阅读说明：本技术 一种阻燃耐热的环氧模塑料及其制备方法 (Flame-retardant heat-resistant epoxy molding compound and preparation method thereof ) 是由 张洪胜 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种阻燃耐热的环氧模塑料,该环氧模塑料的制备方法是由环氧树脂与异氰尿酸酯改性的氯化石蜡的多元胺固化所得,固化后的环氧模塑料具有较高的热分解温度,良好的阻燃性,具有广阔的应用前景。(The invention discloses a flame-retardant heat-resistant epoxy molding compound, which is prepared by curing polyamine of epoxy resin and isocyanurate modified chlorinated paraffin, and has the advantages of higher thermal decomposition temperature, good flame retardance and wide application prospect.)

1. The flame-retardant heat-resistant epoxy molding compound is characterized by comprising the following components in parts by weight:

100 parts of epoxy resin;

75-150 parts of polyamine curing agent with the structure shown in the formula (I);

in formula (I), n ═ 1 or 2 or 3; r₁、R₂Is a chlorinated paraffin chain segment.

2. The flame retardant, heat resistant epoxy molding compound as claimed in claim 1, wherein said epoxy resin is epoxy resin E-42.

3. The flame retardant, heat resistant epoxy molding compound as claimed in claim 1, comprising 75 to 150 parts of polyamine curing agent having the structure of formula (I).

4. A process for preparing a flame retardant and heat resistant epoxy molding compound as claimed in any one of claims 1 to 3, characterized by the steps of:

mixing epoxy resin and polyamine curing agent with the structure shown in the formula (I) under the conditions of heating and stirring to obtain a mixed material;

and heating and curing the mixed material to obtain the flame-retardant heat-resistant epoxy molding compound.

5. The method according to claim 4, wherein the heating temperature is 85 to 120 ℃.

6. The method according to claim 4, wherein the stirring time is 20 to 30min, and the stirring speed is 300 to 600 rpm.

7. The method of claim 4, wherein the curing is performed in a preheated mold.

8. The method according to claim 7, wherein the mold preheating temperature is 70 to 80 ℃.

9. The method according to claim 5, wherein the curing is performed by: heating to 100-120 ℃ for curing for 10-20 min, and then heating to 130-140 ℃ for curing for 30-90 min.

Technical Field

The invention relates to a flame-retardant heat-resistant epoxy molding compound and a preparation method thereof, belonging to the field of flame-retardant heat-resistant materials.

Background

Epoxy resin is an important thermosetting resin, has the advantages of high bonding strength, low shrinkage, good stability, high mechanical strength, good processability and the like, is used as a resin matrix of a high-performance composite material, and is widely applied to the fields of machinery, electronic aviation, ship industry and the like. These fields require epoxy resins with good flame retardant properties, however, epoxy resins are flammable materials, which greatly limits their applications. Therefore, the improvement of the flame retardancy of epoxy resins has become a pressing problem, and has attracted much attention at home and abroad.

The chlorinated paraffin is a chlorinated derivative of paraffin, has the advantages of low volatility, flame retardance, good barrier property, low price and the like, can be used as additives such as a plasticizer, a flame retardant and the like, but the addition type flame retardant is large in addition amount and general in flame retardance, and the addition type flame retardant is easy to migrate out of a polymer network along with the time migration, so that the flame retardance durability is reduced.

Disclosure of Invention

Aiming at the defects of chlorinated paraffin in the application of epoxy resin in the prior art, the invention aims to provide the thermosetting epoxy resin with flame retardant and heat resistance functions, which is cured by isocyanurate modified polyamine and contains the chlorinated paraffin molecules in molecular side chains.

The invention also aims to provide a method for preparing the flame-retardant heat-resistant epoxy resin, which has the advantages of wide raw material source, simple operation and mild reaction conditions.

A flame-retardant heat-resistant epoxy molding compound comprises the following components in parts by weight:

100 parts of epoxy resin;

75-150 parts of polyamine curing agent with the structure shown in the formula (I);

in formula (I), n ═ 1 or 2 or 3; r₁、R₂Is a chlorinated paraffin chain segment.

Preferably, the epoxy resin is epoxy resin E-42.

Preferably, the curing agent comprises 75-150 parts of polyamine curing agent with the structure shown in the formula (I).

The invention provides a preparation method of the flame-retardant heat-resistant epoxy molding compound, which comprises the following steps:

mixing epoxy resin and polyamine curing agent with the structure shown in the formula (I) under the conditions of heating and stirring to obtain a mixed material;

and heating and curing the mixed material to obtain the flame-retardant heat-resistant epoxy molding compound.

Preferably, the heating temperature is 85-120 ℃.

Preferably, the stirring time is 20-30 min, and the stirring speed is 300-600 rpm.

Preferably, the curing is carried out in a preheated mould.

Preferably, the preheating temperature of the die is 70-80 ℃.

Preferably, the curing process is as follows: heating to 100-120 ℃ for curing for 10-20 min, and then heating to 130-140 ℃ for curing for 30-90 min.

The invention has the beneficial effects that: according to the invention, the traditional chlorinated paraffin molecule is introduced into an isocyanurate molecular chain through a chemical bond for the first time, then reacts with polyamine to form a novel polyamine curing agent, and then reacts with epoxy resin to form the epoxy molding compound with flame-retardant and heat-resistant functions. The whole preparation process has the advantages of easily available raw materials, low cost, simple operation, high purity of the obtained product and high yield, and meets the requirements of industrial production.

Drawings

FIG. 1 is an infrared chart of the polyamine curing agent prepared in example 2.

Detailed Description

The invention provides a flame-retardant heat-resistant epoxy molding compound which comprises the following components in parts by weight:

100 parts of epoxy resin;

75-150 parts of polyamine curing agent with the structure shown in the formula (I);

in formula (I), n ═ 1 or 2 or 3; r₁、R₂Is a chlorinated paraffin chain segment.

The invention takes the isocyanuric ester modified polyamine curing agent with the molecular side chain containing chlorinated paraffin molecules as the raw material, provides the flame-retardant epoxy molding compound, and improves the flame-retardant property of the epoxy resin.

In the invention, the epoxy resin is epoxy resin E-42.

Based on 100 parts of the epoxy resin, the flame-retardant epoxy molding compound provided by the invention preferably comprises 75-150 parts of isocyanurate modified polyamine curing agent with a molecular side chain containing chlorinated paraffin molecules and having a structure shown in formula (I).

In the present invention, the preparation method of the isocyanurate-modified polyamine curing agent having a structure represented by formula (I) and a molecular side chain containing a chlorinated paraffin molecule preferably comprises the following steps:

step (1): preparation of chlorinated paraffins containing carboxyl groups

Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;

step (2): preparation of chlorinated paraffins containing acid chlorides

Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, dropwise adding excessive phosphorus trichloride into the reaction kettle, and reacting at the temperature of 50-70 ℃ to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxyl-containing isocyanurate modified chlorinated Paraffin

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the reaction molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 2-2.1: 1, so as to obtain chlorinated paraffin containing hydroxyl;

and (4): preparation of carboxyl-containing isocyanurate-modified chlorinated Paraffin

Adding the hydroxyl-containing chlorinated paraffin obtained in the step (3) and trimellitic anhydride into a reaction kettle, and reacting at the temperature of 60-80 ℃ for 3-7 h to obtain carboxyl-containing isocyanurate modified chlorinated paraffin;

and (5): preparation of polyamines

And (3) adding the chlorinated paraffin modified by the carboxyl-containing isocyanurate obtained in the step (4) and polyamine into a reaction kettle, heating to 130-170 ℃ under stirring, and reacting for 3-6 h, wherein the reaction molar ratio of the chlorinated paraffin modified by the carboxyl-containing isocyanurate to the polyamine is 1:2, so as to obtain the polyamine curing agent, and the polyamine is diethylenetriamine or triethylenetetramine or tetraethylenepentamine.

The invention provides a preparation method of the flame-retardant heat-resistant epoxy molding compound, which comprises the following steps:

mixing epoxy resin and polyamine flame-retardant curing agent with a structure shown in formula (I) under the conditions of heating and stirring to obtain a mixed material;

and heating and curing the mixed material to obtain the flame-retardant heat-resistant epoxy molding compound.

The epoxy resin and the polyamine flame-retardant curing agent with the structure shown in the formula (I) are mixed under the conditions of heating and stirring to obtain a mixed material. In the invention, the heating temperature is preferably 85-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the stirring time is preferably 20-30 min; the stirring speed is preferably 300-600 rpm, more preferably 400-500 rpm, and most preferably 450 rpm.

After the mixed material is obtained, the mixed material is put into a preheated mold for heating and curing, and the flame-retardant epoxy molding compound is obtained.

In the invention, the curing is preferably carried out in a preheated mold, and the preheating temperature is preferably 70-80 ℃, and more preferably 75 ℃.

In the present invention, the curing process is preferably performed at the first curing temperature for 10min to 20min, more preferably 15min to 20min, and at the second curing temperature for 30min to 90min, more preferably 45min to 80 min. In the invention, the first curing temperature is preferably 100-120 ℃, and more preferably 110-115 ℃; the second curing temperature is preferably 130-140 ℃, and more preferably 135-138 ℃.

The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.

Example 1

1) Preparation of chlorinated paraffin 42 containing carboxyl group: dissolving 20g of chlorinated paraffin 42 in 210mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 28g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 42 containing carboxyl.

2) Preparation of acid chloride-containing chlorinated paraffin 42: adding 70mol of chlorinated paraffin 42 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.

3) Preparation of isocyanurate-modified chlorinated paraffin 42: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 201mol of chlorinated paraffin 42 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 42.

4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 42 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 4h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 42 dibasic acid.

5) Preparation of polyamine: 100mol of isocyanuric ester modified chlorinated paraffin 42 dibasic acid and 200mol of diethylenetriamine are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 130 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering, rotary distilling, and vacuum distilling to obtain the polyamine curing agent.

100g of epoxy resin E-42 and 120g of the prepared polyamine flame-retardant curing agent are mixed, heated and stirred, the heating temperature is 120 ℃, the stirring time is 20min, the stirring speed is 300 r/min, the mixture is injected into a preheating mould with the specified size and the temperature of 70 ℃ for curing for 1h, the mixture is heated to 100 ℃ by an oven for curing for 20min, and then the mixture is heated to 130 ℃ for curing for 80min to obtain the flame-retardant epoxy molding compound.

The flame-retardant epoxy molding compound obtained in example 1 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Example 2

1) Preparation of chlorinated paraffin 52 containing carboxyl group: 20g of chlorinated paraffin 52 is dissolved in 220mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 29g of potassium carbonate are added to react for 24h at 65 ℃ under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.

2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of chlorinated paraffin 52 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 containing acyl chloride.

3) Preparation of isocyanurate-modified chlorinated paraffin 52: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 202mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 52.

4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 52 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 52 dibasic acid.

5) Preparation of polyamine: 100mol of isocyanuric ester modified chlorinated paraffin 52 dibasic acid and 200mol of diethylenetriamine are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 3 hours at 170 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering, rotary distilling, and vacuum distilling to obtain the polyamine curing agent.

100g of epoxy resin E-42 and 130g of the prepared polyamine flame-retardant curing agent are mixed, heated and stirred, the heating temperature is 85 ℃, the stirring time is 30min, the stirring speed is 600 r/min, the mixture is injected into a preheating mould with the specified size of 80 ℃ for curing for 1h, the temperature is raised to 120 ℃ by an oven for curing for 15min, and then the temperature is raised to 140 ℃ for curing for 45min, so that the flame-retardant epoxy molding compound is obtained.

The flame-retardant epoxy molding compound obtained in example 2 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Example 3

1) Preparation of chlorinated paraffin 52 containing carboxyl group: dissolving 20g of chlorinated paraffin 52 in 210mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 25g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.

2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 7 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.

3) Preparation of isocyanurate-modified chlorinated paraffin 52: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 201mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 52.

4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 52 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 52 dibasic acid.

5) Preparation of polyamine: 100mol of isocyanurate modified chlorinated paraffin 52 dibasic acid and 200mol of triethylene tetramine are introduced into a reaction kettle, and the reaction is stopped after 4 hours of reaction at 165 ℃ until no water is generated. Cooling, filtering, rotary distilling, and vacuum distilling to obtain the polyamine curing agent.

100g of epoxy resin E-42 and 110g of the prepared polyamine flame-retardant curing agent are mixed, heated and stirred, the heating temperature is 80 ℃, the stirring time is 25min, the stirring speed is 500 r/min, the mixture is injected into a preheating mould with the specified size of 80 ℃ for curing for 1h, the temperature is raised to 116 ℃ through an oven for curing for 18min, and then the temperature is raised to 135 ℃ for curing for 60min, so that the flame-retardant epoxy molding compound is obtained.

The flame-retardant epoxy molding compound obtained in example 3 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Example 4

1) Preparation of chlorinated paraffin 52 containing carboxyl group: 20g of chlorinated paraffin 52 is dissolved in 200mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 27g of potassium carbonate are added to react for 24h at 65 ℃ under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.

2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of chlorinated paraffin 52 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 containing acyl chloride.

3) Preparation of isocyanurate-modified chlorinated paraffin 52: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 204mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 52.

4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 52 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 52 dibasic acid.

5) Preparation of polyamine: 100mol of isocyanuric ester modified chlorinated paraffin 52 dibasic acid and 200mol of tetraethylenepentamine are introduced into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 4 hours at 160 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering, rotary distilling, and vacuum distilling to obtain the polyamine curing agent.

100g of epoxy resin E-42 and 90g of the prepared polyamine flame-retardant curing agent are mixed, heated and stirred, the heating temperature is 80 ℃, the stirring time is 20min, the stirring speed is 450 r/m, the mixture is injected into a preheating mould with the specified size of 80 ℃ for curing for 1h, the temperature is raised to 115 ℃ through an oven for curing for 20min, and then the temperature is raised to 138 ℃ for curing for 70min, so that the flame-retardant epoxy molding compound is obtained.

The flame-retardant epoxy molding material obtained in example 4 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Example 5

1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 70 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.

2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 70 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.

3) Preparation of isocyanurate-modified chlorinated paraffin 70: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 205mol of chlorinated paraffin 70 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 70.

4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 70 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 70 dibasic acid.

5) Preparation of polyamine: 100mol of isocyanurate modified chlorinated paraffin 70 diacid and 200mol of diethylenetriamine are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 5 hours at 135 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering, rotary distilling, and vacuum distilling to obtain the polyamine curing agent.

100g of epoxy resin E-42 and 130g of the prepared polyamine flame-retardant curing agent are mixed, heated and stirred, the heating temperature is 80 ℃, the stirring time is 25min, the stirring speed is 500 r/min, the mixture is injected into a preheating mould with the specified size of 80 ℃ for curing for 1h, the temperature is raised to 115 ℃ through an oven for curing for 17min, and then the temperature is raised to 135 ℃ for curing for 70min, so that the flame-retardant epoxy molding compound is obtained.

The flame-retardant epoxy molding material obtained in example 5 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Example 6

1) Preparation of carboxyl group-containing chlorinated paraffin 70: 20g of chlorinated paraffin 70 is dissolved in 210mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 26g of potassium carbonate are added to react for 24h at 65 ℃ under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.

2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 70 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.

3) Preparation of isocyanurate-modified chlorinated paraffin 70: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 202mol of chlorinated paraffin 70 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 70.

4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 70 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 65 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 70 dibasic acid.

5) Preparation of polyamine: 100mol of isocyanurate modified chlorinated paraffin 70 dibasic acid and 200mol of triethylene tetramine are introduced into a reaction kettle, and the reaction is stopped after 6 hours of reaction at 130 ℃ until no water is generated. Cooling, filtering, rotary distilling, and vacuum distilling to obtain the polyamine curing agent.

100g of epoxy resin E-42 and 120g of the prepared polyamine flame-retardant curing agent are mixed, heated and stirred, the heating temperature is 85 ℃, the stirring time is 30min, the stirring speed is 600 r/min, the mixture is injected into a preheating mould with the specified size of 80 ℃ for curing for 1h, the temperature is raised to 120 ℃ by an oven for curing for 15min, and then the temperature is raised to 140 ℃ for curing for 45min, so that the flame-retardant epoxy molding compound is obtained.

The flame-retardant epoxy molding compound obtained in example 6 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Comparative example 1

100g of epoxy resin E-42, 15g of chlorinated paraffin 42 and 8.25g of diethylenetriamine curing agent are mixed, heated and stirred, the heating temperature is 85 ℃, the stirring time is 30min, the stirring speed is 600 r/m, the mixture is injected into a preheating mould with the specified size of 70 ℃ for curing for 1h, the temperature is raised to 120 ℃ by an oven for curing for 15min, and then the temperature is raised to 140 ℃ for curing for 45min, so that the epoxy molding compound is obtained.

The epoxy molding compound obtained in comparative example 1 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Comparative example 2

100g of epoxy resin E-42, 15g of chlorinated paraffin 52 and 9.75g of triethylene tetramine curing agent are mixed, heated and stirred, the heating temperature is 85 ℃, the stirring time is 30min, the stirring speed is 400 r/m, the mixture is injected into a preheating mould with the temperature of 75 ℃ of a specified size for curing for 1h, the temperature is raised to 115 ℃ through an oven for curing for 20min, and then the temperature is raised to 140 ℃ for curing for 45min, so that the epoxy molding compound is obtained.

The epoxy molding compound obtained in comparative example 2 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

Comparative example 3

100g of epoxy resin E-42, 15g of chlorinated paraffin 70 and 10.82g of tetraethylenepentamine curing agent are mixed, heated and stirred, the heating temperature is 120 ℃, the stirring time is 20min, the stirring speed is 500 r/min, the mixture is injected into a preheating mould with the specified size of 80 ℃ for curing for 1h, the temperature is raised to 120 ℃ by an oven for curing for 15min, and then the temperature is raised to 135 ℃ for curing for 60min, so that the epoxy molding compound is obtained.

The epoxy molding compound obtained in comparative example 3 was subjected to limiting oxygen index and vertical burning tests, and the test results are shown in Table 1.

TABLE 1 Limited oxygen index and vertical burning test results of epoxy molding compounds prepared in inventive examples 1-6 and comparative examples 1-3

Note: v-0 and V-1 are fire test ratings of class V, where V-0 is better than V-1 and NR indicates failure of the test.

In conclusion, the chlorinated paraffin is introduced into the isocyanurate molecular ring through a chemical bond, then reacts with the trimellitic anhydride to form a diacid, then reacts with the polyamine to form a novel polyamine curing agent, and then reacts with the epoxy resin to form the epoxy molding compound, so that the epoxy molding compound has good flame-retardant and heat-resistant properties.