆ ) δ _ppm : 33.32; MS: m/z=610 (M+1) ⁺ .

Example 3 Flame retardant ( η ⁶ -4-(1-(4-hydroxyanilino)-1-DOPO) methyl biphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCPH) synthesis

The synthesis process is shown in the following formula:

Add 50 g (0.13 mol) ( η ⁶ -chlorobenzene) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate, 22.5 g (0.15 mol) 4-formylphenylboronic acid, 2 mol∙ L‾1 Potassium carbonate aqueous solution 100ml, tetrahydrofuran 200ml, tetrakistriphenylphosphine palladium 0.3g, under the protection of nitrogen, heat to reflux ^under the condition of avoiding light. The reaction was monitored by thin-layer chromatography, and the reaction was completed within 12 hours. After cooling, filter to remove insoluble impurities, wash the organic phase three times with water, keep the organic phase, concentrate, add methyl tert-butyl ether to the concentrated solvent, a large amount of yellow solid precipitates, filter to obtain the product, ( η ⁶ -4- Aldehyde biphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (Fc-CHO), yield 87%.

Add 20 g (0.044 mol) ( η ⁶ -4-formyl biphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (Fc-CHO) to a 250 ml round bottom flask, 4.8 g (0.044 mol) 4 -Aminophenol, add 150ml of methanol to dissolve, nitrogen protection, 50°C avoid light reaction, add 9.6g (0.044mol) DOPO after 5 hours of reaction, and monitor the reaction by thin-layer chromatography. After 8 hours, the reaction is complete, and the product precipitates out of the solution. Filtration gave the target product (yield: 86%).

(KBr) ν max (cm ⁻¹ ): 843 (PF ₆ ^- ), 928 (POC), 1232 (P=O), 1458, 1477, 1512, 1651 (Ar ring), 3103 (Ar-H), 3419 (-OH); ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ: 5.05 (s, 5H, CP-H), 5.68 (m, 1H, PCH), 6.44 (d, 3H), 6.54 (t , 2H), 6.62 (d, 2H), 6.81 (d, 2H), 7.22 (d, 1H) 7.35 (t, 1H), 7.47 (m, 2H), 7.70 (d, 2H), 7.78 (t, 1H ), 7.91 (d, 3H), 8.24 (m, 2H), 8.50 (s, 1H, -OH); ³¹ P-NMR (400 MHz, DMSO- d ₆ ) δ _ppm : 31.68; MS: m/z = 610 (M+1) ⁺ .

Example 4 Synthesis of flame retardant ( η ⁶ -4-(1-phenylamino-1-DOPO) methyl biphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (FCP)

The synthesis process is shown in the following formula:

Add 20 g (0.044 mol) ( η ⁶ -4-formyl biphenyl) ( η ⁵ -cyclopentadiene) iron hexafluorophosphate (Fc-CHO), 4.1 g (0.044 mol) aniline to a 250 ml round bottom flask , add 150ml of methanol to dissolve, nitrogen protection, 50 ℃ dark reaction, after 5 hours of reaction, add 9.6g (0.044mol) DOPO, TLC spot plate to monitor the reaction, after 8 hours, the reaction is complete, the product precipitates out of the solution, filtered to get Target product (yield: 83%).

(KBr) ν max (cm ⁻¹ ): 842 (PF ₆ ^- ), 927 (POC), 1229 (P=O), 1458, 1478, 1499, 1600 (Ar ring), 3103 (Ar-H); ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ: 5.06 (s, 5H, Cp-H), 5.33 (m, 1H, PCH), 6.45 (d, 2H), 6.54 (t, 3H), 6.76 ( d, 2H), 6.81 (d, 2H), 6.96 (m, 3H), 7.11 (m, 1H), 7.36 (m, 1H), 7.50 (m, 1H), 7.62 (d, 2H), 7.82 (m , 1H), 7.91 (d, 2H), 8.09 (m, 1H), 8.23 (m, 2H); ³¹ P-NMR (400 MHz, DMSO- d ₆ ) δ _ppm : 28.40; MS: m/z =594 (M+1) ⁺ .

The flame retardancy of embodiment 5 epoxy acrylic resin system

The test specimens used for flame retardancy in the present invention were prepared by photo-initiated curing and then thermal curing under the irradiation of a high-pressure mercury lamp (λ _max = 365 nm, I = 1 mW∙cm ^-2 ). The photoinitiators are four kinds of ferrocene salts (Fc-P) FCOPH, FCOP, FCPH and FCP with flame retardant properties prepared above and containing phosphorus and nitrogen elements. The selected resin system is epoxy acrylate prepolymer, and the structural formula of epoxy acrylate prepolymer is as follows:

The oxygen index (LOI) was measured using a JF-3 type oxygen index meter, which was tested according to the content described in GB/T 2406-1993, and the size of the sample strip was 100 mm×6.5 mm×3 mm.

Add 1wt% ferrocene flame retardant (Fc-P) containing phosphorus and nitrogen elements and excess N-methylpyrrolidone to the epoxy acrylate prepolymer, mix well, pour the resulting liquid mixture Put it into a self-made mold, use a high-pressure mercury lamp to irradiate for 10 minutes, take it out, and polish the cured product to obtain the required spline size, and obtain four cured products EA-FCOPH, EA-FCOP, EA-FCPH, EA-FCP .

The obtained solidified samples were measured by a thermal analyzer for thermal decomposition temperature and residual carbon content, and the data are listed in Table 1. The obtained cured samples were tested for oxygen index, and the data are listed in Table 2.

Comparative experiment: 1wt% of the common free radical photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) was added to the epoxy acrylate prepolymer as a comparative experiment. According to the fixed-size sample strip prepared by the method in Example 5, the obtained content is the cured product EA-TPO. The obtained cured samples were measured by a thermal analyzer for thermal decomposition temperature and residual carbon content, and the data are listed in Table 1. The obtained cured samples were tested for oxygen index, and the data are listed in Table 2.

It can be seen from Table 1 and Table 2 that for sample EA-FCPH, the oxygen index of the system reaches 25.2, the thermal decomposition temperature corresponding to 10wt% weight loss is 408°C, and the carbon residue is 16.59%. All indexes are significantly higher than the cured product EA-TPO obtained in the comparative test.

Table 1 Thermal decomposition data of EA-FCOPH, EA-FCOP, EA-FCPH and EA-FCP systems

Table 2 Flame retardant performance test results of EA-FCOPH, EA-FCOP, EA-FCPH and EA-FCP systems

The flame retardancy of embodiment 6 epoxy resin system

The selected resin systems are epoxy acrylate prepolymer and epoxy prepolymer E-51 respectively. The structural formulas of epoxy acrylate prepolymer and epoxy prepolymer E-51 are as follows:

Add 1wt% of ferrocene flame retardant Fc-P and diaryliodonium salt containing phosphorus and nitrogen to the epoxy prepolymer E-51, and Fc-P is FCOPH, FCOP, FCPH, FCP, after heating and stirring fully, mix evenly, maintain the temperature and stir until the photoinitiator is completely dissolved under the condition of avoiding light. Pour the obtained liquid mixture into a self-made mold, irradiate it with a high-pressure mercury lamp for 30 minutes, take it out, heat it in an oven to 120°C, and then cure it. Grind the cured product into a spline size to obtain cured resins EP-FCOPH, EP-FCOP, EP-FCPH, EP-FCP.

The obtained cured samples were measured by a thermal analyzer for thermal decomposition temperature and residual carbon content, and the data are listed in Table 3. The obtained cured samples were tested for oxygen index, and the data are listed in Table 4.

Comparative test: adding 3wt% of 4,4'-dimethylphenyliodonium hexafluorophosphate (IMO) to epoxy resin and adding 3wt% of 4,4'-dimethylphenyl to epoxy resin Two groups of experiments of iodonium salt hexafluorophosphate (IMO) and 1wt% I-261 were used as comparative experiments, and the sample strips were prepared according to the method of Example 6 to obtain cured products EP-IMO and EP-I-261. The obtained cured samples were measured by a thermal analyzer for thermal decomposition temperature and residual carbon content, and the data are listed in Table 3. The obtained cured samples were tested for oxygen index, and the data are listed in Table 4.

It can be seen from Table 3 and Table 4 that for the sample EP-FCPH, the oxygen index of the system reaches 21.5, the thermal decomposition temperature corresponding to 10wt% weight loss is 390°C, and the carbon residue is 18.31%. All indicators are better than the cured products EP-IMO and EP-I-261 obtained in the comparative test.

Table 3 Thermal decomposition data of EP-FCOPH, EP-FCOP, EP-FCPH and FP-FCP systems

Table 4 Flame retardant performance test results of EP-FCOPH, EP-FCOP, EP-FCPH and EP-FCP systems

Claims (4)

1. a kind of luxuriant molysite containing phosphorus, nitrogen, it is characterised in that should the luxuriant molysite general structure (I) containing phosphorus, nitrogen Or (II) is as follows：

Wherein R₁, R₂, R₃It is selected from：- H ,-R ', phenyl, halogen ,-OH ,-OR ', R ' COO-, halogenated R " or-R " CONHR ', Middle R ' is C₁-C₁₂Alkyl, R " be C₁-C₁₂Alkylidene；

Ar is selected from benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkyl anthracene, carbazole or N- alkyl carbazoles.

2. luxuriant molysite of the one kind containing phosphorus, nitrogen according to claim 1, it is characterised in that described contains phosphorus, nitrogen The synthetic method of the luxuriant molysite general structure (I) of element carries out according to the following steps：With chlorobenzene cyclopentadienyl molysite and the phenol with amino is anti- Should, the luxuriant molysite of generating structure formula (III)；By the luxuriant molysite of structural formula (III) and the cyclopentadienyl of aryl aldehyde reaction generating structure formula (IV) Molysite；The luxuriant molysite of structural formula (IV) is reacted into generating structure formula with the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies (I) the luxuriant molysite containing phosphorus, nitrogen；

Wherein R₁, R₃It is as described in claim 1 with the definition of Ar.

3. luxuriant molysite of the one kind containing phosphorus, nitrogen as described in claim 1, it is characterised in that described contains phosphorus, nitrogen member The synthetic method of the luxuriant molysite general structure (II) of element carries out according to the following steps：With chlorobenzene cyclopentadienyl molysite and the aryl boron with aldehyde radical Acid reaction, the luxuriant molysite of generating structure formula (V)；The luxuriant molysite of structural formula (V) is reacted into generating structure formula (VI) with arylamine Luxuriant molysite；The luxuriant molysite of structural formula (VI) is reacted to generation knot with the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies The luxuriant molysite containing phosphorus, nitrogen of structure formula (II)；

Wherein R₂, R₃It is as described in claim 1 with the definition of Ar.

4. it is according to claim 1 containing phosphorus, nitrogen luxuriant molysite in epoxy resin, acrylate and methyl-prop As the purposes of fire retardant in alkene acid ester resin.