CN111004474B - Expandable epoxy resin composite flame-retardant material and preparation method thereof - Google Patents
Expandable epoxy resin composite flame-retardant material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an expandable novel epoxy resin composite flame-retardant material and a preparation method thereof, belongs to the technical field of flame retardants, and particularly relates to an expandable novel epoxy resin composite flame-retardant material with good flame retardant property. The raw materials in parts by weight include: 67.5 parts of epoxy resin, 22.5 parts of curing agent and 10 parts of flame retardant; the flame retardant comprises 0-10 parts of expandable graphite and 0-10 parts of aluminum hypophosphite. The method has the advantages of simple preparation method, easy operation, wide raw material source, low cost, environmental protection, no need of special equipment in the whole reaction process and the like, and is beneficial to industrial production. Compared with a pure epoxy resin material, the novel expandable epoxy resin composite flame-retardant material disclosed by the invention has higher thermal stability and oxygen index, and has a wide commercial application prospect.
Description
Technical Field
The invention discloses an expandable novel epoxy resin composite flame-retardant material and a preparation method thereof, belongs to the technical field of flame retardants, and particularly relates to an expandable novel epoxy resin composite flame-retardant material with good flame retardant property.
Background
The epoxy resin has good electrical property, mechanical property, chemical corrosion resistance and the like, and is widely applied to the fields of mechanical manufacturing, electronics and electrics, aerospace, wind power generation and the like. However, the epoxy resin is extremely easy to burn, the flame propagation speed is high, the smoke is more, and the heat release rate is high. This poses a potential threat to the spread of fire and escape of people. Therefore, it is important to improve the thermal stability of the epoxy resin material, reduce the heat release rate in the combustion process, and improve the low resistance and smoke suppression performance of the epoxy resin material. Therefore, it is one of the hot spots of the current research to improve the flame retardant property.
The expandable graphite has the advantages of abundant resources, simple manufacture, low price, no toxicity, low smoke and one of the hot spots of research on the intumescent flame retardant. But the use of expanded graphite and epoxy alone forms an expanded carbon layer during combustion. The composite material can not play a good role in smoke suppression and heat insulation, can form an effect of popcorn, can promote the dehydration of the material to form charcoal by adding a phosphorus flame retardant, forms a compact charcoal layer to block the transfer of substances and energy, and inhibits the further degradation and combustion of internal materials; meanwhile, the phosphorus flame retardant can generate free radicals to inhibit chain reaction during combustion, and has good flame retardant effect.
Patent CN108727782A discloses a new epoxy resin flame retardant material, but the use of the nano material is relatively high in cost. Patent CN109880170A also discloses a new epoxy resin flame retardant material, but its flame retardant is synthesized by coprecipitation method and doping element method, and the synthetic route is complicated.
Therefore, a composite material with simple synthetic circuit and good flame retardant property is urgently needed.
Disclosure of Invention
The invention aims to provide the novel expandable epoxy resin composite flame-retardant material and the preparation method thereof, aiming at the defects, the synthetic route is simple, the obtained composite material has good flame-retardant property, and the addition amount and the total amount of the flame retardant are less. The defects of the prior art are well solved.
The invention is realized by adopting the following technical scheme:
the novel expandable epoxy resin composite flame-retardant material comprises the following raw materials in parts by weight: 67.5 parts of epoxy resin, 22.5 parts of curing agent and 10 parts of flame retardant; the flame retardant is 0-10 parts of expandable graphite and 0-10 parts of aluminum hypophosphite.
The curing agent is polyether amine.
Optimally, the weight parts of the expandable graphite and the aluminum hypophosphite in the flame retardant are respectively 9 parts and 1 part.
Most preferably, the parts by weight of the expandable graphite and the aluminum hypophosphite in the flame retardant are 6 parts and 4 parts respectively.
A preparation method of the novel expandable epoxy resin composite flame-retardant material comprises the following steps:
(1) weighing aluminum hypophosphite and epoxy resin, adding into a beaker, and stirring at the rotating speed of 500 revolutions per minute for 10 minutes to obtain a solution A;
(2) weighing expandable graphite, adding the expandable graphite into the solution A, and stirring at the rotating speed of 500 revolutions per minute for 10 minutes to obtain a solution B;
(3) weighing polyetheramine, adding the polyetheramine into the solution B, and stirring at the rotating speed of 500 revolutions per minute for 10 minutes to obtain a solution C;
(4) putting the solution C into a vacuum drying oven, and vacuumizing for 10 minutes under the pressure of 0.08MPa to obtain a solution D;
(5) and pouring the solution D into a mold, and curing and demolding after injection molding to obtain the novel expandable epoxy resin composite flame-retardant material.
The aluminum hypophosphite adopted in the step (1) is aluminum hypophosphite powder.
The expandable graphite adopted in the step (2) is expandable graphite particles.
And (3) adding the flame retardant in the steps (1) and (2) in the sequence of adding aluminum hypophosphite powder and stirring, and then adding expandable graphite particles and stirring.
The steps (1) and (2) are carried out by stirring in a water bath at 60 ℃, and the curing agent in the step (3) is added and then stirred at room temperature.
The addition amount of the flame retardant in the steps (1) and (2) is 1/10 of the total weight of the composite material, and the addition amount of the curing agent in the step (3) is 1/3 of the weight of the epoxy resin.
The curing conditions of the step (5) are as follows: precuring for one night under the condition of room temperature, and then curing for 4 hours under the condition of 120 ℃ in a drying oven.
Compared with the prior art, the invention has the following advantages:
1) the preparation method provided by the invention has the advantages of simplicity, easiness in operation, wide raw material source, low cost, environmental friendliness, no need of special equipment in the whole reaction process and the like, and is beneficial to industrial production.
2) The composite flame-retardant material provided by the invention utilizes a method of compounding a flame retardant and realizing flame retardance, and aluminum hypophosphite is added, so that the problems of fluffy carbon layer, low oxygen index, poor flame retardance and the like caused by the combustion of the expandable graphite epoxy resin composite material are solved.
3) Compared with a pure epoxy resin material, the epoxy resin composite flame-retardant material provided by the invention has higher limit oxygen index and thermal stability, and has wide commercial application prospect.
Drawings
The invention will be further explained with reference to the drawings, in which:
FIG. 1 is a graph of thermogravimetric (left) and rate of thermal weight loss (right) curves in a nitrogen atmosphere after curing of epoxy resin composites provided in examples 1, 2, 3, 4 and 5 of the present invention;
FIG. 2 is a flow chart of the preparation of the novel expandable epoxy resin composite flame-retardant material.
Detailed Description
The present invention will now be described more fully and in detail with reference to the following specific embodiments and the accompanying drawings, but the scope of the invention is not limited to the specific embodiments below.
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products produced by known methods.
The technical scheme adopted by the invention is further explained by combining the drawings and the embodiment.
Example 1:
the preparation of the pure epoxy resin specifically comprises the following steps:
22.5 portions of polyether amine is added into 67.5 portions of epoxy resin, stirred for ten minutes at the rotating speed of 500 revolutions per minute under the condition of room temperature, poured into a mold for precuring overnight at room temperature, cured for 4 hours at the constant temperature of 120 ℃ in a drying oven, taken out and demolded.
Referring to table 1, it can be seen that the oxygen index of example 1 is only 20.4% and there is no vertical burn rating.
Referring to fig. 1 and 2, there are shown thermogravimetric (left) and thermogravimetric (right) rate curves of examples in a nitrogen atmosphere. According to the thermogravimetric graph, the thermal weight loss can be divided into three stages, wherein the first stage is evaporation at 0-300 ℃, the second stage is thermal decomposition at 300-450 ℃, and the third stage is carbonization at 450-800 ℃. The temperature (T) at 5% weight loss of example 1 can be seen5%) 346.7 ℃ temperature at the peak of the rate of thermal weight loss (T)d,max) 385 ℃, the maximum weight loss rate is 1.21%/DEG C, the residual carbon rate is only 8.5% after 800 ℃, and the residual carbon rate is lower, which indicates that the carbon forming effect during combustion is poor.
Example 2:
the preparation method of the epoxy resin composite flame-retardant material with the aluminum hypophosphite added independently comprises the following steps:
adding 10 parts of aluminum hypophosphite into 67.5 parts of epoxy resin, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of water bath at 60 ℃, adding 22.5 parts of polyether amine, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of room temperature, pouring into a mold, precuring for one night at room temperature, curing for 4 hours at the constant temperature of 120 ℃ in a drying oven, taking out and demolding.
Referring to table 1, it can be seen that the oxygen index of example 2 is 22.6%, 2.4% higher than 20.4% of example 1, and the vertical burn is still off grade.
See fig. 1, which is a thermogravimetric (left) and rate of thermal weight loss (right) curve under nitrogen atmosphere for example 2. It can be seen that example 2 has a temperature (T) at which 5% weight loss occurs5%) 313 ℃ temperature at the peak rate of thermal weight loss (T)d,max) 362.5 ℃ and the maximum weight loss rate of 1.37%/deg.C increased by 0.16%/deg.C over 1.21%/deg.C for example 1. The carbon residue of example 2 at 800 ℃ was 17.2%, which is much greater than 8.5% of example 1. Therefore, the addition of the aluminum hypophosphite greatly promotes the carbon formation rate of the composite material.
Example 3:
the preparation method of the epoxy resin composite flame-retardant material with the separately added expandable graphite comprises the following steps:
adding 10 parts of expandable graphite into 67.5 parts of epoxy resin, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of water bath at 60 ℃, adding 22.5 parts of polyether amine, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of room temperature, pouring into a mold, precuring for one night at room temperature, curing for 4 hours at the constant temperature of 120 ℃ in a drying oven, taking out and demolding.
Referring to table 1, it can be seen that the vertical burn of example 3 is still off grade, with an oxygen index of 25.2%, 4.8% higher than 20.4% for example 1 and 2.6% higher than 22.6% for example 2, thus showing that the addition of expandable graphite alone is better than the aluminum hypophosphite in flame retardant effect.
See fig. 1, which is a graph of thermogravimetric (left) and rate of thermogravimetric weight loss (right) under nitrogen atmosphere for example 3. It can be seen that example 3 has a temperature (T) of 5% weight loss5%) 338.7 ℃ higher by 25.4 ℃ than 313.3 ℃ in example 2; temperature (T) of peak rate of thermal weight lossd,max) 387.5 ℃ higher by 25.2 ℃ than 362.3 ℃ in example 2; the maximum weight loss rate was 1.09%/deg.C. Example 3 has a carbon residue of 24.6% at 800 deg.C, which is much greater than 8.5% for example 1 and 7.4% higher than 17.2% for example 2. The expandable graphite has better thermal stability and higher carbon formation rate than aluminum hypophosphite.
Example 4:
the preparation method of the epoxy resin composite flame-retardant material added with the aluminum hypophosphite and the expandable graphite comprises the following steps:
adding 1 part of aluminum hypophosphite into 67.5 parts of epoxy resin, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of water bath at 60 ℃, then adding 9 parts of expandable graphite, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of water bath at 60 ℃, then adding 22.5 parts of polyetheramine, stirring for ten minutes at the room temperature and the rotating speed of 500 revolutions per minute, pouring into a mold, precuring for one night at room temperature, then curing for 4 hours at the constant temperature of 120 ℃ in a drying box, and taking out and demolding.
Referring to table 1, it can be seen that the vertical burning rating of example 4 is still no rating, the oxygen index is 28.1%, which is much greater than 20.4% of example 1, 5.6% higher than 22.6% of example 2, and 2.9% higher than 25.2% of example 3, indicating that the addition of aluminum hypophosphite to the composite flame retardant can improve the flame retardant performance of the composite material.
See fig. 1, which is a thermogravimetric (left) and rate of thermal weight loss (right) curve under nitrogen atmosphere for example 4. It can be seen that example 4 has a temperature (T) at which 5% weight is lost5%) 330.7 deg.C, 17.4 deg.C higher than 313.3 deg.C for example 2, and 8% lower than 338.7 deg.C for example 3; temperature (T) of peak rate of thermal weight lossd,max) 374 ℃ higher than 362.3 ℃ of example 2 and 13.5 ℃ lower than 387.5 ℃ of example 3; the maximum weight loss rate was 1.19%/deg.C. Example 4 has a carbon residue of 16.3% at 800 c, which is also much greater than 8.5% of example 1.
Example 5:
adding 4 parts of aluminum hypophosphite into 67.5 parts of epoxy resin, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of water bath at 60 ℃, then adding 6 parts of expandable graphite, stirring for ten minutes at the rotating speed of 500 revolutions per minute under the condition of water bath at 60 ℃, then adding 22.5 parts of polyetheramine, stirring for ten minutes at the room temperature and the rotating speed of 500 revolutions per minute, pouring into a mold, precuring for one night at room temperature, then curing for 4 hours at the constant temperature of 120 ℃ in a drying box, and taking out and demolding.
Referring to table 1, it can be seen that the vertical burning grade of example 5 reached the highest grade V-0 grade, and examples 1, 2, 3, and 4 were all no grade; and it can be seen that the oxygen index of example 5 is 32.9%, 4.8% higher than 28.1% of example 4, and both are much higher than the oxygen indexes of examples 1, 2, and 3, which indicates that the compound flame retardant of example 5 has the optimal proportioning, so that the material achieves the optimal flame retardant performance.
See fig. 1, which is a thermogravimetric (left) and rate of thermal weight loss (right) curve under nitrogen atmosphere for example 5. It can be seen that example 5 has a temperature (T) of 5% weight loss5%) 317.3 ℃ lower by 13.4 ℃ than in example 4; temperature (T) of peak rate of thermal weight lossd,max) 375 ℃ higher than 374 ℃ in example 4 by 1 ℃; the maximum weight loss rate was 1.34%/deg.C, 0.15%/deg.C higher than 1.19%/deg.C for example 4. Example 5 carbon residue at 800 deg.C21.3% and is also much greater than 8.5% for example 1, 5% higher than 16.3% for example 4. The fact that the addition of the two flame retardants can promote the carbon formation of the material is shown, and the example 5 has better thermal stability and higher carbon formation rate than the example 4 while improving the flame retardant performance.
The limited oxygen index and the vertical burning grade of the novel expandable epoxy resin composite flame-retardant material prepared by the embodiment are shown in the following table 1:
TABLE 1 examples 1, 2, 3 and 4 Limited oxygen index and vertical burn rating
Thermogravimetric data of the novel expandable epoxy resin composite flame-retardant material prepared by the embodiment under a nitrogen atmosphere are shown in table 2:
table 2 thermogravimetric data under nitrogen atmosphere for examples 1, 2, 3 and 4
Claims (7)
1. An expandable epoxy resin composite flame-retardant material is characterized by comprising the following raw materials in parts by weight: 67.5 parts of epoxy resin, 22.5 parts of curing agent and 10 parts of flame retardant; the flame retardant comprises 6 parts of expandable graphite and 4 parts of aluminum hypophosphite.
2. The expandable epoxy resin composite flame retardant material of claim 1, wherein the curing agent is a polyetheramine.
3. A method for preparing the expandable epoxy resin composite flame-retardant material of claim 1, which comprises the following steps:
(1) weighing aluminum hypophosphite and epoxy resin, adding into a beaker, and stirring at the rotating speed of 500 revolutions per minute for 10 minutes to obtain a solution A;
(2) weighing expandable graphite, adding the expandable graphite into the solution A, and stirring at the rotating speed of 500 revolutions per minute for 10 minutes to obtain a solution B;
(3) weighing polyetheramine, adding the polyetheramine into the solution B, and stirring at the rotating speed of 500 revolutions per minute for 10 minutes to obtain a solution C;
(4) putting the solution C into a vacuum drying oven, and vacuumizing for 10 minutes under the pressure of 0.08MPa to obtain a solution D;
(5) and pouring the solution D into a mold, and curing and demolding after injection molding to obtain the expandable epoxy resin composite flame-retardant material.
4. The method for preparing the expandable epoxy resin composite flame-retardant material as claimed in claim 3, wherein the aluminum hypophosphite used in the step (1) is aluminum hypophosphite powder.
5. The method for preparing expandable epoxy resin composite flame retardant material according to claim 3, wherein the expandable graphite used in the step (2) is expandable graphite particles.
6. The method for preparing the expandable epoxy resin composite flame-retardant material as claimed in claim 3, wherein the steps (1) and (2) are carried out by stirring in a water bath at 60 ℃, and the curing agent in the step (3) is added and then stirred at room temperature.
7. The method for preparing the expandable epoxy resin composite flame retardant material according to claim 3, wherein the curing conditions of the step (5) are as follows: precuring for one night under the condition of room temperature, and then curing for 4 hours under the condition of 120 ℃ in a drying oven.
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