CN113234228A - Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof - Google Patents
Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of flame-retardant polymer materials, in particular to a boron-containing polyphosphazene amide flame retardant with high-efficiency flame retardance and smoke suppression, and a preparation method and application thereof. The boron-containing polyphosphate amide flame retardant is an efficient flame-retardant smoke suppressant simultaneously containing three flame-retardant elements of phosphorus, boron and nitrogen, can effectively improve the flame retardance, smoke suppression and mechanical properties of an epoxy resin condensate under low addition amount due to the synergistic flame-retardant effect of different flame-retardant elements, and keeps the transparency of the epoxy resin condensate, the limiting oxygen index can reach more than 33%, the UL-94 grade reaches V-0 grade, the peak value of the heat release rate and the total smoke release amount are obviously reduced, the mechanical strength and toughness are obviously improved, and the optical transparency can be kept at about 80%.
Description
Technical Field
The invention relates to the technical field of flame-retardant polymer materials, in particular to a boron-containing polyphosphazene amide flame retardant with high-efficiency flame retardance and smoke suppression, and a preparation method and application thereof.
Background
Epoxy resin has excellent properties of adhesion, chemical corrosion resistance, electrical insulation, heat resistance, mechanics and the like, and is widely applied to the fields of rail transit, aerospace, electronic and electrical products, civil engineering and construction and the like. However, most of epoxy resin is composed of C, O, N, H elements, so that the epoxy resin belongs to flammable materials, generates a large amount of molten drops during combustion and releases a large amount of toxic gases, and the wide application of the epoxy resin brings great fire threat to people; therefore, the flame retardant modified flame retardant has to be modified, so that the flame retardant and smoke suppression performance of the flame retardant modified smoke suppression performance is required to reduce fire threat.
The halogen compound is a high-efficiency flame retardant and is often used for flame retardant modification of epoxy resin. However, there are problems of bio-enrichment and generation of corrosive gases and carcinogenic substances such as hydrogen halide and dibenzofuran during combustion, and thus various halogen-based flame retardants have been prohibited.
In recent years, phosphorus flame retardants are one of the most promising halogen-free flame retardants because of their halogen-free, environmental-friendly, low-toxicity, and low-smoke properties. However, the single phosphorus-containing flame retardant generally has the problem of low flame retardant efficiency, and the flame retardant performance of the epoxy resin can be effectively improved only by using a large amount of the phosphorus-containing flame retardant. Due to the synergistic flame-retardant effect of phosphorus and nitrogen, the polyphosphate flame retardant has higher flame-retardant efficiency than a single phosphorus-containing flame retardant, can endow epoxy resin with excellent flame-retardant performance under a lower addition amount, but has no smoke suppression effect because smoke is increased in the combustion process of the epoxy resin due to the flame-retardant effect of the polyphosphate flame retardant in a gas phase. The boron-containing flame retardant can form a compact glassy carbon layer on the surface (condensed phase) of an epoxy body in the combustion process, so that smoke release can be inhibited. Therefore, the boron-containing polyphosphate amide flame retardant is expected to simultaneously realize two functions of flame retardance and smoke suppression, and further the high-performance flame-retardant smoke-suppression epoxy resin is prepared.
Chinese patent application document (publication No. CN110527100A) discloses a polyphosphazene flame retardant and a preparation method and application thereof, the polyphosphazene flame retardant containing a phosphaphenanthrene structure has the characteristics of high phosphorus and nitrogen content, excellent heat resistance and char formation performance, but has no smoke suppression performance and low flame retardant efficiency, so that the physical performance of a flame-retardant composite material is reduced due to high addition amount when the flame-retardant composite material is prepared by the flame-retardant composite material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a boron-containing polyphosphate fire retardant which can simultaneously exert the flame retardant effect of gas phase and condensed phase and has high-efficiency flame retardance and smoke suppression and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the boron-containing polyphosphate amide flame retardant has the following structure:
the boron-containing polyphosphate amide flame retardant disclosed by the invention simultaneously contains three flame retardant elements of phosphorus, boron and nitrogen, can achieve the effects of high-efficiency flame retardance and smoke suppression, and simultaneously due to the polyphosphate amide structure, the mechanical strength and toughness of a flame-retardant composite material formed after the flame-retardant composite material is added into epoxy resin are further improved, and the flame-retardant composite material is not easy to precipitate in the actual application process.
The invention also provides a preparation method of the boron-containing polyphosphoric acid amide flame retardant with high-efficiency flame retardance and smoke suppression, which comprises the following steps:
s1, uniformly mixing 3-amino-1, 2-propylene glycol, an organic solvent and deionized water in a reaction kettle, adding 1, 4-phenyl diboronic acid into the reaction kettle, stirring, and purifying to obtain a boron-containing intermediate product;
s2, uniformly mixing the boron-containing intermediate product and the organic solvent in the reaction kettle, then dropwise adding the organic solvent containing phenylphosphonic dichloride into the reaction kettle, stirring, and purifying to obtain the boron-containing polyphosphoric amide flame retardant.
The boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression is prepared by two-step synthesis, wherein in the first step, 3-amino-1, 2-propylene glycol and 1, 4-phenyl diboronic acid are used as raw materials to synthesize a boron-containing intermediate product, and in the second step, the boron-containing polyphosphate amide flame retardant is uniformly mixed with an organic solvent in a reaction kettle and then reacts with the 1, 4-phenyl diboronic acid to synthesize the boron-containing polyphosphate amide flame retardant.
In the preparation method of the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression, in the step S1, the mass ratio of 3-amino-1, 2-propylene glycol, the organic solvent and the distilled water is 1: (5-20): (0.01-0.05). The 3-amino-1, 2-propanediol, the organic solvent and the distilled water are mixed, and the proportion of the three is controlled, so that the 3-amino-1, 2-propanediol can be completely dissolved in the organic solvent, and the subsequent reaction is convenient to carry out.
In the preparation method of the boron-containing polyphosphazene amide flame retardant with high-efficiency flame retardance and smoke suppression, in the step S1, the mass ratio of 1, 4-phenyl diboronic acid to 3-amino-1, 2-propylene glycol is 1: (1.05-1.65). The invention mainly aims to improve the reaction degree of the 1, 4-phenyl diboronic acid and the 3-amino-1, 2-propylene glycol and avoid the generation of impurities by controlling the proportion of the 1, 4-phenyl diboronic acid and the 3-amino-1, 2-propylene glycol.
In the preparation method of the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression, the organic solvent is one of tetrahydrofuran, acetone, acetonitrile, dichloromethane, chloroform, dioxane, dimethylformamide and dimethyl sulfoxide.
In the preparation method of the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression, the mass ratio of the boron-containing intermediate product to the organic solvent in the step S2 is 1: (5-20).
In the preparation method of the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression, the mass ratio of the boron-containing intermediate product to the phenylphosphonic dichloride in the step S2 is (1.4-2.8): 1. the invention mainly aims to obtain the macromolecular polyphosphazene amide flame retardant by controlling the mass ratio of the boron-containing intermediate product to the phenylphosphonic dichloride, and avoid obtaining the phosphamide flame retardant which is easy to precipitate and has poor practicability.
In the preparation method of the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression, the concentration of the organic solvent containing phenylphosphonyl dichloride in the step S2 is 0.3-1 mol/L.
In the preparation method of the boron-containing polyphosphazene amide flame retardant with high-efficiency flame retardance and smoke suppression, the purification treatment comprises any one or more of filtration, washing, reduced pressure distillation and vacuum drying.
The invention also provides a flame-retardant composite material which comprises epoxy resin and the high-efficiency flame-retardant smoke-suppressing boron-containing polyphosphoric acid amide flame retardant.
Preferably, the preparation of the flame-retardant composite material specifically comprises the following steps: placing the high-efficiency flame-retardant smoke-suppressing boron-containing polyphosphazene amide flame retardant and the glycidyl ether epoxy resin into a three-neck round-bottom flask, heating and stirring until the mixture is uniform, then adding 4, 4-diaminodiphenylmethane, continuously stirring, placing the mixture in a vacuum environment for defoaming, pouring the mixture into a preheated mold while the mixture is hot, then carrying out curing treatment, and finally naturally cooling the mixture to room temperature to obtain the flame-retardant composite material.
Preferably, 100g of the flame-retardant composite material contains 1-15g of the boron-containing polyphosphazene flame retardant with high-efficiency flame retardance and smoke suppression.
Preferably, 100g of the flame-retardant composite material also comprises 10-40g of a curing agent.
Preferably, the curing agent includes one or more of aromatic amines, aliphatic amines, imidazoles, acid anhydrides, polyphenols, and polyamides.
Preferably, the epoxy resin contains two or more epoxy groups in the molecular chain, and includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.
Preferably, the curing treatment is specifically: curing at 120 deg.C, 140 deg.C, 160 deg.C and 180 deg.C for 1-3 hr.
Compared with the prior art, the invention has the following beneficial effects:
1. the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression can play a role in gas-phase and condensed-phase flame retardance when an epoxy matrix is combusted, and has two functions of high-efficiency flame retardance and smoke suppression.
2. The boron-containing polyphosphazene amide flame retardant with high-efficiency flame retardance and smoke suppression can effectively keep the transparency of epoxy resin due to small addition amount.
3. The boron-containing polyphosphazene amide flame retardant with high-efficiency flame retardance and smoke suppression can effectively improve the mechanical strength and toughness of epoxy resin due to the polymer and the benzene ring-rich structure.
Drawings
FIG. 1 is a synthetic route for the boron-containing polyphosphazene flame retardant of example 1 with high flame and smoke suppression.
Fig. 2 is a graph of heat release rate of a cone calorimetry test performed on the flame retardant composite of application example 1, application example 4, application example 5, and application comparative example 1.
Fig. 3 is a graph of total smoke release of a cone calorimetry test performed on the flame retardant composite of application example 1, application example 4, application example 5, and application comparative example 1.
Fig. 4 is a stress-strain graph of a tensile test conducted on the flame retardant composite material of application example 1, application example 4, application example 5 and application comparative example 1.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
s1, 9.895g of 3-amino-1, 2-propanediol, 141g of dimethylformamide and 0.3g of distilled water are uniformly mixed in a single-neck round-bottom flask for 10 minutes; adding 9g of 1, 4-phenyl diboronic acid in batches within 2 hours at room temperature, and reacting for 24 hours at room temperature; after the reaction is finished, filtering, washing with dimethylformamide for three times, and drying to obtain a boron-containing intermediate product.
S2, stirring 3.0g of boron-containing intermediate product and 38g of dimethylformamide in a three-neck flask with a magnetic stirring device, a nitrogen protection device, a constant pressure dropping funnel and a reflux condenser tube for 30 minutes; then, 20mL of dimethylformamide in which 1.9g of phenylphosphonic dichloride is dissolved is dropwise added into a three-neck flask within 2 hours, after the dropwise addition is finished, the temperature is raised to 90 ℃, and the stirring is continued for 6 hours; after the reaction is finished, the boron-containing polyphosphoric amide flame retardant is obtained through reduced pressure distillation and vacuum drying.
Example 2:
the only difference from example 1 was that the amount of phenylphosphonyl dichloride added in S2 was 2.0 g.
Example 3:
the difference from example 1 was only that the amount of phenylphosphonyl dichloride added in S2 was 1.5 g.
Application example 1:
putting 1g of the flame retardant in example 1 and 78.4g of glycidyl ether epoxy resin into a three-neck round-bottom flask, heating and stirring at 80 ℃ for 30 minutes until the mixture is uniform, then adding 20.6g of 4, 4-diaminodiphenylmethane, continuously stirring for 10 minutes, then placing the mixture in a vacuum environment at 80 ℃ for deaeration for 3 minutes, pouring the mixture into a mold preheated to 100 ℃ while the mixture is hot, then sequentially curing at 120 ℃, 140 ℃, 160 ℃ and 180 ℃ for 2 hours, and naturally cooling to room temperature to obtain the flame-retardant composite material.
Application example 2:
putting 1g of the flame retardant in example 2 and 78.4g of glycidyl ether epoxy resin into a three-neck round-bottom flask, heating and stirring at 80 ℃ for 30 minutes until the mixture is uniform, then adding 20.6g of 4, 4-diaminodiphenylmethane, continuously stirring for 10 minutes, then placing the mixture in a vacuum environment at 80 ℃ for deaeration for 3 minutes, pouring the mixture into a mold preheated to 100 ℃ while the mixture is hot, then sequentially curing at 120 ℃, 140 ℃, 160 ℃ and 180 ℃ for 2 hours, and naturally cooling to room temperature to obtain the flame-retardant composite material.
Application example 3:
putting 1g of the flame retardant in example 3 and 78.4g of glycidyl ether epoxy resin into a three-neck round-bottom flask, heating and stirring at 80 ℃ for 30 minutes until the mixture is uniform, then adding 20.6g of 4, 4-diaminodiphenylmethane, continuously stirring for 10 minutes, then placing the mixture in a vacuum environment at 80 ℃ for deaeration for 3 minutes, pouring the mixture into a mold preheated to 100 ℃ while the mixture is hot, then sequentially curing at 120 ℃, 140 ℃, 160 ℃ and 180 ℃ for 2 hours, and naturally cooling to room temperature to obtain the flame-retardant composite material.
Application example 4:
the only difference from application example 1 is that 2g of the flame retardant of example 1, 77.6g of glycidyl ether epoxy resin, and 20.4g of 4, 4-diaminodiphenylmethane were added to this application example, and the rest is the same as application example 1, and will not be described again here.
Application example 5:
the difference from application example 1 is only that 3g of the hyperbranched flame retardant of example 1, 76.8g of the glycidyl ether epoxy resin, and 20.2g of 4, 4-diaminodiphenylmethane in application example 1 are added, and the rest is the same as application example 1, and will not be described again here.
Application comparative example 1:
the difference from application example 1 is that the boron-containing polyphosphoric acid amide flame retardant of example 1 is not added to application comparative example 1, and the rest is the same as application example 1, and the description is not repeated.
The flame-retardant composite materials prepared in application examples 1 to 5 and application comparative example 1 were subjected to cone calorimetry and tensile tests.
Table 1: application examples 1-5 and application comparative example 1
FIG. 1 shows the synthetic route of the flame retardant of example 1, and it can be seen that the boron-containing polyphosphoric acid amide flame retardant of the present invention contains three flame retardant elements of phosphorus, boron and nitrogen, and the synthetic route is relatively simple.
FIG. 2 is a graph showing the heat release rate in the cone calorimetry test of the flame-retardant composite materials of application example 1, application example 4, application example 5 and application comparative example 1, and it can be seen that the peak heat release rate of the cured product of the flame-retardant epoxy resin obtained by the present invention can be reduced by about 25%.
FIG. 3 is a graph showing the total smoke heat release of the flame-retardant composite materials of application example 1, application example 4, application example 5 and application comparative example 1 in a cone calorimetry test, and it can be seen that the total smoke heat release of the cured product of the flame-retardant epoxy resin obtained by the present invention can be reduced by about 23%.
FIG. 4 is a stress-strain curve diagram of a tensile test conducted on the flame-retardant composite material of application example 1, application example 4, application example 5 and application comparative example 1, and it can be seen that the tensile strength and elongation at break of the cured product of the flame-retardant epoxy resin obtained by the present invention can be improved by about 30% and about 28%.
In conclusion, the boron-containing polyphosphate amide flame retardant with high-efficiency flame retardance and smoke suppression can exert the flame-retardant effect of gas phase and condensed phase when an epoxy matrix is combusted, has two functions of high-efficiency flame retardance and smoke suppression, and can effectively improve the mechanical strength and toughness of epoxy resin.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (10)
1. The boron-containing polyphosphate amide flame retardant is characterized by comprising the following structures:
2. a method for preparing the boron-containing polyphosphazene flame retardant with high flame retardance and smoke suppression as set forth in claim 1, wherein the method comprises the steps of:
s1, uniformly mixing 3-amino-1, 2-propylene glycol, an organic solvent and deionized water in a reaction kettle, adding 1, 4-phenyl diboronic acid into the reaction kettle, stirring, and purifying to obtain a boron-containing intermediate product;
s2, uniformly mixing the boron-containing intermediate product and the organic solvent in the reaction kettle, then dropwise adding the organic solvent containing phenylphosphonic dichloride into the reaction kettle, stirring, and purifying to obtain the boron-containing polyphosphoric amide flame retardant.
3. The method for preparing the boron-containing polyphosphate amide flame retardant with high flame retardance and smoke suppression effects according to claim 2, wherein the mass ratio of the 3-amino-1, 2-propylene glycol to the organic solvent to the distilled water in the step S1 is 1: (5-20): (0.01-0.05).
4. The preparation method of the boron-containing polyphosphazene amide flame retardant with high flame retardance and smoke suppression as claimed in claim 2, wherein the mass ratio of the 1, 4-phenyl diboronic acid to the 3-amino-1, 2-propanediol in the step S1 is 1: (1.05-1.65).
5. The preparation method of the boron-containing polyphosphate amide flame retardant with high flame retardance and smoke suppression effects as claimed in claim 2, wherein the organic solvent is one of tetrahydrofuran, acetone, acetonitrile, dichloromethane, chloroform, dioxane, dimethylformamide and dimethyl sulfoxide.
6. The method for preparing the boron-containing polyphosphazene amide flame retardant with high flame retardance and smoke suppression effects according to claim 2, wherein the mass ratio of the boron-containing intermediate product to the organic solvent in the step S2 is 1: (5-20).
7. The method for preparing the boron-containing polyphosphazene amide flame retardant with high flame retardance and smoke suppression effects as claimed in claim 2, wherein the mass ratio of the boron-containing intermediate product to the phenylphosphonic dichloride in the step S2 is (1.4-2.8): 1.
8. the method for preparing the boron-containing polyphosphate amide flame retardant with high flame retardance and smoke suppression effects as claimed in claim 2, wherein the concentration of the organic solvent containing phenylphosphonyl dichloride in the step S2 is 0.3-1 mol/L.
9. A flame retardant composite comprising an epoxy resin and the highly effective flame retardant, smoke suppressant, boron containing polyphosphoric acid amide flame retardant of claim 1.
10. The flame-retardant composite material according to claim 9, wherein the preparation of the flame-retardant composite material specifically comprises the steps of: placing the boron-containing polyphosphate amide flame retardant and the glycidyl ether epoxy resin which are efficient in flame retardance and smoke suppression into a three-neck round-bottom flask, heating and stirring the materials uniformly, adding 4, 4-diaminodiphenylmethane, continuously stirring the materials, placing the materials in a vacuum environment for defoaming, pouring the materials into a preheated mold while the materials are hot, curing the materials, and naturally cooling the materials to room temperature to obtain the flame-retardant composite material.
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| CN116120562A (en) * | 2022-12-09 | 2023-05-16 | 江苏宝源高新电工有限公司 | Halogen-free flame retardant, and preparation method and application thereof |
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