Melamine-based nitrogen and phosphorus-containing compound, preparation method and application thereof, and flame-retardant epoxy resin composition of melamine-based nitrogen and phosphorus-containing compound

A melamine-based and melamine-based benzene technology is applied in the field of melamine-based nitrogen-containing phosphorus compounds and can solve the problems of flammability of epoxy resins and the like

Active Publication Date: 2021-04-20

CHINA PETROLEUM & CHEM CORP +1

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AI-Extracted Technical Summary

Problems solved by technology

[0005] Aiming at the flammability problem of existing epoxy resins, the present invention prov...

Abstract

The invention discloses a melamine-based nitrogen and phosphorus-containing compound as well as a preparation method and application thereof. The method comprises the following steps: firstly, carrying out condensation reaction on raw materials including melamine, paraformaldehyde and aromatic phenol to prepare a melamine benzoxazine intermediate, and then reacting the intermediate with DOPO to obtain the compound. The compounds are useful as flame retardants for epoxy resins. The method is cheap in raw materials, wide in source, simple in process, efficient, safe, environmentally friendly and beneficial to batch production. The flame retardant overcomes the defects that a traditional flame retardant is large in combustion smoke, pollutes the environment, is poor in compatibility, is easy to separate out and the like. When the flame retardant is added into epoxy resin, the flame retardant property of an epoxy resin cured product can be remarkably improved, and when the addition amount of P in the epoxy resin reaches 1.0 wt%, the vertical combustion grade reaches UL94 V-0 grade, the limit oxygen index is 35-40, the charring rate at 800 DEG C reaches 23-27%, and the glass-transition temperature reaches 130-137 DEG C.

Application Domain

Group 5/15 element organic compounds

Technology Topic

ParaformaldehydeFlame resistance +10

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Examples

Experimental program(3)
Comparison scheme(1)

Example Embodiment

[0038]Example 1】

[0039]R1Hydrogen atom, r2The epithanatic compound synthesis step is as follows:

[0040]7.77 g of melamine (commercially available), 12.21 g of polyformaldehyde (commercially available), 17.39 g of phenol (commercially available) added to three flasks with stirring devices, add a quantity of triethylamine (commercially available) regulation PH to 9, the reaction was carried out at a temperature of 100 ° C, and after the reaction was completed, it was vacuum to give an intermediate product; then, 19.2 g of the above intermediate and 30.24 gdopo (commercially available) (Mold the molar ratio of the intermediate and DOPO) In a three-mouth flask with a stirring device, a solvent is added to 250 g of THF, and the reaction is stirred at a temperature of 40 ° C. After the reaction is complete, the reaction is complete, the filtration washed, and the powder-shaped melamine group was obtained. Nitrogen-containing compound (a).

[0041]The test analysis results of the melamine-containing phosphorus compound (A) are as follows:

[0042]1H-NMR (PPM, DMSO-D6), δ = 4.21 (6H, -N-CH2-AR -), 4.26 (6H, -N-CH2-P -), 6.48-8.13 (39H, Aromatic H), 9.47 (OH).

[0043]13C-NMR (DMSO-D6), δ = 49.7, 50.9, 114.8, 118.6, 119.7, 121.3, 123.3, 123.6, 123.8, 128.6, 133.7, 135, 130.8, 133.7, 135.3, 148.7, 154.8 .

[0044]31P-NMR (DMSO-D6, PPM): 38.718.

[0045]FTIR (KBR): 814CM-1(Triazine Ring), 1228cm-1(P-o stretch), 1551cm-1(-C = n-stretch), 1746cm-1(C = o stretch).

[0046]The above 15 g of melamine-containing compound (A) was added to 100 parts by weight of epoxy resin E-51 (commercially available), and the curing agent 4,4'-diaminobenzyl is added, and uniform mixed by mechanical stirring, then Pour into the homemade mold. The mold is placed in a blower oven, which is heated according to the curing process of 140 ° C / 2H + 180 ° C / 2H, and the like is cooled to room temperature to obtain an epoxy resin cured product. When the cyclic oxygen-containing amount is 1.0% by weight, the vertical combustion level reaches the UL94 V-0, the ultimate oxygen index reaches 39, and the gas production rate is 27%, the glass transition temperature is 135 ° C.

[0047]The ultimate oxygen index test is implemented by the ASTM D2863 standard and is tested on the HC-2C oxygen index. The UL94 vertical combustion test is performed is the ASTM D3801 standard. The measurement of the glass transition temperature was carried out on the TA Q10 DSC instrument, the test conditions: the temperature increase rate of 10 ° C / min, the test range is 40 ° C to 200 ° C, and the nitrogen atmosphere is surrounded. The gas production rate was carried out on the Mettler TGA / SDTA851 thermal analysis instrument, and the test temperature range was 30 ° C to 800 ° C, the temperature rise rate of 20 ° C / min, and the nitrogen atmosphere was performed.

Example Embodiment

[0048][Example 2]

[0049]R1 is a hydrogen atom, and R2 is a methyl morelamine-containing nitrogen-containing compound synthesis step as follows:

[0050]7.77 g of melamine (commercially available), 12.21 g of polyformaldehyde (commercially available), 19.98 g 4-methylphenol (commercially available) was added to three flasks with stirring devices, and a certain amount of triethylamine was added dropwise. Commercially available) Adjustings pH to 9, the reaction is carried out at a temperature condition of 100 ° C, after the reaction is completed, the vacuum is dried to obtain an intermediate product; then, 20.88 g of the above intermediate and 30.24 g of DOPO (commercially available) (medium sales) The molar ratio of DOPO was 1: 3) was added to a three flask with a stirring device, and a solvent was added to 250 g of THF (commercially available), and the reaction was stirred at a temperature of 40 ° C for 24 h, and the reaction was complete, cooled, filtered to wash After vacuum drying, the powder melamine-containing compound (B) was obtained.

[0051]The test results of the melamine-containing compound (B) are as follows:

[0052]1H-NMR (PPM, DMSO-D6), δ = 2.38 (9H, -CH3), 4.10 (6H, -N-CH2-AR -), 4.18 (6H, -N-CH2-P -), 6.40-7.92 (36h, Aromatic H), 9.48 (OH).

[0053]13C-NMR (DMSO-D6), δ = 49.1, 51.2, 113.7, 117.9, 119.3, 121.8, 122.8, 123.6, 124.0, 129.0, 132.3, 134.0, 149.7, 153.7 .

[0054]31P-NMR (DMSO-D6, PPM): 37.818.

[0055]FTIR (KBR): 815CM-1(Triazine Ring), 1226CM-1(P-o stretch), 1551cm-1(-C = n-stretch), 1748cm-1(C = o stretch).

[0056]The above 15 g of melamine-containing-containing compound (B) was added to 100 parts by weight of epoxy resin E-51 (commercially available), and the curing agent 4,4'-diaminobenzyl is added, and uniform mixed by mechanical stirring, then Pour into the homemade mold. The mold is placed in a blower oven, which is heated according to the curing process of 140 ° C / 2H + 180 ° C / 2H, and the like is cooled to room temperature to obtain an epoxy resin cured product. When the epoxy curing is 1.0 wt%, the vertical combustion level reaches the UL94 V-0, the ultimate oxygen index reaches 37, and the gas production rate is 25%, and the glass transition temperature is 137 ° C.

[0057]Test methods for resin performance parameters and the methods in Example 1.

Example Embodiment

[0058][Example 3]

[0059]R1 is methyl, R2 is the methylamine-containing nitrogen-containing phosphorus compound synthesis step as follows:

[0060]7.77 g of melamine (commercially available), 12.21 g of polyformaldehyde (commercially available), 22.57 g 2,4-dimethylphenol (commercially available) added to three flasks with stirring devices, and a certain amount of three Ethylamine (commercially available) adjusted pH to 9, reacting at a temperature of 100 ° C for 8 h under stirring and 100 ° C, after the reaction, vacuum dried to give an intermediate product; then, 22.56 g of the above intermediate and 30.24 g of DOPO (commercially available) (The molar ratio of the intermediate and DOPO was 1: 3) added to a three flask with a stirring device, and the solvent 250 g THF (commercially available) was added, and the reaction was stirred at a temperature of 40 ° C for 24 h, and the reaction was complete, cool, Washing, washed with vacuum, gave a powder-shaped melamine-containing nitrogen-containing compound (C).

[0061]The results of test analysis of melamine-containing compound (C) are as follows:

[0062]1H-NMR (PPM, DMSO-D6), δ = 2.37 (9H, -CH3), 2.64 (9H, -CH3), 4.32 (6H,-CH2-AR -), 4.32 (6H,-CH2 -P -), 6.58-7.86 (33h, Aromatic H), 9.40 (OH).

[0063]13C-NMR (DMSO-D6), δ = 50.1, 50.8, 113.9, 119.2, 123.4, 124.0, 125.1, 125.8, 128.2, 111.8, 132.3, 135.1, 147.2, 153.6 .

[0064]31P-NMR (DMSO-D6, PPM): 38.612.

[0065]FTIR (KBR): 814CM-1(Triazine Ring), 1229CM-1(P-o stretch), 1552cm-1(-C = n-stretch), 1745cm-1(C = o stretch).

[0066]The above 15 g of melamine-containing compound (C) was added to 100 parts by weight of epoxy resin E-51 (commercially available), and the curing agent 4,4'-di-di-dibenzyl is added, and mixed by mechanically stirring, then Pour into the homemade mold. The mold is placed in a blower oven, which is heated according to the curing process of 140 ° C / 2H + 180 ° C / 2H, and the like is cooled to room temperature to obtain an epoxy resin cured product. When the cyclic oxygen-containing amount is 1.0% by weight, the vertical combustion level reaches the UL94 V-0, the ultimate oxygen index reaches 35, and the gas production rate reaches 23%, the glass transition temperature is 132 ° C.

[0067]Test methods for resin performance parameters and the methods in Example 1.

PUM

Property	Measurement	Unit
Glass transition temperature	135.0	°C
Glass transition temperature	137.0	°C
Glass transition temperature	132.0	°C

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