CN113234228B - 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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- 239000003063 flame retardant Substances 0.000 title claims abstract description 116
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 59
- 239000000779 smoke Substances 0.000 title claims abstract description 44
- 150000001408 amides Chemical class 0.000 title claims abstract description 40
- 230000001629 suppression Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920002627 poly(phosphazenes) Polymers 0.000 title claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 23
- 239000001205 polyphosphate Substances 0.000 claims abstract description 23
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KQIGMPWTAHJUMN-UHFFFAOYSA-N 3-aminopropane-1,2-diol Chemical compound NCC(O)CO KQIGMPWTAHJUMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 10
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007792 addition Methods 0.000 description 5
- 238000004786 cone calorimetry Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 resins have excellent properties such as adhesion, chemical resistance, electrical insulation, heat resistance, and mechanical properties, and thus are widely used in the fields of rail transportation, aerospace, electronics, 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 polypropylene composite material needs to be subjected to flame retardant modification, so that the flame retardant and smoke suppression performance of the composite material is improved, and the fire threat is reduced.
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 distilled 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 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 efficient flame-retardant and smoke-suppressing boron-containing polyphosphoric amide flame retardant and the glycidyl ether epoxy resin in a three-neck round-bottom flask, heating and stirring the mixture uniformly, then adding 4, 4-diaminodiphenylmethane, continuously stirring the mixture, 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 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 schematic diagram of the synthesis of the boron-containing polyphosphazene flame retardant of example 1.
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 only difference from application example 1 is that 3g of the flame retardant in example 1, 76.8g of glycidyl ether epoxy resin, and 20.2g of 4, 4-diaminodiphenylmethane in this application example were added, and the rest is the same as in 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 distilled 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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