CN109280218B - Phosphorus and fluorine-containing flame retardant, preparation method thereof and flame-retardant epoxy resin modified by phosphorus and fluorine-containing flame retardant - Google Patents
Phosphorus and fluorine-containing flame retardant, preparation method thereof and flame-retardant epoxy resin modified by phosphorus and fluorine-containing flame retardant Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 126
- 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 116
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 60
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- 239000011737 fluorine Substances 0.000 title claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 24
- 239000011574 phosphorus Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 7
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- CDIDGWDGQGVCIB-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 CDIDGWDGQGVCIB-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims 2
- -1 flame retardant modified flame-retardant Chemical class 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 4
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a phosphorus-fluorine-containing resistorA flame retardant, a preparation method thereof and flame-retardant epoxy resin modified by the flame retardant, wherein the chemical structural formula of the flame retardant containing phosphorus and fluorine is shown as the following formula. The phosphorus-fluorine-containing flame retardant contains two elements of phosphorus and fluorine, the flame retardant performance of a polymer matrix can be improved by the synergistic flame retardant effect of the two elements, and the phosphorus-fluorine ratio of the flame retardant can be adjusted by condition control; the flame retardant contains fluorine elements, so that the flame retardant can migrate in a matrix, the flame retardant can migrate to the surface of a resin matrix in the using process, and the flame retardant forms concentration gradient distribution in the resin matrix, so that the flame retardant performance and the hydrophobic performance of the material can be improved under the condition of low addition amount.
Wherein R is-H or
Description
Technical Field
The invention belongs to the technical field of organic flame retardants, and particularly relates to a phosphorus and fluorine containing flame retardant, a preparation method thereof and flame retardant epoxy resin modified by the phosphorus and fluorine containing flame retardant.
Background
Due to the flammable characteristic of most polymer materials, the flame retardant modification of polymer materials has been a concern of researchers. In order to improve the flame retardant property of the polymer material, and from the viewpoints of safety, high efficiency and environmental protection, the flame retardants widely used at present include phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, inorganic flame retardants, and the like. 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a widely used high-efficiency phosphorus flame retardant, and Chinese patent application CN201110346692.1 discloses a DOPO flame-retardant modified natural fiber reinforced phenolic resin composite material, which improves the flame retardant property of the composite material and keeps the mechanical property of the material. However, with the development of polymeric flame retardants, the demand for flame retardants has been gradually increased from the original single flame retardant property to the multifunctional property, and it is desired to modify the flame retardancy and to provide new functions and properties to the materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a phosphorus-fluorine-containing flame retardant, a preparation method thereof and flame-retardant epoxy resin modified by the phosphorus-fluorine-containing flame retardant.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a phosphorus and fluorine-containing flame retardant having the formula:
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the phosphorus-fluorine-containing flame retardant comprises the following synthetic route:
the method comprises the following specific steps:
adding 3, 5-bis (trifluoromethyl) aniline, DOPO, paraformaldehyde and a solvent into a reaction container, carrying out reflux reaction for 8-72 h at 40-120 ℃, then cooling and standing until the solvent separates out a solid, and separating the separated solid to obtain the phosphorus-fluorine-containing flame retardant.
In one embodiment: the molar ratio of the 3, 5-bis (trifluoromethyl) aniline to the DOPO to the paraformaldehyde is 1: 1-10: 1-10; the volume ratio of the 3, 5-bis (trifluoromethyl) aniline to the solvent is 1: 8 to 100.
In one embodiment: the solvent is at least one of carbon tetrachloride, chloroform, tetrahydrofuran and N, N-dimethylformamide.
In one embodiment: and after separating the precipitated solid, placing the separated solid in vacuum drying for 22-26 h at the temperature of 55-65 ℃ to obtain the phosphorus-fluorine-containing flame retardant.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
the flame-retardant epoxy resin modified by the phosphorus-fluorine-containing flame retardant comprises an epoxy resin prepolymer, the phosphorus-nitrogen-containing flame retardant and a curing agent, wherein the phosphorus-fluorine-containing flame retardant accounts for 0.1-50 wt% of the epoxy resin prepolymer.
In one embodiment: the phosphorus and fluorine containing flame retardant is introduced into the epoxy resin in a blending mode to prepare the corresponding flame retardant epoxy resin.
In one embodiment: the epoxy resin prepolymer is E51 bisphenol A epoxy resin.
In one embodiment: the curing agent is 4, 4-diaminodiphenylmethane (DDM).
In one embodiment: the mass ratio of the epoxy resin prepolymer to the curing agent is 3-5: 1.
the fourth technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the flame-retardant epoxy resin comprises the following steps: and (2) adding the phosphorus-fluorine-containing flame retardant into the epoxy resin prepolymer at the temperature of 60-140 ℃, stirring until the mixture is transparent, then adding the curing agent, and after the mixture is completely dissolved, sequentially curing at the temperature of 110-130 ℃ for 3-5 h, at the temperature of 130-150 ℃ for 1-3 h and at the temperature of 170-190 ℃ for 1-3 h to obtain the flame-retardant epoxy resin.
The invention has the beneficial effects that:
(1) the phosphorus-fluorine-containing flame retardant contains two flame-retardant elements of phosphorus and fluorine, and the two flame-retardant elements have a synergistic flame-retardant effect in practical application, and the corresponding flame-retardant epoxy resin has the advantages of high thermal stability and good flame-retardant property; by changing the reaction conditions, two flame retardants with different structures can be obtained respectively, the phosphorus-fluorine contents of the two flame retardants are different, the two flame retardants have respective advantages, the flame retardant with the DOPO as the R group is better in flame retardant effect with the DOPO as the R group under the condition of the same addition amount, and the flame retardant can be selected according to the requirements of practical application.
(2) The flame retardant contains fluorine, and the material containing the fluorine has the characteristic of low surface energy, so that the hydrophobicity of the material can be improved; the fluorine element has the characteristic of migrating to the surface of the material, a flame-retardant protective layer can be formed on the surface of the material along with the migration of the flame retardant, and the flame-retardant property of the material is further improved in the using process; in addition, the migration of the flame retardant can also be accelerated by an increase in the ambient temperature.
(3) From the economic perspective, due to the migration performance of the flame retardant, the flame retardant forms a concentration gradient distribution in the resin (figure 1), so compared with other flame retardants, the invention can prepare the resin with high flame retardant performance and hydrophobic performance under the condition of low flame retardant addition, reduces the production cost, and has more advantages in practical application.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 shows the concentration gradient distribution of the phosphorus and fluorine-containing flame retardant in the epoxy resin.
FIG. 2 is a NMR chart of the phosphorus and fluorine-containing flame retardant of example 1.
FIG. 3 is a graph showing the water contact angles before (left) and after (right) the phosphorus and fluorine-containing flame-retardant epoxy resin having a gradient distribution of concentration in example 1 was subjected to heat treatment.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
In the following examples, the epoxy resin prepolymer was an E51 bisphenol A type epoxy resin.
Example 1
1. Preparing a phosphorus-fluorine-containing flame retardant:
adding 1mL (6.43mmol) of 3, 5-bis (trifluoromethyl) aniline, 3.47g (16.07mmol) of DOPO, 0.48g (16.07mmol) of paraformaldehyde and 30mL of chloroform into a reaction bottle, carrying out reflux reaction at 50 ℃ for 24H, then cooling and standing until a white crystal is separated out from the solvent, filtering to obtain a white solid, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24H to obtain the phosphorus-containing fluorine flame retardant with the R group as-H.
2. Preparing flame-retardant epoxy resin:
weighing 20g of epoxy resin prepolymer, heating to 100 ℃, adding 10 wt% of phosphorus-fluorine-containing flame retardant, stirring to be transparent, then adding 5g of curing agent 4, 4-diaminodiphenylmethane (DDM) until the mixture is completely dissolved, then pouring the mixture into an aluminum mould, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 2h and 180 ℃ for 2h to obtain the phosphorus-fluorine-containing flame-retardant epoxy resin with concentration gradient distribution.
The obtained flame-retardant epoxy resin is placed in an oven at 120 ℃ for treatment for 24h, and the water contact angle before and after the treatment is measured, as shown in fig. 3, the water contact angle of the flame-retardant epoxy resin after the heat treatment is increased from 63.9 degrees to 90.1 degrees, and the hydrophobicity of the resin is obviously increased.
The oxygen index of the epoxy resin was determined to be 29.6% according to GB/T2406-2009.
Example 2
1. Preparing a phosphorus-fluorine-containing flame retardant:
adding 1mL (6.43mmol) of 3, 5-bis (trifluoromethyl) aniline, 2.92g (13.5mmol) of DOPO, 0.41g (13.5mmol) of paraformaldehyde and 30mL of chloroform into a reaction bottle, carrying out reflux reaction at 55 ℃ for 24H, then cooling and standing until a white crystal is separated out from the solvent, filtering to obtain a white solid, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24H to obtain the phosphorus-containing fluorine flame retardant with the R group as-H.
2. Preparing flame-retardant epoxy resin:
weighing 20g of epoxy resin prepolymer, heating to 100 ℃, adding 10 wt% of phosphorus-fluorine-containing flame retardant, stirring to be transparent, adding 5g of curing agent 4, 4-diaminodiphenylmethane until the mixture is completely dissolved, pouring the mixture into an aluminum mould, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 2h and 180 ℃ for 2h to obtain the phosphorus-fluorine-containing flame-retardant epoxy resin with gradient distribution of concentration.
The oxygen index of the epoxy resin was determined to be 29.6% according to GB/T2406-2009.
Example 3
1. Preparing a phosphorus-fluorine-containing flame retardant:
adding 1mL (6.43mmol) of 3, 5-bis (trifluoromethyl) aniline, 2.92g (13.5mmol) of DOPO, 0.41g (13.5mmol) of paraformaldehyde and 30mL of N' -N-dimethylformamide into a reaction bottle, carrying out reflux reaction at 60 ℃ for 24H, then cooling and standing until a white crystal is separated out from the solvent, filtering to obtain a white solid, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24H to obtain the phosphorus-containing fluorine flame retardant with the R group being-H.
2. Preparing flame-retardant epoxy resin:
weighing 20g of epoxy resin prepolymer, heating to 100 ℃, adding 10 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, then adding 5g of curing agent 4, 4-diaminodiphenylmethane until the mixture is completely dissolved, then pouring the mixture into an aluminum mould, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 2h and 180 ℃ for 2h to obtain the phosphorus-fluorine-containing flame-retardant epoxy resin with gradient distribution of concentration.
The oxygen index of the epoxy resin was determined to be 29.6% according to GB/T2406-2009.
Example 4
1. Preparing a phosphorus-fluorine-containing flame retardant:
adding 1mL (6.43mmol) of 3, 5-bis (trifluoromethyl) aniline, 3.47g (16.07mmol) of DOPO, 0.48g (16.07mmol) of paraformaldehyde and 30mL of N' -N-dimethylformamide into a reaction bottle, carrying out reflux reaction at 65 ℃ for 24H, then cooling and standing until a white crystal is separated out from the solvent, filtering to obtain a white solid, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24H to obtain the phosphorus-containing fluorine flame retardant with the R group being-H.
2. Preparing flame-retardant epoxy resin:
weighing 20g of epoxy resin prepolymer, heating to 100 ℃, adding 10 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, then adding 5g of curing agent 4, 4-diaminodiphenylmethane until the mixture is completely dissolved, then pouring the mixture into an aluminum mould, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 2h and 180 ℃ for 2h to obtain the phosphorus-fluorine-containing flame-retardant epoxy resin with gradient distribution of concentration.
The oxygen index of the epoxy resin was determined to be 29.6% according to GB/T2406-2009.
Example 5
1. Preparing a phosphorus-fluorine-containing flame retardant:
adding 1mL (6.43mmol) of 3, 5-bis (trifluoromethyl) aniline, 3.47g (16.07mmol) of DOPO, 0.48g (16.07mmol) of paraformaldehyde and 30mL of chloroform into a reaction bottle, carrying out reflux reaction at 50 ℃ for 24H, then cooling and standing until a white crystal is separated out from the solvent, filtering to obtain a white solid, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24H to obtain the phosphorus-containing fluorine flame retardant with the R group as-H.
2. Preparing flame-retardant epoxy resin:
weighing 20g of epoxy resin prepolymer, heating to 100 ℃, adding 5 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, then adding 5g of curing agent 4, 4-diaminodiphenylmethane until the mixture is completely dissolved, then pouring the mixture into an aluminum mould, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 2h and 180 ℃ for 2h to obtain the phosphorus-fluorine-containing flame-retardant epoxy resin with gradient distribution of concentration.
The oxygen index of the epoxy resin was determined to be 28.8% according to GB/T2406-2009.
Example 6
1. Preparing a phosphorus-fluorine-containing flame retardant:
adding 1mL (6.43mmol) of 3, 5-bis (trifluoromethyl) aniline, 3.47g (16.07mmol) of DOPO, 0.48g (16.07mmol) of paraformaldehyde and 30mL of N' -N-dimethylformamide into a reaction bottle, carrying out reflux reaction at 110 ℃ for 24h, then cooling and standing until a white crystal is separated out from the solvent, filtering to obtain a white solid, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24h to obtain the phosphorus-containing fluorine flame retardant with the R group being DOPO.
2. Preparing flame-retardant epoxy resin:
weighing 20g of epoxy resin prepolymer, heating to 100 ℃, adding 5 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, then adding 5g of curing agent 4, 4-diaminodiphenylmethane until the mixture is completely dissolved, then pouring the mixture into an aluminum mould, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 2h and 180 ℃ for 2h to obtain the phosphorus-fluorine-containing flame-retardant epoxy resin with gradient distribution of concentration.
The oxygen index of the epoxy resin was determined to be 28.4% according to GB/T2406-2009.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A phosphorus and fluorine-containing flame retardant characterized by: the phosphorus-fluorine-containing flame retardant is represented by the following formula:
2. A method for preparing a phosphorus-fluorine-containing flame retardant according to claim 1, characterized in that: adding 3, 5-bis (trifluoromethyl) aniline, DOPO, paraformaldehyde and a solvent into a reaction vessel, carrying out reflux reaction for 8-72 h at 40-120 ℃, cooling and standing to separate out solids, and separating the separated solids to obtain the phosphorus-fluorine-containing flame retardant.
3. The method for producing a phosphorus-fluorine-containing flame retardant according to claim 2, characterized in that: the molar ratio of the 3, 5-bis (trifluoromethyl) aniline to the DOPO to the paraformaldehyde is 1: 1-10: 1-10; the volume ratio of the 3, 5-bis (trifluoromethyl) aniline to the solvent is 1: 8 to 100.
4. The method for producing a phosphorus-fluorine-containing flame retardant according to claim 2, characterized in that: the solvent is at least one of carbon tetrachloride, chloroform, tetrahydrofuran and N, N-dimethylformamide.
5. The method for producing a phosphorus-fluorine-containing flame retardant according to claim 2, characterized in that: and after separating the precipitated solid, placing the separated solid in vacuum drying for 22-26 h at the temperature of 55-65 ℃ to obtain the phosphorus-fluorine-containing flame retardant.
6. The phosphorus-fluorine-containing flame retardant modified flame-retardant epoxy resin according to claim 1, wherein: the flame-retardant epoxy resin comprises an epoxy resin prepolymer, the phosphorus-nitrogen-containing flame retardant and a curing agent, wherein the phosphorus-fluorine-containing flame retardant accounts for 0.1-50 wt% of the epoxy resin prepolymer.
7. The flame retardant epoxy resin according to claim 6, wherein: the phosphorus and fluorine containing flame retardant is introduced into the epoxy resin in a blending mode to prepare the corresponding flame retardant epoxy resin.
8. The flame retardant epoxy resin according to claim 6, wherein: the epoxy resin prepolymer is E51 bisphenol A epoxy resin; the curing agent is 4, 4-diaminodiphenylmethane.
9. The flame retardant epoxy resin according to claim 8, wherein: the mass ratio of the epoxy resin prepolymer to the curing agent is 3-5: 1.
10. a method for preparing the flame-retardant epoxy resin according to claim 6, characterized in that: and (2) adding the phosphorus-fluorine-containing flame retardant into the epoxy resin prepolymer at the temperature of 60-140 ℃, stirring until the mixture is transparent, then adding the curing agent, and after the mixture is completely dissolved, sequentially curing at the temperature of 110-130 ℃ for 3-5 h, at the temperature of 130-150 ℃ for 1-3 h and at the temperature of 170-190 ℃ for 1-3 h to obtain the flame-retardant epoxy resin.
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