PREPARATION METHOD OF PHOSPHAPHENANTHRENE-STRUCTURE REACTIVE FLAME RETARDANT AND APPLICATION THEREOF

Abstract

Disclosed are a phosphaphenanthrene-structure reactive flame retardant and an application thereof. The preparation method comprises: enabling 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), p-hydroxy benzaldehyde (4-HBA), and 5-aminomethyl-1,3-diphenyl-1,3,5-diphosphonitryl heterocycles to react under a certain condition to obtain the reactive flame retardant with a benzene ring rigid structure containing polyhydroxy. Compared with an ordinary flame retardant, the phosphaphenanthrene-structure reactive flame retardant has the characteristics that polyfunctionality is achieved, the molecular structure is stable, the hydrolysis resistance is better, and less migration in epoxy resin, moreover, the flame retardant property of the epoxy resin can be remarkably improved.

Claims

1. (canceled)

2. (canceled)

3. A preparation method of the phosphaphenanthrene-structure reactive flame retardant ##STR00003## comprising the steps: under the protection of nitrogen, the reactant 5-aminomethyl-1,3-diphenyl-1,3,5-diphosphonitryl heterocycle, 4-hydroxybenzaldehyde, DOPO and solvent are sequentially added to a vessel, and then p-toluene sulfonic acid is added as a catalyst, the mixture is heated and react for a period of time, a pale yellow solution is obtained, the solvent is removed by concentration, and the crude product is separated by column chromatography to obtain the phosphaphenanthrene-structure reactive flame retardant; wherein, the molar ratio of the 5-aminomethyl-1,3-diphenyl-1,3,5-diphosphonitryl heterocycle, 4-hydroxybenzaldehyde, DOPO is 1:2-6:3-7; the use amount of the catalyst p-toluene sulfonic acid is 1%-10% of the mass fraction of the 5-aminomethyl-1,3-diphenyl-1,3,5-diazophosphorus heterocycle; the solvent is toluene, the reaction temperature is 100-180, the reaction time is 8-20 h.

4. The preparation method of the phosphaphenanthrene-structure reactive flame retardant according to claim 3, wherein the molar ratio of the 5-aminomethyl-1,3-diphenyl-1,3,5-diphosphonitryl heterocycle, 4-hydroxybenzaldehyde, and DOPO is 1:3-5:4-6.

5. The preparation method of the phosphaphenanthrene-structure reactive flame retardant according to claim 3, wherein the use amount of the catalyst p-toluene sulfonic acid is 2%-8% of the mass fraction of the 5-aminomethyl-1,3-diphenyl-1,3,5-diazophosphorus heterocycle.

6. The preparation method of the phosphaphenanthrene-structure reactive flame retardant according to claim 3, wherein the solvent is toluene, the reaction temperature is 120-160 C., the reaction time is 10-16 h.

7. The preparation method of the phosphaphenanthrene-structure reactive flame retardant according to claim 3, wherein the column chromatography is performed by using 300-400 mesh silica gel as the stationary phase, ethyl acetate:petroleum ether volume ratio=4:1 as the mobile phase, and 5 ml of glacial acetic acid is added to every 100 mL of the eluent.

8. (canceled)

9. A preparation method of flame retardant polymer material, comprising the following steps: epoxy resin prepolymer is taken, heated to a certain temperature, stirred, a certain mass fraction of the phosphaphenanthrene-structure reactive flame retardant according to claim 3 is added, stirred until the mixture is uniformly transparent, then, a curing agent is added by stoichiometric ratio, poured into an aluminum mould after the curing agent is completely dissolved, then a curing procedure is set to cure the mixture, and a flame retardant epoxy resin is obtained.

10. The preparation method of flame retardant polymer material according to claim 9, wherein epoxy resin prepolymer is taken, heated to 85-100 C., stirred for 20-40 min; the mass fraction of the phosphaphenanthrene-structure reactive flame retardant added is 1-30%, and continue to be stirred for 40-80 min; the curing procedure is at 120-130 C. for 4 h, continue to be kept at 130-150 C. for 2 h, and finally kept at 150-170 C. for 2 h.

Description

DRAWINGS

[0023] FIG. 1 shows the nuclear magnetic hydrogen spectrum of the flame retardant in embodiment 1.

[0024] FIG. 2 shows the nuclear magnetic phosphorus spectrum of the flame retardant in embodiment 1.

DETAILED DESCRIPTION

[0025] The present invention is further described below by means specific embodiments.

Embodiment 1

[0026] 2.16 g (0.01 mol) of DOPO, 0.732 g (0.006 mol) of 4-HBA, 0.722 g (0.002 mol) of substance I were added in a three-neck flask respectively, 0.0864 g (the mass fraction relative to substance I is 4%) of p-toluene sulphonic acid was added, protected by nitrogen, heated to 130 C., and magnetically stirred for 12 h. After completion of the reaction, silica gel was used as stationary phase, ethyl acetate:petroleum ether=4:1 as eluent, 5 mL of glacial acetic acid was added to every 100 mL of the eluent, and the product was separated by column chromatography.

[0027] The NMR spectra were shown in FIG. 1 and FIG. 2.

Embodiment 2

[0028] 2.592 g (0.012 mol) of DOPO, 0.732 g (0.006 mol) of 4-HBA, 0.722 g (0.002 mol) of substance I were added in a three-neck flask respectively, 0.0864 g (the mass fraction relative to substance I is 4%) of p-toluene sulphonic acid was added, protected by nitrogen, heated to 130 C., and magnetically stirred for 16 h.

[0029] After completion of the reaction, silica gel was used as stationary phase, ethyl acetate:petroleum ether=4:1 as eluent, 5 mL of glacial acetic acid was added to every 100 mL of the eluent, and the product was separated by column chromatography.

Embodiment 3

[0030] 2.592 g (0.012 mol) of DOPO, 0.976 g (0.008 mol) of 4-HBA, 0.722 g (0.002 mol) of substance I were added in a three-neck flask respectively, 0.0864 g (the mass fraction relative to substance I is 4%) of p-toluene sulphonic acid was added, protected by nitrogen, heated to 130 C., and magnetically stirred for 16 h. After completion of the reaction, silica gel was used as stationary phase, ethyl acetate:petroleum ether=4:1 as eluent, 5 ml of glacial acetic acid was added to every 100 mL of the eluent, and the product was separated by column chromatography.

Embodiment 4

[0031] 2.592 g (0.012 mol) of DOPO, 0.732 g (0.006 mol) of 4-HBA, 0.722 g (0.002 mol) of substance I were added in a three-neck flask respectively, 0.0864 g (the mass fraction relative to substance I is 4%) of p-toluene sulphonic acid was added, protected by nitrogen, heated to 130 C., and magnetically stirred for 16 h. After completion of the reaction, silica gel was used as stationary phase, ethyl acetate:petroleum ether=4:1 as eluent, 5 mL of glacial acetic acid was added to every 100 mL of the eluent, and the product was separated by column chromatography.

[0032] The preparation of the pure epoxy resin and modified epoxy resin with the flame retardant, and the procedures of the fire retardant tests were as follows:

[0033] (1) Preparation of Pure Epoxy Resin

[0034] 20 g of epoxy resin E-51 was taken, heated to 100 C., 4 g of curing agent 4,4-diaminodiphenylmethane was added, stirred well, poured into a mould, heated at 120 C. for 4 h, then kept at 140 C. for 2 h, and finally kept at 160 C. for 2 h.

[0035] (2) Preparation of Reactive Flame Retardant-Modified Epoxy Resin

[0036] 20 g of epoxy resin E-51 was taken, heated up to 100 C., 2.13 g of the flame retardant (the mass of the phosphorus element was 1% of the mass of the epoxy resin, the following addition amount of flame retardant was based on the mass of phosphorus element), after stirred and dissolved, the small molecular substance were removed under vacuum, 4 g of curing agent 4,4-diaminodiphenylmethane was added, stirred well, poured into the mould, kept at 120 C. for 4 h, then kept at 140 C. for 2 h, finally, kept it at 160 C. for 2 h, and the reactive flame retardant-modified epoxy resin was obtained. According to this method, modified epoxy resin was prepared by adding 6.39 g and 10.66 g of the flame retardant (corresponding phosphorus content was 3% and 5% respectively) to 20 g of epoxy resin respectively.

[0037] (3) The limiting oxygen index of the obtained sample was tested according to the method of GB/T 2406.2-2009.

[0038] The results of the limiting oxygen index test were shown in Table 1.

TABLE-US-00001 TABLE 1 The results of the limiting oxygen index for the epoxy resins modified with different content of phosphorus Phosphorus Control content group 1% 3% 5% Oxygen index 26.3 32.2 36.2 38.4 (LOI)

[0039] As mentioned above, these are only preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly. That is, the equivalent changes and modifications made according to the patent scope and description content of the present invention should still be within the scope of the present invention.